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Volatile organic components of municipal primary sewage effluent after chlorination and dechlorination Mori, Brian Tomio 1976

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VOLATILE ORGANIC COMPONENTS OF MUNICIPAL PRIMARY SEWAGE EFFLUENT AFTER CHLORINATION AND DECHLORINATION by BRIAN TOMIO MORI B.Sc., Uniyersity.Bof Brit-isliJCol'iimbia-, 1971 A THESIS SUBMITTED IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE ii-. tfrinD'thei-Departments of Chemistry and Civil Engineering We accept this thesis as conforming to the required standard THE UNIVERSITY OF BRITISH COLUMBIA JurJuly9M76 (o) Brian Tomio Mori, 1976 In presenting this thesis in partial fulfilment of the requirements for an advanced degree at the University of British Columbia, I agree that the Library shall make it freely available for reference and study. I further agree that permission for extensive copying of this thesis for scholarly purposes may be granted by the Head of my Department or by his representatives. It is understood that copying or publication of this thesis for financial gain shall not be allowed without my written permission. Department of Chemistry The University of British Columbia 2075 Wesbrook Place Vancouver, Canada V6T 1W5 Date June 1976 ABSTRACT i The extraction, separation and identification of volatile organic com ponents of primary effluent before and after chlbrination was undertaken to ascertain whether the chlorination of treatment plant effluents results in the formation of new volatile chlorinated organics. Extraction efficiencies of 70 to 90 percent of an aqueous solution of phenols were obtained by both continuous solvent extraction and sorption on a column of a macroreticular resin. Tests with primary effluent showed that the macroreticular resin recovered a slightly larger number of compounds than the solvent extractor which also suffered from emulsion problems.' Since the resin was also expedient in handling replicate samples it was adopted and further studies indicated that it had a capacity of 1.7 mg TOC/cc of resin and re coveries of the phenols were unaffected by pH or detergents. Preliminary separation of the. .components on the basis of acidity with .05'M^NaOH and diethyl ether and by thin layer chromatography on silica gel with pet ether and methanol proved to be useful. Gas chromatographic (GC) studies with various silicone liquid phases demonstrated that OV-101, 0V-17, and 0V-225 all provide good separation after optimization of temperature programs. Primary effluent samples taken from Lion's Gate Treatment Plant in North Vancouver on Monday mornings proved to be remarkably consistent in their GC 63 traces as monitored by Ni electron capture (EG) and flame ionization (FID) detectors. A series of spectacular new peaks was consistently observed by EC as a result of chlorination, but the FID showed only minor changes. Dosage levels of up to 120 mg/1 Cl^ (NaOCl) produced similar chromatograms while a dosage of 200 mg/1 produced a new set of changes not found at the dosage levels used in treatment plants. Gas chromatographic studies with a micro-ii electrolytic conductivity detector showed that 10 or 11 new halogenated peaks in the neutral and basic fraction and 6 or 7 new halogenated peaks in the acidic fraction result from chlorination. These compounds all of which are in ng/l concentrations account for only 0.01 percent of the applied chlorine dosage but make up about 40 percent of the more volatile organically bound halogen present in chlorinated primary effluent. After a series of partially successful attempts by retention time, GC-MS and GC effluent trapping, a number of components were positively identified by a computerized GC-MS. TRirty-one compounds were positively identified by mass spectra and GC retention times,another 24 were tentatively identified by mass spectra and an additional seven were very tentatively identified by GC re tention times.. Only three of the compounds resulting from chlorination were positively identified. All compounds identified by mass spectra are present in concentrations in primary effluent. The implications of this study and suggestions for further investigations are also discussed. Research Supervisor. iii TABLE OF CONTENTS Page Abstract i Table of Contents » iii List of Tables v List of Figures viAcknowlegments , ix Symbols and Abbreviations x CHAPTER I INTRODUCTION, PURPOSE AND SCOPE 1 Definitions ,, 1 Introduction ,Purpose and Scope of This Research 2 CHAPTER II LITERATURE REVIEW , 4 A. Preface 4 B. Composition of Domestic Sewage and Effluents .............. 4 1. Organics . 4 2. Inorganics 20 C. A Simplified Model of the Chlorination Process 20 D. Reactions of Chlorine with Organics in Aqueous Media ...... 24 1. Reactions with Nitrogenous Compounds , , 24 2. Reactions of Chlorine with Other Organics 27 3. Reactions of N-Chloro Compounds with Organics 30 E. The Effects of Chlorine on Sewage Effluents 31 1. Practices In Treatment Plants 32. Biological Effects of Residual Chlorine 31 3. Toxic Effects of Chlorinated Organics ,. 4 4. Chemical Effects of Chlorinations 36 F. Analytical Methods 41. Sampling and Preservation ............ 41 2. Extraction and Concentration 42 3. Separation , 45 4. Chemical Analysis 50 CHAPTER III EXPERIMENTAL 4 A. Outline of the Problems , , 54 B. Apparatus and Techniques  54 1. General Methodology 52. Sampling and Preservation 56 3. Design and Test of Extraction Methods 57 a. Solvent Extractorb. Extraction with XADV2 Resin 59 c. Comparison of XAD-2 and Solvent Extractor 62 d. Extraction of Particulates .......... . 62 iy 4. Separation Experiments ................................. 63 a. Preliminary Separation , 63 b. , GC Optimization 64 c. TLC of Acidity Separated Fractions ,, ,. 64 5. Effects of Chlorination , 65 a. Changes in Soluble TOC upon Chlorination ,. 65 b. Effects Detectable by GC with EC and FID Detectors .. 65 c. Effects Monitored by MEC Detector and GC Correlations 65 d. GC-rMS Studies on the MS-rl-2 66 e. Tentative Identification by Retention Time 6f. Trapping of GC Peaks 6g. GCr-MS-Computer , 7 CHAPTER IV RESULTS AND DISCUSSION , , , . . , 69 A. Extraction Experiments  69 1. Solvent Extractor 62. Extraction with XAD-2 Resin , , 72 B. Separation Experiments 81. Preliminary Separation2. GC Optimization , . , . , , ,. 85 3. TLC of Acidity Fractions .,, 87 C. Effects of ChlorinaMon on Primary Effluent , 92 1, Soluble TOC ,, ,  , 92' 2, Effects Monitored by EC and FI Detectors',, 92 3, GC 4, GC^MS Studies 5, Tentative Identification Fy Retention. Time 124 6, GCrrMS^ComputerSSfeuddses , . 130 7, Correlations Among GC Chromatograms 146 CHAPTER V SUMMARY, IMPLICATIONS AND SUGGESTIONS FOR FURTHER STUDIES 153 Summary ,,,,,.,,,.,,,,,,,,,,.,.,,,,,,....,,,...,...>.<,.. 153 Implications , 154 Recommendations for Further Studies ........................... 158 BIBLIOGRAPHY  160 APPENDIX I REFINEMENTS TO THE AQUEOUS CHLORINETAMMONIA MODEL 179 1. Reactions of Chlorine with Water 172 . Decompositions of H0C1 and OCl" , ,. ,  180 3, Reactions.of H0C1 and OCl' with Ammonia 181 4, Thermodynamic Properties of Chloramines ,,,, 185 APPENDIX IT SUMMARY OF CHROMATOGRAMS OF EFFLUENT SAMPLES , 186 APPENDIX III GC CONDITIONS FOR FIGURES 188 APPENDIX IV MASS SPECTRA OF COMPOUNDS POSITIVELY IDENTIFIED IN CHLORINATED PRIMARY EFFLUENT ,., 190 APPENDIX V MASS SPECTRA OF UNIDENTIFIED COMPONENTS OF CHLORINATED PRIMARY EFFLUENT , 196 -y LIST OF TABLES Table Page 2.1 Major Inputs to Domestic Sewage 5 2.2 Typical Strength Distributions in Raw Sewages 7 2.3 General Composition of an American Domestic Sewage 9 2.4 General Composition of an English Domestic Sewage 10 2.5 Amino Acid Content of Raw Sewage 11 2.6 Organic Components of Primary Effluent 13 2.7 Volatile Components of Human Urine , 6 2.8 General Composition of Secondary Effluent 18 2.9 Organic Components of Secondary Effluents 9 2.10 Inorganic Composition of Lion's Gate Effluent 21 2.11 Summary of Reaction Conditions for Organics in Sewage 28 2.12 Toxicity of Selected Compounds to Aquatic Life 35 2.13 Chlorinated Compounds Formed by Chlorination of Primary Effluent 39 4.1 Recoveries of Phenols by Solvent Extractor 70 4.2 Solvent Loss Due to Entrainment 71 4.3 Recoveries of Phenols from Distilled Water by XAD-2 74 4.4 Effects of LAS on Recoveries of Phenols by XAD-2 75 4.5 Breakdown of Losses for XAD-2 System 76 4.6 Breakthrough Study for Sewage on XAD-2 7 4.7 Effect of Chlorination on Soluble TOC 96 4.8 Effects of Chlorination by GC Analysis with FID and EC Detectors 98 4.9 Concentrations of Halogen as Chlorine in Primary Effluent ... 116 4.10 Chlorine Uptake by Volatiles 118 4.11 Retention Times of Test Compounds , 125 4.12 Compounds Identified by GC Retention Time 128 4.13 Performance Check of Finnigan 3000 131 4.14 File Names for GC-MS-Comp Studies , 132 4.15 Summary of RGC Data 134 4.16 Phthalates and Septum Bleed by LMRGC 140 4.17 Results of Spectral Searches and Retention Time Checks for CL.1202 142 4.18 Results of Spectral Searches and Retention Time Checks for C-HALL 3 4.19 Compounds Positively Identified by Mass Spectrum and Retention Times 145 yi Table Page 4.20 Compounds Tentatively Identified by MS 147 4.21 Spectrum Numbers of Halogenated Neutral and Basic Organics 149 4.22 Spectrum Numbers of Halogenated Acidic Organics 150 5.1 Guide to Environmental Effects of Identified Compounds 155 yii LIST OF FIGURES Figure Page 3.1 Flowchart of the Project 55 3.2 Continuous Solvent Extractor 8 3.3 Macroreticular Resin Extraction Apparatus 61 4/1 Recovery of Organics from Primary Effluent By XAD-2 Resin , , . 79 4.2 Continuous Solvent and XAD-2 Resin Extraction of Organics from Primary Effluent Monitored by GC 81 4.3 Soxhlet Extracts of Particulates Analyzed by GC 83 4.4 Silica Gel Column Fractionation of Primary Effluent Extracts Analyzed by GC 84 4.5 Acidity Separation of Primary Effluent Extracts Analyzed by GC 86 4.6 GC Optimization - N + B by EC 88 4.7 GC Optimization - WA by EC ,.. 89 4.8 GCCOptimization - N + B by FID , 90 4.9 GC Optimization - WA by FID  91 4.10 TLC of N + B Fraction; Silica Gel, Pet Ether 93 4.11 TLC of N + B/TLC Fraction; Silica Gel, Methanol 94 4.12 Flowchart of Separation Procedure 9.5 4.13 Effects of Chlorination by GC - N + B by EC-1 9-9. 4.14 Effects of Chlorination by GC - N + B by FID-1 100 4.15 Effects of Chlorination by GC - WA by EC , 101 4.16 Effects of Chlorination by GC - WA by FID 102 4.17 Effects of Chlorination by GC - SA by EC 103 4.18 Effects of Chlormna£ionbbyGGC--SSAbbyFFI'D 104 4.19 Effects of Chlorination by GC - N + B by EC-2 105 4.20 Effects of Chlorination by GC - N +BB by FID-2 106 4.21 Effects of Chlorination by GC - A by EC 107 4.22 EfEffects of Chlorination by GC - A by FID 108 4.23 Effects of Chlorination by GC - A by MEC ,,. 112 4.24 Effects of Chlorination by GC - N + B by MEC-1 113 4.25E Effects of Chlorination by GC - N + B by MEC-2 114 4.26 CaC^libratiofiu.eurveoforrSMECeDetector 115 4.27 Total Ion Current Plot for N + B Fraction by .MS-12 122 4.28 Mass Spectra from MS^12 j,',,,,,,,,,,,,,,,,,,,,,,', ,-.*v...... 123 Figure 4.29 GC Retention Times of Test Compounds 4.30 RGC's of Acid Fractions 4.31 RGC's of Neutral and Basic Fractions 4.32 RGC's of TLC Fractions 4.33 : RGC's and LMRGC's of Blanks, 4.34 MEC - GC-MS Correlations ix ACKNOWLEDGEMENTS The author wishes to express his sincere gratitude to Dr. K. J. Hall for his patience, encouragement and guidance during this project. A special grat itude is extended to Dr. J..,-N. Blazevitch (U.S. Environmental Protection Agency) for his willing cooperation and generous hospitality during the days the author spent in Seattle. Thanks are also expressed to Sue Harper for the in organic c analysis of primary effluent. A large number of other people have each contributed in no small way to the completion of this project by very willingly and generously providing their advice, cooperation and: material support. Although limitations of space pre vent a proper expression of gratitude to all of them the author would like to especially thank Liza McDonald, Dr. R. Bose and Dr. J. Farmer for their help. This thesis is dedicated to my parents and to my wife Catherine and son Michael who through their love and understanding contributed greatly to its completion. SYMBOLS AND ABBREVIATIONS A Acidic Fraction BOD Biochemical Oxygen Demand CIMS Chemical Ionization Mass Spectroscopy COD Chemical Oxygen Demand CRT Cathode Ray Tube DO Dissolved Oxygen EC Electron Capture EIMS Electron Impact Mass Spectroscopy EMW Estimated Molecular Weight FID Flame Ionization Detector •G'G'IR ', ^ Gas; rChroffiaeograpHyInfrared ,,_GC-MS-(Com) Gas* CferomatograpfciyMass Spectrometer-(Computer) GLC Gas-Liquid Chromatography GPC Gel permeation Chromatography GSC Gas-Solid Chromatography GVRD Greater Vancouver Regional District IR Infrared LCn Lethal Concentration for n Percent of Population LC Liquid Chromatography LLC Liquid-rLiquid Chromatography LSC Liquid-S^lid Chromatography MEC Microelectrolytic Conductivity..(Detector) MLD Minimum Lethal Dose For Death of One or More Members of the Group Neutral and Basic Fraction Nuclear Magnetic Resonance Signal to Noise Suspended Solids Tolerance Limit (Median), for 50. Percent of the Population Thin Layer Chromatography Total Organic Carbon Total Solids United States Environmental Protection Agency Ultra Violet Volatile Solids N + B NMR S/N SS TLm TLC TOC TS USEPA UV VS' CHAPTER I INTRODUCTION, PURPOSE AND SCOPE Definitions The terminology used in this thesis is that commonly used by those in volved with environmental sciences and technologies. To avoid any misunder standings however, some definitions will be stated. Sewage is defined as untreated- wastewater. The standard definitions of domestic, storm, combined and industrial sewages are adhered to. Municipal sewage is that sewage in the municipal sewage system. The terms primary, secondary, and tertiary efflu ents are used to describe the effluents from the various types of municipal as opposed to industrial sewage treatment plants unless otherwise indicated. Standard abbreviations are used throughout this thesis and a list of abbrevia tions is provided on page x. Introduction In the United States, domestic sewage constitutes about .a quarter of the total aqueous organic wastes. (ACS Subcommittee 1969). The amount of organic 9 material in terms of BOD present in domestic sewage in 1963 was 7.3 x 10 lb, 9 9 compared to BOD values of 9.7 x 10 lb for chemical industries, 5.9 x 10 lb 9 for pulp and paper industries, 4.3 x 10 lb?for food processing industries, 9 and 0.5 x 10 lb for the petroleum and coal industry. It should be empha sized that these are wastewaters and not effluents. Values for effluents should be 0.3 to 2 orders of magnitude lower. The response offantecosystem-tdnthe discharge-of "^organics in wastewaters will naturally depend upon the type of compound and the type of ecosystem. Vallentyne (1957), and Croll (1972), have reviewed the types of organics . found in natural waters. Little (1970) and Ongerth et al. (1973) report that only 66 of a suspected 456 organic chemicals in water have been positively identified. Most organics from domestic sewage are rapidly degraded by micro organisms, so rapidly in fact that depletion of dissolved oxygen in the receiv ing water often results from the discharge of untreated sewage. However, some compounds may be recalcitrant, metabolized to toxic material, or toxic. If a compound is recalcitrant concentration in the food chain of the ecosystem can occur as with DDT, (Woodwell efal., 1967), or it may even become ubiquitous. For example, carbon tetrachloride is now a normal constituent of the atmosphere (Iliff, 1972) and some drinking waters (Dowty et al., 1975a). Dugan (1972) suggested that chlorination of domestic sewage may result in the formation of toxic and or recalcitrant chlorinated organic compounds. Zillich (1972), Brungs (1973), and Servizi and Martens (1974) have demonstrated or reviewed the toxicities of chlorinated effluents to aquatic ecosystems. There is little doubt that most of this toxicity is due to Cl+ species. Current investigations by Jolley (1973), Glaze et al. (1973), Rook (1974) and Bellar et al. (1974) however, show that chlorinated organics are definitely formed during the chlorination of sewage or natural waters. These results have recently been sensationalized by the lay and scientific press (Time, 1974; Vancouver Sun, 1974; Marx, 1974). In order to maintain a proper perspective, calculations based on the data presented by Lillian et al. (1975), Jolley (1973) and JWPCF (1974) shows that well over 99.99 percent of chlorinated organics produced by man are intentionally produced industrially. Some organisms also produce and metabolize chlorinated organics (Doonan 1973). Moreover the fact that an or ganic compound contains chlorine does not necessarily mean that it is harmful or even recalcitrant. Purpose and Scope of This Research This present investigation will focus on the organics in primary effluents which are relatively volatile. The objectives will be to: 3 1. ) develop an efficient method for the recovery and concentration of these materials, ( 2. ) determine whether changes in the composition profile of the volatile organics in primary effluent occur as a result of chlorination, 3. ) separate and identify the products and precursors of the reaction of chlorine with primary effluent. CHAPTER II LITERATURE REVIEW A. Preface This chapter will be divided into five sections. The first three sections will be devoted to predictions of the types of chlorination reactions which will occur during the chlorination of sewage. In order to accomplish this the composition of sewage and primary effluent will be reviewed, a simplified chemical model of the chlorination process will be presented, and the known reactions of chlorine with organics will be briefly reviewed. The final two sections will be devoted to a review of the known effects of the chlorination of sewage and of the analytical methods relevant to this and other similar investigations. B. Composition of Domestic Sewage and Effluents 1. Organics Sources The composition of sewage will naturally depend upon which indus tries are discharging into the collection system. Among the sewages from households, it has been found that although relative amounts vary, the major types of organic material present in domestic sewage are similar in the United States and England. The major inputs to domestic sewage are presented in Table 2.1. Excreta account for practically all of the organic-nitrogen but only 80 percent of the organic-carbon. .Physical Forms Raw sewage is a heterogeneous mixture of floating, suspended, emulsified and dissolved inorganic and organic matter in water. The composition equilibrium is affected by evaporation, solubility equilibria, sorption pro cesses, precipitation, and biological metabolism. Due to the wide variation in physical forms of organic material in sewage and the corresponding variation 5 Table 2.1 Major Inputs to Domestic Sewage. Component Organic Carbon Organic Nitrogen NH3 + Urea as N Faeces* 17 1.5 Urine* 5 1.7 10.5 Dishwashing and Food Preparation** 8 0.2 0 Personal and Clothes Washing** 7 3.4 10.5 * Units are g/adult/day. **UUnits are g/person/day. a) Painter and Viney (1959) ( 6 of degradation efficiency in sewage treatment plants or in natural waters, chemical analysis of sewage is more meaningful after segregation of organics by physical means. A disadvantage of mechanical separation of organics is that sorbed volatile materials (Fishbein, 1972b, Khan, 1972), and metal com-plexed organics (Chau, 1973) may not be included in the soluble fraction. While no standard segregation method has been adopted, sewages are generally classified as to settleable, colloidal, supracolloidal and soluble fractions. The soluble material has a particle size less than 0.2 to 1.0 microns. A description of the size fractions of raw sewage in terms of engineering par ameters is presented in Table 2.2. From this table i:t can be seen that about one third of the organic carbon in sewage is dissolved, while the organic nitrogen is equally distributed amongst the four fractions. Molecular Size Distribution Several gel permeation chromatographic (GPC) studies have been conducted to determine the molecular size of the organic compounds in raw sewage. Zuckermann and Molof (1970) found only two fractions, one with an Estimated Molecular weight (EMW) of 400 and another of EMW 1200+. Hardt et al.,(1971), iad Robertson (1972), and Clesceri (1973) all found more complex molecular weight profiles. Robertson also found evidence of solute -gel interaction, thus some inaccuracies are inherent in the assignment of EMW values. The profiles are so different that as Robertson points out, no gener alizations should be made. It can be said however that 20-60 percent of the &i§§SlY§& .8£§§&4es©apfc@n -ha^ign EMWEOI© Ie's'sj5tha:nd35_0,sand.<may thus be amenable £9 .seRSIStianabX-ogaS. &hromato&r1apJhy the upper limits of t:--amenable tc GC separation. Co:•-nr,G'en@rail-Ghem'i'ca-lq<G-lasses Two major studies have been undertaken to clas sify the organic material in sewage by chemical groupings. Both studies, one in England (Painter et al. 1959, 1961, Painter 1971), and the other in the Eastern United States (Hunter and Heukelekian, 1965; Henkelekian and Table 2.2 Typical Distributions in Raw Sewages Fraction Particle Size TS . . VS TOC Organic-N abc b d b a c be At m AC mg/1 % mg/1 % mg/1 % mg/1 % mg/1 % mg/1 % mg/1 . % . Soluble <0.2 <1 <1.0 284 65 827* 63 88 42 46 42 90 29 2.0 27 10 37 Colloidal 1-10 3 31 7 20 10 12 11 40 15 1.1 11 5.4 20 Supra colloidal 103-10 5 44 10 482* 37 36 17 22 20 68 22 3.1 34 5.4 20 Settleable > 10 5 79 18 64 31 29 27 105 34 3.7 23 6.2 23 * Only values for soluble versus suspended were given, a Rickert and Hunter (1971) b Hunter and Heukelekian (1965), Rudolfs and Balmat (19 52), Heukelekian and Balmat (1959) c Painter and Viney (1959) d Painter, Viney and Bywaters (1961) 8 Balmat, 1959; Rickert and Hunter, 1971; Hunter, 1971) employed classical solvent and TLC separation procedures followed by wet chemical quantification techniques. The results of the studies are presented in Tables 2.3 and 2.4. Direct comparison of these studies is difficult since the data is expressed in different units. It is noteworthy that the carbohydrates, proteins, vol atile acids., and anionic surfactants account for most of the soluble carbon. The amount of soluble organics recoverable by solvent extraction or sorption and sufficiently volatile for gas chromatographic analysis is of particular interest. In the American study it was found that 80 mg/1 or 85 per cent of the dissolved organics were ether soluble. Volatile acids accounted for 30 mg/1, but any compounds volatile at 103°C were lost during analysis since VS was used to measure organic matter. In the English study, non-volatiles and volatile acids accounted for about 80 percent of the dissolved carbon. The remaining 20 percent of the carbon was unclassified rather than volatile enough to be lost during the concentration procedures. Thus one can conclude that the volatiles, exclusive of the volatile acids constitute only a very small portion of the soluble organic material. Specific CGompounds Prior to 1972, very few specific compounds had been identified in sewage. Most of the work wasxlimited to amino acids (Painter and Viney, 1959; Hunter and Heukelekian, 1965) and to volatile acids (Viswana-.; than et al. 1962; Murtaugh and Bunch, 1965; Loehr and Kukar, 1965). The results of the amino acid studies are presented in Table 2.5. The volatile acid analyses generally show the presence of all acids from formic through pentanoic with acetic acid accounting for around 80 percent of the total weight of these ccompounds. The only attempt to comprehensively survey the individual components of sewage was conducted in the Southeastern United States by Katz et al. (1972) and Jolley (1973). These investigators used liquid chromatography for initial separation followed by derivitization and GC and MS analysis. Table 2.3 General Composition.of an American Domestic.Sewage, Constituent Settleable Supra Colloidal Colloidal Soluble a b a b a b 11.70* 15.27 9.57 17.25 3.55 12.82 0.89 0.46 1.70 0.78 1.48 0.66 0.18 0.08 0.24 0.12 0.20 0.12 0.71 0.38 1.46 0.56 .1.28 0.54 0.004 0.002 0.002 0.08 0.14 0.10 6.45 10.43 4.48 12.76 1.7?. 8.42 1.13 2.49 0.88 1.56 0.24 1.68 5.33 7.94 3.60 11.20 1.48 • 6.74 0.00 0.00 0.02 0.10 0.04 0.08 2.99 2.22 2.16 2.30 1.86 2.42 1.92 1.41 1.09 ' 0.74 0.38 0.26 0.34 0.37 0.51 18.05 19.6 10.60 6.25 6.09 6.57 1.48 0.13 2.16 0.13 1.35 0.57 3.53 2.60 4.32 0.74 1.33 •1.40 11.50 11.8 3.15 0,68 2.43 1.32 1.54 5.12 0.97 0.86 0.98 3.28 0.26 0.13 0.10 8.59 15.44 12.84 6.44 5.37 19.52 9.45 6.64 3.58 '. 0.04 0.02 0.03 72.5 94.1 77.8 94.5 81.9 95.5 Total Grease Free Fatty Acids Unsaturated Saturated Phenols Detergents Glyceride Fatty Acids Unsaturated Saturated Phospholipids Unsaponifiables Aliphatic Aromatic Oxygenated Total Carbohydrates and Lignin Pectin Hemicellulose Cellulose Lignin Hexose Pentose Amino Acids Bases Amphoterics .Neutrals Cholesterol Uric Acid Creatine - Creatinine Percent Volatile Solids Accounted for 22.56 0.12 3.94 9.77 0.77 9.05 3.24 4.80 13.59 0.03 0.33 0.20 88.2 * All concentrations are in mg/1 a Hunter and Heukelekian (1965) b Heukelekian (1959) Table 2.4 General Composition of an English Domestic Sewage3' Constituent Settleable Supracolloidal Colloidal Soluble Carbohydrates 9.3* 2.5 2.7 28.2 Amino Acids Combined /' 10.0 6.8 8.0 6.9 Free 2.8 Acids Soluble 2.1 2.2 0.8 23.9 Insoluble 26.8 21.8 15.7 Volatile/non-volatile 10.2/13.7 Esters 16.6 9.1 4.5 0 Anionic Surfactants 1.4 1.0 1.5 10.1 Amino Sugars 0.3 0.1 0.6 0 Urea (as N) 12 Ammonia (as N) 31 Creatinine 2.7 Total Carbon 105 68.2 46.3 90 % Total Carbon Accounted For 63.3 63.7 72.2 82.1 * All concentrations are in mg/1 carbon, unless otherwise stated, a Painter and Viney (1959) b Painter (1971) 11 Table 2.5 Amino Acid Content of Raw Sewage' Amino Acid , Concentration (mg/1) Free Total Particulate Cystine Lystine & Histidine Histidine Lysine Arginine Serine, Glycine and Aspartic Acid 0-trace trace present absent/ present trace 0.02-0.13 1.4-5.7 5.1-9.7 present^ absent present 4.6-11.0 9.4-19.4 1.90 (3.51) 2.03 1.48 1.83/3.39/4.29 (9.51) Threonine and Glutamic Acid 0.01 -0.18 4.5r24.8 1.85/5.18 (7.03) Alanine Proline Tyrosine Methionine and Valine 0.02-0.09 0 0.06-0.09 0.05-0.024 5.1-11.9 0 1.7-6.4 0.09-15.7 4.42 1.87 4.21 Phenylalanine Leucine Tryptophane ;0.02-0.33 0.06-0.28 present 4.7-16.8-4.2-13.1:-present 5.42 a Hunter (1971) 12 The compounds identified are relatively non-volatile and present in^g/1 concentrations. Other studies of more limited scope have been undertaken by Rudolfs and Heihemann (1939) , Smith and Gourdon (1969), Bennett et al. (1973) , Buehler et al. (1973), Farrington and Quinn (1973), Kolattukudy and Purdy (1973), and Singley et al. (1974). The results of these studies are summarized in Table 2.6. Spector (1956) and Katz e_t al. (1968) have compiled a list of the rela tively non-volatile compounds in urine and feces along with their excretion rates. This data can be used to estimate the concentrations of these compon ents assuming no loss due to biological activity or physical processes. With the assumptions of an average body weight of forty-five kilograms and an average sewage flow of four hundred litres per capita per day, the concentra tion in sewage of each component can be estimated by the following formula. Some idea of which volatile compounds one may expect to find in sewage can be garnered from the studies on urine. Zlatkis et al. (1973a, b, c) used headspace extraction followed by GC - MS analysis and identified about 50 volatile urine components which are listed in Table 2.7. Most of these com pounds are present in mg/1 to /cg/1 concentrations inlur.Ine (Zlatkis ,1975) and one might expect to find them in/zg/1 to ng/l concentrations in sewage. The organic compounds identified in secondary effluents along with their concentrations are summarized in Tables 2.8 and 2.9. A comparison of these concentration values with those for primary effluents will yield some infor mation on removal and/or biodegradability of the constituents. It is interest ing to note that removal may be airfunC'tionf ojfoieon'.cen-fration in that volatile acids are 99% removed while some of the trace constituents such as p-cresol and Excretion rate (mg/kg) x 0.1 kg/1 eg. cholesterol estimated 0.7 mg/1 found 0.3 mg/1 Table 2.6 Organic Components of Primary Effluent Compound Concentration Reference /fg/1 Aromatics (Benzenoid) Phenol 6 ' 2 p-Cresol 20 2 Pentachlorophenol 4 1 2- Hydroxybenzoic Acid 73- Hydroxybenzoic Acid 40 2 4- Hydroxybenzoic Acid _4- Hydroxypheriylacetic Acid 190 2 3-Hydroxyphenyl-proprionic Acid 203-Hydroxyphenylhydra-crylic Acid 6 2 Lignins 1500 7 Folic Acid _,Benzoic Acid  2 Phenylacetic Acid 10Hippuric Acid _ 5 Hexachlorophene 30 1 Aromatics (Heterocyclic) N-Methyl-2-fyridone 5-carboxamide 10 3 N-Methy1-4-pyridone-3-carboxamide 10 2 Niacin 14 7 Uracil 3 3 5- Acetyl-6-amino-3-methyl uracil 30Thymine 7 2 Thiamine 29 - 7 Inosine . 50Orotic Acid 5 2 T Theobromine 3 q Caffeine 10 2 Xanthine 70Hypoxanthine 251-Methylxanthine 17 2 3-Methylxan thine7-Methylxanthine . 3 1,7-Dimethylxanthine -ZZ.-Table .2.6 cont'd. Compound Concentration Reference Uric Acid 20 2 Guanosine 50Adenosine —Riboflavin 22 7 Urocanic Acid  2 IndicanCobalamin 0.8 7 Unsaturates . Oleic Acid 17000;' 7 Linoleic Acid 10000Biotin 3Pantothenic Acid —Ascorbic Acid  7 Cholesterol 300Saturates Formic Acid — 5 Acetic Acid 10000Proprionic Acid 2600Butyric Acid 1000 5 Pentanoic Acid 400,Laurie Acid 120 7 Myristic Acid 240^Palmitic Acid 11700;*,.Stearic Acid 4606 7 Lactic Acid — 5 Pyruvic AcidGlycollic AcidOxalic Acid — 7 Glutaric Acid  5 Citric AcidSuccinic Acid — 2 Cutin —c 4 Glycerine  2 Corprostanol 100 7 5j& -CHolestan-3^-ol — 6 Allulose — 3 Glucose  2 GalactoseMannose — 3 FructoseRhamnoseSorbose and/or xylose — 3 Arabinose —Ribose15 Table 2.6 cont'd. Compound Concentration Reference Sucrose Maltose Lactose Muramic Acid 3 2 3 2 a. See also Table 2.5. b. Concentration found in whole sewage, concentration in effluent is unknown but probably 1-3 orders of magnitude lower. c. Identified in sludge only. d. References 1. Buehler et al. (1973) 2. Katz et al. (1972) 3. Jolley (1973) 4. Kolatt'ukudy and Purdy (1973) 5. Painter and Viney (1959) , Painter et al. (1961) 6. Smith and Gourdon (1969) 7. Hunter (1971) Table 2.7 Volatile Components of Normal Human Urine' Component Chloroform Ethanol 1- Butanol Proprionaldehyde Furfural Acetone 2- Butanone 3- Methyl-2-butanone 2,3-Butanedione 2- Pentanone 3- Methy1-2-p ent anone 4- Methyl-2-pentanone 3-Methylcyclopentanone 3- Hexanone 5- Methyl-3-hexanone 2- Heptanone 4- Heptanone 6-Methyl-3-heptanone 3- 0ctanone 2- Nonanone Piperitone Carvone 3- Penten-2-one ^ 4- Methyl-3-penten-2-one Thiolan-2-one Toluene ^ p-Methyl propenylbenzene Benzaldehyde pfCresol 2.3- Dimethylfuran 2.4- Dimethylfuran 2-Methyl-5-Ethylfuran 2,3,5-TrimeMiylfuran C^-Furan 2-n-Pentylfuran Acetylfuran Pyrrole 1- Methylpyrrole 2- Methylpyrrole Dimethylpyrrole 1- ButylpyrroleD Methylpyrazine 2,3-Dimethylpyrazine 2,5 or 2,6-Dimethylpyrazine 2,3,5-Trimethylpyrazine 2,Methyl-6-ethylpyrazine Vinylpyrazine 2-Methyl-6-vinylpyrazine ytl-Pinene Allylisothiocyanate Table 2.7 cont'd. Component Dlmethyldisulphide a Zlatkis et ah (1973 b,c) b Identification is tentative Table; 2.8 General Composition of Secondary Effluent Component Percent by Weight of Organic Matter Humic Acids 40 - 50 Fulvic 23 Humic 11 Hymanthomelanic .8 Ether Extractables 8 Anionic Detergents 14 Carbohydrates 2 Proteins 2Tannins 2 a Rebhum and Manka (1971); Manka et al. (1974) Table 2.9 Organic Components of Secondary Effluents 19 Compound Concentration Reference Carbohydrates Glucose Fructose Sucrose Mannose Allulose Xylose Raffinose Glycerine Formic Acid Acetic Acid Fr op'd'o'nU'd-cA^d?d~d Butyric Acid Iso-butyric Acid Iso-valeric Acid Caproic Acid Uric Acid Polycyclic Aromatics Pyrene 1 Perylene r Benzepyrenes J DDT BHC Dieldrin Uracil 5-Ac etylamino-6-amino-3-Me thy1 Inosine 1-Methyl Inosine 1-Methyl Xanthine 7-Methyl Xanthine 1,7-Dimethyl Xanthine p-Cresol 2-50 1 2 10 1 20510 1 105010 1 101 1 0.1 1 0.10.1 1 30 2 uracil 3020 2 806 2-5 2 690 2 1. Painter (1973) 2. Jolley (1973) 20 methyl xanthine are hardly removed at all. 2. Inorganics The main purpose of reviewing the inorganic composition of sewage effluents is to assess their effects upon the aqueous chemistry of chlorine through various complexation reactions with both organics and species containing Cl+. In view of the voluminous amount of literature available and the complexity of primary effluent as a chemical system, this review will only attempt to estimate the amounts of inorganics available for such interactions. The inorganic compositions of whole sewages were reviewed by Painter (1971) . Tanner e_t al. (1973) and Koch e_t al. (1976) have surveyed the concen trations of some heavy metals in Vancouver sewages and treatment plant efflu ents. A sample of unchlorinated effluent from Lion's Gate Treatment Plant was surveyed in this study and the results ase presented in Table 2.10 are similar to those of the other studies. In order to estimate the amount of each constituent actually available to influence the chlorination process, ratios of dissolved/total calculated from the data of Heukelekian and Balmat (1959) are also included in Table 2.10. C. A Simplified Model of the Chlorination Process The Process in the Sewage Treatment Plant The mechanics of effluent chlorination hav«been discussed in detail by White (1971). The first step involves the preparation of a concentrated solution of chlorine from either chlorine gas or chlorinated lime. This concentrated solution is then added to the treatment plant effluent. In some plants the final effluent is dechlorinated with sulphur dioxide. Chemical Model The purpose of this model is to estimate the concentrations of species containing Cl+. The importance of these species lies in their ability to react with organics to form stable carbon - chlorine bonds. There are many 21 Table 2.10 Inorganic Composition of Lion's Gate Effluent Component Total Concentration Fraction Dissolved/Total3 mg/1 Al 0.095c 0.12 As <0.006 B <0.05 Ba <0.02c; Be <0.05 Ca 8.7° 0.88 Cd <0.001c • Cl" 28 Co <0.005t( Cr 0.011c Cu 0.10S' 0.92 F" 0.07 Fe 1.05c 0.35 Hg <.<0.002c K 6.7s 0.95 Mg 2.989 0.96 Mn 0.04^ 0.94 Mo <0.02g NH3-N 15b Ni 0.011s Pb 0.013f 0.0 Se 0.008& Si 2.8r 0.11 Ti <0.2C' V <0.07© Zn 0.105e. 0.0 a For primary effluent as opposed to whole sewage as calculated from data of Heukelekian and Balmat (1959) b GVRD data c Total HCI - HNO digestible components and factors which should be included in the model. These include the sources of chlorine, the solvent, ammonia, other inorganics, particulates, organics, pH, reaction time, mixing, temperature and sunlight. In order to keep the model simple only three factors will be considered. 1) the hydrolysis of chlorine, 2) the dissociation of hypochlorous acid, and 3) the reactions of chlorine and hypochlorous acid with ammonia to form chloramines. The following equilibria and reactions will be used. 1) Cl„, * + HO ^ H' + Cl :+ H0C1 2(aq) 2 2) H0C1 + H20 * H30+ + 0C1 3) NH.. . + H„0 =? NH,+ + OH" 3(aq) 2 4 4) NH3 + H0C1 NH2C1 + HO 5) NH2C1 + H20 -*H0C1 + NH^ KJJ Q = 4.2 x 10"* at 25°C 0C1 = 2.5 x 10 8 at 20°C = 1.8 x 10 5 at 20°C k = 9.7 x 10 exp(-3000/RT) 1 mole sec k = 8.7 x 10 exp(-17,000/RT) sec -1 6) NH2C1 + H0C1 NHC12 + H*0 7) 2NH.C1 NHCl. + NH • 2s 2 j k2 = 7.6 x 10 exp (-7300/RT) 1 mole sec k3 = 80 exp (-4300/RT) 1 mole"1sec~1 From Q it can be seen that at pH 4 all of the chlorine is in the form of hypochlorous acid. Now if A =[H0Cl] -+• [0C1~J B = [NHJ + [NH!]" then 8. [HOC!], = A 9. [NHj = B Since k^» k2»k-3 the concentration of monochloramine is to a rough approxima tion independent of the concentration of dichloramine. From the equilibrium 11. NH2C1 + H20 = H0C1 + NH3 it can be seen that 12 la From equations 6 and 7 it can be seen that The final concentrations of hypochlorous acid and hypochlorite ion can be calculated as follows: The individual concentrations of the acid and ion can be calculated from equation 8. From these equations a solution of the initial composition: [NH^-Nj -1 x 10~3M, [total Cl+]- 1 x 10 ^M; pH - 7.0; and reaction time - 10 minutes; will have the following final composition: Limitations of the Model There are many limitations to this model. The most important are that the reduction of Cl+ to Cl through reaction with reducing agents and the decompositions of the chloramines to nitrogen gas and other products have not been included. Other less important factors not included are 1) formation of chlorine hydrate, 2) decomposition reactions of hypochlorous acid and hypo chlorite ions, and 3) the formation of other N-chloro compounds. These factors are discussed in Appendix I. Validity of the Model Palin (1950) and Isomura (1967) h'ave conducted studies on the composi tions of d'ilute ammonia - chlorine solutions in distilled water. At ammonia/ chlorine mole ratios of 1:1 both investigators found that the ammonia was al most totally converted to monochloramine. Unfortunately due to the detection 14. and •2,4 limits of the analytical methods no quantification of dichloramine and hypochlorous acid could be made. A general feeling for the validity of the aqueous ammonia-chlorine system --. as a model of the primary effluent-chlorine system can be obtained from the plots of residual chlorine against added chlorine for the two systems. The plot for the aqueous ammonia-chlorine system was called the 'breakpoint curve' by Griffin and Chamberlain (1941a,b). An example of the plot for a primary effluent-chlorine system can be found in the study by McKee et al. (1960). The overall shapes of the two curves and the forms of the residuals are sim ilar which indicates that the model is essentially valid. There are however, two differences between the curves in the region of the chlorine/ammonia ratio normally used in sewage treatment plants. Firstly, primary effluent instant-aneously consumes 0.4 - 1.1 x 10 moles/l of Cl^ wM/Te^the ammonia system has :no instantaneous /demand., and secondly, with primary effluent the slope of the line is between 0.82 and 0.92 rather than 1.0 as noted in the ammonia-chlorine system. In other words, primary effluent dosed with 28 mg/1 of Cl^ will con sume 4.9 - 11.2 mg/1 Cl2 in fifteen minutes. The instantaneous consumption of 2.8 - 8.7 mg/1 is probably due to oxidations of inorganics and/or some very rapid reactions with organics. The slower consumption of 2.1 - 3.5 mg/1 as manifested in the differences in slopes tentatively suggests the occurrence of oxidation and substitution reactions with organics. In summary, -the form of the residual chlorine in a treatment plant is es sentially mono and dichloramines as was predicted by the simple model. The val ue of a more refined model which includes minor interactions is tempered by the tremendous complexity of the chlorine-primary effluent system. There is some indication that reactions of Cl+ sources with organics do occur. D. Reactions of Chlorine With Organics in Aqueous Media 1. Reactions With Nitrogenous Compounds . 25 Engineering Oriented Studies Taras (1950, 1953) conducted a comprehen sive study of the chlorine demands and nitrogen losses of amino acids as well as some proteins and other compounds. Smaller studies were conducted by Wright (1926), Norman (1936), and Palin (1950). Strict comparison of the behaviour of these compounds to chlorine is not possible on the basis of these studies due to the differences in Cl/N ratios and analytical problems. From the results of Taras (1950, 1953) however some general trends can be observed with initial mole ratios of 4:1 (Cl/Albuminoid-N) and near neutral pH: a) primary CK and /£ -amino groups, mercapto and thioethereal groups all consume two mole* equivalents of Cl^ in fifteen minutes, b) the £ and £" -amino groups and peptide linkage nitrogen atoms react very slowly with chlorine, c) aromatic substitution of chlorine probably occurs in tyrosine and tryptophane, and d) losses of ni trogen in a one hour occur only for cX and j&-amino acids and range from 25 to 50 percent. Zaloum (1973) investigated the reaction of varying dosages of chlor ine on some amino acids and other compounds. At mole ratios of less than 2:1 (Cl/N) no loss of chlorine residual was observed except in the case of histidine. His result for histidine indicates that electrophilic addition or substitution to carbon probably occurs. He also demonstrated that with Cl/Glycine mole ratios greater than 21:1 oxidation of glycine with loss of carbon occurs. Pure Chemistry Oriented Studies A conGise picture of N-chlorination of amines was presented by Morris (1965) in the form of a Bronsted type plot of pK^ vs log k^/k^, where k^ and k^ are the respective competitive molecular reaction rate constants of H0C1 with the amine and ammonia. A good linear correlation with a slope of 0.5 was obtained. It should be noted however that ammonia itself showed a significant deviation of the type usually attributed, to steric hindrance. Investigations by Dakin (1916) among others indicated that the reaction of Of-amino acids with NaOCl and other chlorinating agents results in deamination and/or decarboxylation to form the corresponding aldehyde or nitrile. A study 26 by van Tamelen et al. (1968) yielded the following: a) with dimethylglycine decarboxylation occurs most readily with a pH of 1.5 and a Cl/N mole ratio of 2:1, carbon dioxide, formaldehyde, and chlorodimethylamine were identified as products, b)decarboxylation most likely involves N-chlorination rather than formation of the acyl hypochlorite and definitely involves a trans, coplanar arrangement, and c) other complex reactions also occur with compounds such as trytophan. Patton et al. (1972) present the following observations on the aqueous chlorination of cytosine: at a 1:1 mole ratio only 4,N-chlorination occurs, b) at a 2:1 mole ratio Cl/Cytosine the 4,iN-chloro (I), 4,N-chloro, 5-chloro (II), 4,N-chloro, chlorohydrin (III), and 1,4N-dichloro-chlorohydrin (IV) were all formed, c) increasing the Cl/Cytosine mole ratio increased the yield of III and IV and at a 5:1 moijie ratio a tetrachloro derivative was formed which decomposed on standing to I and II. Subsequent investigations by Pereira et al. (1973) at pH 4 and a 2:1 Cl/substrate mole ratio with some amino acids and dipeptides yielded the following: a) with tyrosine only the ring chlorinated aldehyde or nitrile rather than the ring chlorinated amino acids were observed which conflicts with the claims of Thompson (1954), b) with L-phenylalanirie the nitrile/aldehyde ratio was 95/5, kc) with glutamic acid only the carboxyl group alpha to the amino group was removed d) only terminal N-chlorination is observed with dipeptides with possible decomposition of the dichloramine to a chlorimine and e) no N-chlorination is observed with N-acetyl L-alanine; ' f) with cysteine only oxidation of the sulphur to cysteic acid and some dimer ization to cystine was observed, cystine was oxidized to cysteic acid. Addition al studies on the reaction of other organic sulphides with chlorine are discussed by Baker et al. (1946). Hoyano e_t al. (1973) studied the reactions of some uracils and purines with aqueous hypochlorous acid at HOCl/substrate mole ratios of 2 and 4:1. With the uracils, N-chlorination precededdelectrophilic substitution. The purines yielded 20-90 percent parabanic acids in seven days. Thus oxidative 27 degradation may be an important reaction with these compounds. A somewhat special case is observed in the chlorination of cyanuric acid, (Brady e_t al., 1963; Sancier et_ al. , 1964) where N-chlorination occurs only in the keto-tautomer. The stability of the N-chlorinated keto-tautomer combined with the facile release of chlorine from the enol and the fact that there are three tautomeric sites on the triazine ring has made cyanuric acid an important "chlorine stabilizer" in swimming pools (Gardiner,1973; Canelli, 1974). 2. Reactions of Chlorine with Other Organics Introduction The reactions of chlorine with organics can be classified into four groups: nucleophilic attack of Cl , electrophilic attack of Cl+, photochemical, and oxidation reactions. Excellent reviews of chlorination reac-^ tions in pure systems have been published by House (1965), Eisch (1966), Buehler and Pearson (1970) and Dorn (1972). In reading these reviews, it must be kept in-mind that most of the yields quoted have been optimized. Furthermore, a yield of less than one percent is usually insignificant to a classical synthetic chemist whereas such a yield may be very important to an environmental chemist. Therefore a brief summary of conditions in a treatment plant is provided in Table 2.11 in order to obtain a feeling for the relative importance and possible magnitudes of these reaction groups in primary effluent. These groups will now be discussed in the most probable order of importance. Oxidation Reactions These reactions have been reviewed by Barker (1964). The mechanisms are not completely understood. In most cases oxidation with H0C1 is as rapid as with molecular Cl^ however, factors such as acid and base catalysis, the greaterppropensity to oxidation of anions, e.g. formic acid, and hydrate formation e.g. aldehydes make generalization somewhat tenuous. It is well known that aldose sugars are oxidized to acids by hypochlorite. Several investigations of the oxidation of aromatic rings have been carried out. In acidic solutions, Van Buren and Dence (1967) working with lignin model com pounds estimated that 20 - 80% of the products are oxidation rather than sub-28 Table 2.11 Summary of Reaction Conditions for Organics in Sewage a. Conditions in the Main Body of Water Component Remarks Solvent Buffers PH Temperature Mixing • Cl2/HOCl/OCl" NH3 Cl" Br" Organic compounds Bacteria Heavy metals Reaction time Water Acetic acid/Acetate Carb onate/B icarb ona t e 6.5 - 8.5 2-12°C Variable Approximately 50/50 in H0C1/0C1" very little of each available Martially converted to chloramines [Total C1+J* = 10"4 M ~10"3MM *~10~4 M [individual] ~10"6 - 10"4 M [TotalJ-10"3 -10"4 M --10 mg/1 0.001 - 10 mg/1 20 - 50 minutes b. Conditions at the Surface Component Remarks ;. Solvent Floating organics = 0.1 - 2.0% of the area Polywater? Temperature (air) 2 - 37° C Reaction time 15-30 minutes UV light Variable, direct sunlight sometimes -7-i- i.able Cl2 Possibly present Chloramines Present Organics Abundance of some types is greater at the surface "T" "Cl " refers to all species containing chlorine in the +1 oxidation state as opposed to hi|drated Cl+ ions. No Cl+(aq)is expected to be present (Swain and Crist 1972). 29 stitution or displacement products, while Vollbracht et al. (1968) determined that exhaustive chlorination of some other phenols yielded chlorinated cyclo-hexenones. In neutral solutions, EPA (1972) postulated ring cleavage of phenols. In basic solution, Moye and Sternhell (1966) state than phenol is converted to a chlorinated cyclopentane carboxylic acid probably by a Favorskii rearrange ment arid oxidation of the cyclolpentenone' intermediate. Electrophilic Reactions Aromatic electrophilic substitutions of chlorine for hydrogen using sodium hypochlorite were reviewed by Hopkins and Chisholm (1946) and Soper and Smith (1926). The kinetics of the aqueous chlorination of phenolwere investigated by Burttschell et al. (1959), and Lee-and Morris (1962) among others. Eliasek and Jungwirt (1963) studied the exhaustive chlorination of phenol, ortho-cresol and pyrocatechol by sodium hypochlorite. They found that the completely o,p substituted phenol is initially formed followed by oxi dation to a chloroquinone. The chloroquinone was then either further chlorinat-. ed, or in the presence of light, converted to a hydroxychloroquinone which poly merized at pH>7 to humic acid type compounds. An unspecified type of oxida tive decomposition was observed in the case of pyrocatechol to the extent of 60 per cent. Van Buren and Dence (1967) observed the substitutive displacement of the propyl moiety from guaiacyl ethyl carbinol and veratryl ethyl carbinol. Electrophilic addition is known to occur in aqueous solution or suspension, eg. Emerson (1945). Investigations by Gunstone and Pereira (1973) among others demonstrated that halogenation of unsaturated fatty acids and alcohols of the appropriate stereochemistry can respectively yield significant amounts of halogenated oxolanes and oxanes. Hawkins (1973) natsnt-sd anones .NaOCl and an ammonium sal-j Zz Uv.5 r,--Jia-tion zi •' -•vane..c Photochemical Reactions Meiners and Morriss (1964) studied the effect of UV irradiation on the chlorine oxidation of starch in acidic aqueous solution. More recently Kobayashi and Okuda (1972) found significant photochemical up-30 take, cf chlorine by a large number of compounds in dilute aqueous solution. Catalysis by Hg(II) and PbXXT)- W^as, also noted, Nucleophilic Reactions Due to the competitive hydrolysis reactions, nucleophilic substitutions are unlikely to play an important role in sewage effluents. It should be noted however that halide exchanges involving the addition of chloride will make the compound more stable with respect to hy drolysis. 3. Reactions of N-Chloro Compounds with Organics It has been noted by Burttschelle6:fga:-1> (1959'),*;andxotR'ersT^that; the rate of chlorination of phenol in the presence of ammonia is very slow. Zaloum (1973) observed oxidative type chlorination reactions of amino acids by chloramines. The classical mechanism of chlorination involves catalysis by acid and chloride with the limiting step being the dissociation of the chloramine to the amine and molecular chlorine, e.g. Hurst and Soper (.1949). Some evidence has been presented for the direct chlorination (electrophilic substitution) by morpholinum ions l(CarraaridB.Englarid(1958) , dichloramine-T .(jHiguchi and Hussain, 19.6#')\,s and diethylchloramine X'BrownaaridFSpper^1953) , An important facet of the investigation of Brown and Soper is that rate of chlorination of phenols 3 with N-chlorodiethyl amine at neutral pH is 10 times greater than that of chlorination with H0C1 probably due to the significant amounts of RR'NC1H+ present. Onuska (1973) was unable to detect diethyl amine in sewage, although Rains et al. (1973) tentatively identified a series of alkyl amines in sludges. West and Barret (1954) observed the production of 5-chlorouracils from the reac tions of some uracils with N-chlorosuccinimide ih?acetic acid. Chlorination of styrene by monochlorourea was discussed by Hanby and Rydon (1946). The alpha-chlorination of unsymmetrical benzylic sulphides with N-chlorosuccinimide in carbon tetrachloride was observed by Tuleen (1967). Substituted hydrazines have been prepared from chloramine and a substituted amine (Audrieth and Dia mond, 1954; Diamond and Audrieth, 1955), or by other chlorinating agents (Audrieth et al., 1956, Colton et_ al., 1954). Hawkins (1973) patented the use of cyclohexanone, NaOCl and an ammonium salt for the production of 1 - chloro-amino cyclohexanol. Other examples of the reactions of chloramines can be found in the reviews by Drago (1957) and Kovacic et al. (1970). Free radical addition of chloramines to unsaturated compounds in H^SO^/ HOAc resulting in^-chloroamines hass been noted (Kovacic et al., 1970). Gas phase reactions tend to yield only chlorinated products (Prakash and Sisler,1970). E970)The Effects of Chlorine on Sewage Effluents 1. Practices in Treatment Plants The latest estimates of chlorine usages in the United States (JWPCF, 1974) are 1.87 x 10^ tons/year for wastewater, 2.5 x 10"* tons/year for water supplies and 2.1 x 10^ tons/year for swimming pools. The composition of gaseous chlor ine was discussed by Laubusch (1959). The purity is 99.5% or better with the major impurities being N2 and CO^ although some halogenated methane, ethane and benzene derivatives may be present in ppm quantities. The uses of chlorine in wastewater treatment have been described by White (1972). The dosage applied varies according to the strength of the effluent. For example, during the night when the sewage is essentially infiltration, only 1-2 mg/1 Cl^ may be added while during peak loads and, especially dur ing dumping of digestors, 30 mg/1 Cl^ may be added to the effluent. Contact times vary from 0.25 to 0.5 hr depending upon the flow and length of line be tween the plant and receiving water. The combined chlorine residuals in the effluents range from 0.0 to 5.0 mg/1 depending on the time of year and whether or not dechlorination is practiced. Free residual chlorination is not the usual practice. 2. Biological Effects of Residual Chlorine Disease Control The historical trends of water borne disease outbreaks have been reviewed by Craun (1972), Craun and McCabe (1973) and Kittrell and Furfai,(1963). There can be no doubt that chlorination of water supplies has effected a significant decrease in diseases, however a total eradication has not occurred. The effect of waste-water chlorination on disease outbreaks has not been documented and is very difficult to establish. The effects of chlorination of effluents on coliform counts at a beach in the receiving water are ambiguous due to regrowth of col-iforms and various environmental factors affecting dieoff (Kittrell and Furfai 1963). In addition, Silvey et al. (.1974) found salmonellae bacteria in chlor inated effluents and receiving water. Toxicities to Various Forms of Life The addition of material to an eco system can cause population changes due to specific or general toxicity, car cinogenicity, mutagenicity, teratogenicity, behavioural modification or its being a specific limiting nutrient. Toxicity of residual chlorine is a func tion of pH, temperature, form of the residual and other factors. In addition, toxic and other detrimental effects can be complicated due to synergistic and antagonistic effects (Longbottom, 1972; Ongerth, 1973). Studies or re views of the toxicities of residual chlorine have been undertaken by Merkens (1958), Zillich (1972), White (1972) and Brungs (1973). Microorganisms (Bacteria, Viruses and Algae). The effect of chlorine on sewage bacteria, especially coliforms has been discussed by Fair et_ al. (.1948) and Heukelekian and Faust (1961) among others, and reviewed by White (1972). Although it is a function of pH, effective control (99.9% kill) of bacteria requires 0.1 to 5.0 mg/1 combined residual for 10 minutes, while viruses require 0.2 - 0.5 mg/1 free residual. In receiving waters, regrowth is a function of many factors including temperature, pH, and nutrients. Kittrell and Furfai (1963) state that a re growth of 4 to 8 times the original population of coliforms occurred in 0.5 days followed by a decline. Salmonellae, fecal coliforms, and fecal strepto cocci do not appear to exhibit this regrowth in surface waters (Silvey e_t al., 1974) . 33 Inhibition of algal growth was effected by 0.15 - 3.0 mg/1 (McKee and Wolf, 1971). Studies by Kott (Kott and Edlis, 1969; Betzer and Kott, 1969; Kott, 1969) showed that chlorine is algistatic to chlorella pyrenoidosa and C. sorokiniana at 0.4 mg/1 and to cladophora sp. at about 1 mg/1. He also showed that 10 mg/1 residuals of chlorine are necessary to kill these species while bromine or a mixture of chlorine and bromine killed chlorine resistant algae eg. Cosmarium and other algae at residuals of 0.4 to 2.0 mg/1 total halogen. In addition he noted that the availability of light and the timing of dosages also affect the toxicity. Invertebrates.. Some/values for toxic levels of residual chlorine taken from McKee and Wolf (1971) are chironomous (Blood worms) 15 - 50 mg/1, chir-onomous larvae 0.65 mg/1 in 24 hrs., mussels, snails, sponges 2.5 mg/1, nem atodes 95 - 100 mg/1, and shellfish pumping rates are reduced by 0.01 - 0.05 mg/1. Daphnia were killed in 48 hrs. by 4 mg/1 of chlorine. Other studies have been conducted by McLean (1973) on the combined effects of chlorine and temperature and weteci.nco,nclusiv.e^. TvSh. From the reviews by Brungs (1973), McKee and Wolf (1971) and Zillich (1972) it can be stated that toxic effects range from Brown trout exposure to 0.04 mg/1 free for 2 minutes results in 100 % mortality in 24 hrs., to white suckers, 1.0 mg/1 free Cl^ is lethal in 0.5 to 1.0 hrs. White (1972) correlates this to scale size. Other effects such as "depressed acti vity" in brook trout are observed at concentrations as. low as 0.005 mg/1 free Cl. Servizi and Martens(1974) and Martens and Servizi(1974) working with various types of effluents found mortalities of salmon and rainbow trout at combined residuals of 0.02 mg/1 which is the detection limit of the amperometric titrator. ' They also found evidence of gill damage after prolonged exposure to chlorine and. that, Cpho salmon do not necessarily avoid" areas containing lethal . (1.3 mg/1) concentrations of chlorine'. 34 Plant Life. The effect of chlorine on plant life in aquatic systems is essentially unknown. A study on kelp indicated 5-10 mg/1 significantly reduces photosynthetic activity (McKee and Wolf, 1971). Mammals. Muegge (1956) reports that humans have high tolerances for residual chlorine. Concentrations of 50 mg/1 and higher in the form of free chlorine have no acute toxic effects. It should be noted however that aller genic - type responses have been reported (Watson and Kibler, 1934), and that eye irritations have also been observed at concentrations of 0.5 mg/1 (McKee and Wolf 1971). 3. Toxic Effects of Chlorinated Organics A large volume of information is available on the toxic effects of in dustrially produced chlorinated organics. The acute toxic effects of these com pounds have been reviewed by Fishbein and Flam (1972) and Gribble (1974). Their mutagenic effects were reviewed by Fishbein (1973b) while Miller (1974) discussed some teratogenic effects. A study by Das et al. (1969) showed that various chlorocatechols and chloro-o-benzo-quinones from bleached kraft chlor ination effluent had 1-3 hr LC-^QQ values of about 20 mg/1 for young Salmo salar (Atlantic Salmon). Preliminary studies by Gehrs e_t al. (1974) on 4-chlorores-orcinol and 5-chlorouracil indicated deleterious effects on hatching of carp eggs occur at concentrations of 0.1 and 5 mg/1 respectively. While it is obvious that some chlorinated compounds are very toxic, the important question relating to the chlorination of sewage is whether halogenation or oxidation of an organic compound makes it more toxic to aquatic life. In considering this question it is useful to separate two facets of acute toxicity 1) the numerical yaiuenexpressing the. toxicity-pfpa .particular compound to an organism and 2) the structural features of a molecule which tend to make it toxic. An example of the first facet is the comparison of the toxicities of a series of benzene derivatives to aquatic life Table 2.12. Two problems arise., when attempting to compare the toxicities of different compounds by a liter-Table 2.12 Toxicities of Selected Compounds to Aquatic Life' Compound Organism Toxicity . • „. • - b Criterion Concentration ^ .Benzene Sunfish LC 46 II Mosquito Fish 48 hr TLM 490 it Rainbow Trout ^100 13-26 ,6-Dichlorobenzene Fish LC50 2.2 p-D ichlo robenz ene Fish LC100 34 Phenol Goldfish MTE° 1.00° ^hS-CMforopnenol n II 1.58° m-Chlorophenol n II 2.10° p-Chlorophenol II II 2.58° Phenol Bluegill Sunfish 48 hr TLM 21 6-Chlorophenol Bluegill Fingerlings/96 hr-TLM-6.6 Pentachlorophenol Various Fish 24 hr TLM 0.75-0.22 Benzoic Acid Mosquito Fish TLM 200 II Goldfish 7-^-916 hr L LC100 _160 2,3,5-Trichlorobenzoic Acid Large Mouth Bass 24 hr TLM 67 2,3,6-Trichlorbbenzoic Acid Large Mouth Bass 24 hr TLM 670 Phenol Daphnia JT_.D MLD 17 ti Scenedesmus (Alga) it 43 II Microregma (Protozoan) it 32 II E. Coli (Bacterium) " 1100 Quinone Daphnia 0.37 II Scenedesmus 5.5 II Microregma " 0.18 II E. Coli " 46 Hydroquinone Daphnia " 16 II Scenedesmus 7.3 tt Microregma it 45 n E. Coli 27 Toluene Daphnia 6.5 Benzyl Alcohol it 48 hr MLD 33 Benzoic Acid it prolonged MLD 12 a. From McKee and Wolf (1971) unless otherwise indicated b. Units are 10^ times moles per litre unless otherwise indicated c. Data from Gersdorff and Smith (1940); MTE = maximum toxic effect ex pressed in units of 1 mole-! min~l normalized to phenol; a larger number indicates a greater toxicity. ature review. The first problem is that toxicities are reported in units of mg/1. While the numbers generated from the use of these units are indicative of the absolute toxicities of the compounds, they do not reflect the relative toxicities of a series of compounds on a molecule for molecule basis. There fore for this review toxicity values have been converted to units of moles per litre. The second and more serious problem arises out of the non-standardized conditions used in the generation of toxicity data. As a result of this prob lem it is presumptuous to arbitrarily establish a minimum difference between 'the toxicity values for two compounds which must be considered significant. A study of the second facet of toxicity is furnished by Table 2.12 as well as the reviews of the industrially produced chlorinated organics. From Table 2.12 is appears that chlorination or oxidation increases the toxicity of the compound only in certain cases and that toxicity is related to position of substitution and numbers of chlorine atoms present. From other studies it appears that although the toxicity cannot be easily predicted from structure the two are related. Important factors or coincidental properties appear to be: a) stability with respect to degradation, e.g. DDT, aldrin b) position of chlorine substitution, e.g. chlorinated dibenzodioxins; c) other forms of stereoisomerisms, e.g. BHC; and d) water solubility e.g. dichlorobenzenes (McKee and Wolf, 1971). Sublethal effects such as interference with or duplication of pheromones and alarm substances (Vallentyne, 1967) are probable but have not been inves tigated. These sublethal effects may be even more important than acute toxic effects due to the low concentrations of organics in primary effluents. 4. Chemical Effects of Chlorination Engineering Studies The reactions with oxidizable inorganics have been previously discussed. (O'lve'rc et al. (1974) noted the solubilization of heavy metals from sewage sludges exhaustively chlorinated. This effect is probably 37 due to pH reduction, rather than oxidation by chlorine. Apart from the breakpoint curve, some investigators have noted a BOD reduction of the dechlorinated sewage. A recent investigation by Zaloum (1973) refutes these claims and postulates that the observed changes in BOD,, were due to differences in initial microbial population during the BOD test. He did not observe any detectable reduction in TOC upon chlorination. Chemical Studies The first major studies of the effects of chlorine on organics in wastes dealt with kraf t mill bleaching wastes (Van Buren e_t al. , 1969; Das et al., 1969; Rogers and Keith, 1974). Chlorinated quinones and phenols were found in these effluents. A major investigation of the effects of chlorination on municipal treat ment plant effluents was undertaken by Jolley (1973). He limited his investiga tion to the relatively non-volatile compounds and investigated the following areas: 1) primary effluent -a) the effects of various dosages of non-radioactive chlorine b) the magnitude of the uptake of radioactive chlorine by organics at a dosage of 26 mg/1 Cl^ c) the separation and identification of the chlorinated compounds formed during chlorination. 2) secondary effluent a) the magnitude of the uptake of radioactive chlorine by organics and inorganics b) the effects of dechlorination upon chlorine uptake c) an evaluation of the effects of using NaOCl instead of Cl^ (g) upon chlorine uptake d) the identification of chlorinated compounds formed during chlor-•f ination. 38 His concentration procedure involved rotary evaporation followed by lyophil-ization. Separation was accomplished by anion exchange liquid chromatography with a UV detector and continuous fraction collector for the radioactivity counts and cation exchange LC. Identification was based on chromatographic retention time. The most striking result of Jolley's experiments with non radioactive chlorine and primary effluent was the disappearance of UV absorbing compounds with increasing dosages of chlorine. Several new peaks were also observed in the chlorinated samples. Some important results of his radioactivi ty work are as follows. Forty-nine of the sixty-two radioactive compounds appeared at similar concentrations in both primary and secondary effluents. Between 44 and 52 radioactive peaks were observed in the individual chromato-36 grams, at a detection limit of about 50 ng=/l Cl in unconcentrated sewage. The concentrations of the individual compounds ranged from 0.1 to 15y#g/l as chlorine in sewage. He found that reaction time only slightly affects the yields of chlorinated compounds while the form of the applied chlorine affects the formation of at most six compounds. Dechlorination had no significant effect upon the number of stable organo-chlorine compounds formed. A very important calculation showed that about 0.6 percent of the applied chlorine eluted in peaks other than chloride while another 0.4 percent remained in the resin. This means that about 1 percent of the chlorine applied to primary and secondary effluent at dosages of 6.0 and 2.6 mg/1 Cl^ respectively ends up in stable organo-chlorine compounds. This value may be even higher since the losses due to volatilization (Pitt and Scott, 1973) and insolubility during the concentra tion procedure were not further investigated. A list of the compounds identified by Jolley appears in Table 2.13. Most of the products are those expected from direct electrophilic substitution, although the meta-substituted phenol, 5-chlorosalicylic acid, and 6-chloro-guanine are obvious exceptions. Somewhat surprising is the 1:4 ortho-para 39 Table 2.13 Chlorinated Compounds Formed by Chlorination of Primary Effluent Compound 2- Chlorophenol 3- Chlorophenolb>d 4- Chlorophenold 4- Chloro-3-methyl-phenold 3- Chloro-4-hydroxy-benzoic Acidd 5- Chlorosalicylic acid 4- Chlororesorcinold 5- Chlorouracil 5- Chlorouridine 8-Chloroxanthine 8-Chlorocaffeine 6- Chloroguanined 2- Chlorobenzoic acid 3- Chlorobenzoic acid^»d 4- Chlorobenzoic acidd 4-Chlorophenylacetic acid 4-Chloromandelic acid Concentration in Primary Effluent jlg/1 MxlO8 Concentration of Probable Precursor (/lg/1) MxlO8 7.6 6.0 10.6 11.3 (0.51) (0.40) (0.69) (0.54) (1.5) (1.1) (1.3) 0.80 — 0.74 0.51 • 7 5.5 (1.2) (0.83) 26.2 17.6 40 35 20.4 8.2 4.5 2.4 70 45 6.7 . 3.1 10 5.5 (0.9) (0.48) 0.38 0.26 :(0.62) (0.42) — (1.1) (0.75) — 11.1 7.0 17c 13.6 1.9 1.1 a. Jolley (1973) b. Identified as either or both of these compounds. c. From total of compounds in chlorinated effluent, converted to equivalent concentration of unchlorinated species. d. Not found in primary effluent, concentrations in parentheses refer to secondary effluent. 40 substitution ratio; of the benzoic acid (Smith 1934). The yields of chlorinated compounds range from 5 to 50 mole percent based on the organic precursor. The high yield of 2-chlorophenol conflicts with the observations of Burttschell et al. (1959) although it should be pointed out that Burttschell's group worked with pure solutions rather than sewage. Another study on sewage has been undertaken by Glaze ejt al. (1973) using XAD resin extraction. He found that volatile chlorinated compounds were formed at 10-100 mg/1 Cl^, thus Jolley's estimate of the amount of chlorine in new stable organochloririe compounds may be low. Glaze doubly filtered his sewage before chlorination; thus the uptake of chlorine by bacteria and other solids was eliminated and, in addition, some loss of ammonia may have occurred. He also acidified his effluent to pH 2 - 3 which may have resulted in premature saturation of the resin with volatile acids. The only compound he has iden tified to date is chloroform.v Adams and Middlebrook (1973) studied closed loop hypochlorite systems such as those used in recreational boats and vehicles. Their analytical technique of extraction of flash evaporated or (Unconc'entratedfie'fiffl'Uents with ether or chloroform followed by evaporative concentration and direct NMR and IR analysis is of limited value. The presence of halogen in the ether extract was detected by AgNO^. They postulated the presence of chlorinated fatty acids. Rook (1974) established that haloform reactions occur with colored matter in natural water. This work was directed to drinking water and thus is not directly comparable. Aagroup £n-9flj?nnes'o't'afOGaglsdn(197-3)"5Carlsondettalir(T975) ,is investigating the chlorination reactions of a number of model organic compounds in dilute aqueous solution at different pH. These studies are not yet complete, however, as an example of his results, the chlorination of oi. -terpinol yielded a mixture of eight products. The composition of the product mixture was pH dependent. 41 Toxicity tests showed that all the products except the dichloride have about the same toxicity as -terpinol to Daphnia magna, i.e.: 48 hrs «/120 mg /l whereas the dichloride had an LC^Q 48 hrs of about 15 mg/1 (Carlson and Capple, 1974). These workers are also involved in developing methods for relating the physical properties of a molecule to its ability to bioaccumulate and to exhibit toxicity. F. Analytical Methods The analysis of environmental samples is an especially difficult problem due to the complex nature of the samples and the very small concentrations of materials to be analyzed. Two general approaches to the problem are used: a) the complete physical separation of components followed by analysis and b) the quantitative determination of specific compounds in the presence of others through the use of specific detection methods. In this study, the first approach will ultimately be used although the second will be a valuable aid in the development of the techniques to be used. The overall approach to the problem will involve techniques of sampling and preservation, concentration, separation and chemical analysis. These techniques will be briefly reviewed in the following sections. 1. Sampling and Preservation Hunter and Heukelekian (1965) used 24-hour composite samples in their analysis of sewage to allow for the diurnal fluctuations in composition. This approach has several drawbacks. The concentration of slugs of compounds will be underestimated, automatic samplers which sample at a specific depth will miss floating material and finally, the storage time of the first sample is a minimum of 24 hours. Grab samples on the other hand, will overemphasize or entirely miss slug loads. In addition, when samples are taken by hand there is the psychological tendency to either catch or miss obviously rich portions or areas. 42 Various methods have been evaluated for preservation of sewage samples for specific analyses. The losses of materials are attributed to two main causes, biological decomposition and physical losses due to evaporation, precipitation and sorption on the sampling vessel and particulates. Loehr and Bergeron (1967) and Hellwig (1967) have reviewed the chemical preserva tives used for sewage. Loehr and Bergeron (1967) found that storage at 1°C alone is satisfactory for preventing changes of COD, BOD, pH, DO and SS for six days. Lichtenberg (1973) found that storage in a cold, dark environment did not prevent loss of PCB's and recommended the addition of 15 mg/1 of formaldehyde. Desbaumes and Imhoff (1972) in their study of hydrocarbons stated that only glass or stainless steel containers are suitable because;of sorption. They also indicated that substantial losses occur if storage time exceeds 10 hours although no details as to the mechanism of the loss are given. Adsorption onaglass may also be a problem as Leithe (1973) states that glass containers should be extracted for 1 hour with pet ether for pesticide samples. Ahnoff and Josefsson (1974)^found that 5% of the DDT in an 8ytg/l aqueous solution was adso^be'ded on the glass container. Desbaumes and Imhoff (1972) also identified some substituted benzenes leached by water from plastic bottles. The type of plastic was not identified. Phthalate esters and other plasticizers are also leached by water from plastics and some steel containers (Mathur, 1974). 2. Extraction and Concentration Four general methods, namely, solvent extraction, adsorption, freeze concentration and gas stripping have been used for the concentration of organ ics from water. Solvent Extraction Hunter and Heukelekian (1965) and Hites and Biemann (1972) used the separatory funnel technique. Methylene chloride, Freons, and a mixture of methylene chloride and diethyl ether are favourite solvents for 43 this technique. Continuous extractions, both with solvent distillation (Goldberg et al., 1973) and without.solvent distillation (Ahnoff and Josefsson, 1974) have been used. Two or three of these extractors are usually set up in 'a series - and total recoveries of 70 to 110% are reported by Goldberg et al. (1973) at flow rates of 8 1/hr. Adsorption The optimum procedures for carbon adsorption of organics from wastewaters have been discussed by Buelow et al. (1973a, b). Studies on desorption have been conducted by Hoak (1964) and Allen et_ al. (1971), and the desorption of phenols from activated charcoal for example, ranges from 22 to 70 percent. Cookson e_t al. (1972) have noted the oxidation of n-butylmercaptan to n-butyldisulphide during adsorption on charcoal, presumably due to the presence of molecular oxygen and quinone. Lee et al. (1965)used carbon adsorption to extract organics from Lake Mendota. Generally speaking carbon adsorption is not used for trace analysis of unknowns due to the activity of the carbon surface and the difficulty in eluting some material from carbon. Kennedy (1973) and Gustafson and Paleos (1971) have reviewed the kinetics and applications of macroreticular resins for adsorption of organics from wat er, while Kim et al. (1974) discussed the engineering uses of synthetic resins for water treatment. Junk et al. (1974) have determined and optimized re coveries and concentration procedures for 99 different compounds using XAD-2 or XAD-4 resin. Recoveries vary from 80 to 100% except for short chain ali phatic alcohols, acids and some phenols whose recoveries are affected by pH and salt concentration,';, Webb (1973) found these resins ineffective for ali phatic hydrocarbons. Pitt and Scott (1973) report poor recoveries of non-vol-atiles from domestic effluent. These resins can be selectively and/or complete ly regenerated depending upon choice of solvent. XAD-2 has been used in LSC of phenols (Grieser and Pietryzk, 1973). Examples of applications of macro reticular resins to environmental work are the studies by Burnham e_t al. (1972), 44 Harvey (1973), Glaze et al. (1973), Vinson et al. (1973) and Rogers and Mahood (1974). Columns of polyurethane foam plugs with, acetone and hexane elution have been used by Chow et al. (1971) to recover 20 ppb of PCB's with 91-98% efficiency. In a study on pesticide recoveries, however, Uthe et al. (1972) found it necessary to coat the plugs with selective adsorbents. Webb (1973) found both coated and uncoated plugs ineffective for most other organics. Aue e_t al. (1972) used surface bonded silicones on 40 - 60 mesh Chromosorb G with methanol/benzene cleanup and pentane elution to recover ppt, levels of pesticides and PCB's. Recoveries varied from about 30% for lindane to 100% for aldrin in column tests. Ion exchange resins (Burnison, 1972) and chelo-trophic resins (Siegl and Degens, 1966; Webb and Wood, 1966) have been used for the recovery of amino acids from natural water. Freeze Concentration and Lyophilization Freeze concentration (Baker, 1965; Kobayashi and Lee, 1964) involves slowly J freezing '.the solution from bottom to top from the outside inwards.iand then separating the pure ice from the concentrate. Lyophilization involves freezing the sample and subliming the water. It has the advantage of leaving the non-volatile material as an anhydrous powder. Both these techniques involve removing the water from the organic material and are quite slow. Samples of more than two litres are difficult to handle. Hunter and Heukelekian (1965), Painter (1971), Katz et al. (1972) and Jolley (1973) have all used one or both of these techniques for studies on sewage. Air Stripping and Headspace Analysis Novak et al. (1973) originally applied this technique to the analysis of drinking water. They used He as a stripping gas and a liquid nitrogen trap for collection. Kaiser (1973, 1974) used tubes packed with GC column material followed by elution by N^ and got recoveries of 25 percent. Zlatkis et al. (1973a) tested Poropak P, Carbosieve and Tenax GC as trapping materials. They also heated the aqueous solution -45 to 100°C for better recoveries. Bellar and Lichtenberg (1974). tested the use of a number of adsorbents and found Tenax GC and Chromosorb 103 useful. Grob and Grob (1974) analyzed concentrations as low as 1 ng/l of individual pet--roleum components in water using 1 mg of charcoal and five 1.5^1 portions of CS2 for elution. Bellar, Lichtenberg and Kroner (1974) also used stripping to analyze for chlorinated solvents in drinking water and report that for components with boiling points less than 150°C and 500 mg of sample, detection limits are AJ 1/bg/l. Concentration The recommended method for concentration of organics in organic solvents is the use of Kuderna - Danish (K-D)cconcentrator (Leithe, 1973). Webb (1973) reports 85% recovery of compounds concentrated from 100 to 1 ml in CHCl^ in a rotary evaporator compared to 90% in a K-D concentrator. He also recommends the airstream method for volumes less than 0.25 ml. When working with solvents such as chloroform or diethyl ether which dissolve in water, drying is necessary before concentration. Sodium sulphate is the usual drying agent. It should be heated to 600°C for 2 hr before use, to remove organic impurities (Garrison, 1972). Losses of about 6' percent ofoc-terpinol and 2-methyl napthalene occurred from CHCl^ solutions due to drying with sodium sulphate (Webb, 1973). 3. Separation Two general problems of separation occur when working with natural waters. The first is the physical separation of the particulate matter from the sol uble compounds and the second is the separation of the components of the or ganic extracts or residues. The first problem is usually solved by filtration or centrifugation as exemplified by the studies of Hunter and Heukelekian (1965) and Painter (1971). The usual definition of dissolved organics is those of size less than 0.1 - l.OyU. Typical glass fibre filters have pore sizes, of 0.3 - 1.0^. The cellulose acetate membrane filters are available from 0.2^pore size. Fil tration times of 24 hr/1 for moderately polluted waters are common for 0.45/t filters (Andelman and Caruso, 1971). The separation of organic extracts and residues is generally accomplished by chromatographic methods. Acid-base separations using the H^SO^/HCCr^NaOH system are commonly used prior to chromatographic separation. Chromatography For a comprehensive treatment of the subject of chroma tography, the reader is referred to the volume by Heftmann (1967). This dis cussion will be limited to some examples of applications of, or new develop ments in, the various types of chromatography used in the environmental field. For a review of the chromatographic separations of some environmentally im portant chemicals, the volumes by Fishbein (1972a, 1973a)are recommended. Thfn Layer 'Thin layer chromatography has been used as a cleanup procedure in pesticide analysis before quantification by GLC (EPA, 1971). This type of application typifies the use of TLC in environmental work. In a number of cases, however, TLC has advantages over GLC and LC and is in some instances, the optimum separation method. The determination of the optimum conditions for resolution of a mixture of unknowns can be accomplished in a much shorter time for TLC than for GC and LC. The results of TLC sep arations can be used as a guide for the application of other chromatographic methods, especially LSC (Hurtubise et al., 1973). In air pollution work, arenes have been separated, identified, and quantified by TLC in combination with direct spectofluorimetry, UV absorption spectrophotometry, and colour reactions on the TLC plate (Sawicki and Sawicki, 1972). Detection limits are about l/i g by UV and 1 to 10 ng by fluorescence. Majer et al. (1970) des cribes the use of TLC - Mass Spectrophotometry for arene analysis and reports -11 -14 detection limits of 1 x 10 g for anthracene and 1 x g for benzopyrene When working with mixtures rendered less complex by prior separation and chem ical workup, characterization of the components by infrared or NMR methods is much more expedient following separation by TLC than GLC or LC, An example of this is: the work hy Hall (19JQX on the determination of sjjme of the al kaline CuO and Na/Hg degradation products of naturally occurring coloured organics. Some of the problems with these techniques such as photo-oxidation, wet spots and charge transfer spectra among others are discussed in Sawicki's review. The problem of reproducibility of values has been reviewed by de Zeeuw (1972), while the impurities in silica gel have been discussed by Spitz (1969) and Amos (1970). l£4q:iwiid! 6feoma:tQei;trap'feyr^Although florisil column clean-up techniques are routinely employed in pesticide analysis, high speed and high pressure LC methods will be emphasized in this review. An excellent summary of the principles, techniques, instrumentation and applications of LC is provided in the volume edited by Kirkland (1971). To date silica is a favourite material for LSC although, other materials such alumina, charcoal and florisil are also used. Florisil has a tendency to irreversibly bond even some non-polar compounds and thus is not usually used for the analysis of a mixture of unknowns. Good reproducibility can be obtained through the use of commercially prepared supports and a solvent of non-varying composition but gradient elution is hampered by the problems associated with maintaining a constant or reproducible level of deactivating water on the support. Some applications of LSC in the environmental field include the work on organophosphate larvicides (Henry et al., 1971), nitrotoluenes in munition wastes (Walsh et al'., 1973), phenols (Bhatia, 1973), aromatic hydrocarbons (Zsolnay, 1973), total hydro carbons (Zsolnay, 1974) and non-ionic alkylphenol surfactants (Krejci et al., 1974). High pressure IEC still suffers from retention times as long as 40 hr for the analysis of unknowns. Examples of the use of high pressure IEC include the separation of 100 120 UV absorbing peaks in human urine (Scott et al., 48 1970) and 77 absorbing peaks in municipal wastewater after 500 fold concen tration by vacuum distillation and freeze drying (Katz et al., 1972). Jolley (1973) used essentially the same system as Scott e_t al. (1970) and Katz et al. (1972) in his study on the effects of chlorination on sewage. Detection limits by UV require concentrations in the range of 40 mg/1 for unsaturated non-aromatics and 20^g/l for aromatics. Thus 40^<yg/l of non-aromatic and 20 ng/1 of aromatic unsaturated hydrocarbons can be detected through concentration techniques. Refractive Index detectors are usually one or two orders of magnitude less sensitive. A fluorescence detector based upon the uncatalyzed reduction of Ce (IV) to Ce (III) was developed and tested by Katz and Pitt (1972). Detection limits for organic acids and other reducing com pounds range from O.ljig to 0.5^g using this technique. Gel Permeation Chromatography~Although the development of semi-rigid polystyrene and polyvinylacetate gels has made high speed GPC possible, envir onmental application of GPC has been limited to the soft and, in most cases, dextran gels. The use of Sephadex gels for the molecular size fractionation of organics, mainly humic acids, in natural waters has been reviewed by Hall (1970) and Christman and Minear (1971). The GPC studies of sewage and treat ment plant effluents has been previously discussed. Gas Chromatography^This discussion will be limited to a few applications of GLC separation of organics in environmental samples. Direct coupling to a mass spectrometer will be discussed in a separate section. The selection of a stationary phase and packing is a problem encountered by everyone working with GLC. A wide variety of stationary phases has been used in environmental work Fishbein (1972a,1973a). The trend in pesticide analysis today is toward the use of the OV or SP series of silicones as the variation in composition between different lots of these phases is smaller 49 than the older silicone phases (Trash, 1973; Coleman, 1973). The favourite support in environmental analysis is silanized Chromosorb W. The graphitized carbons (Carbopak) deactivated by hydrogen treatment and coating with around 0.3% of a liquid phase show promise in the direct analysis of aqueous solutions (Supina, 1974). Both polar and non-polar phases have been used in the analy sis of volatile organics in sewage. Dowty and Laseter (1975b) used a mixture of 10% GE SF - 96 and 1% Igepal CO whereas Glaze et al^ (1973) used 5% Carbo-wax 20 M/TPA. Open tubular columns are finding increasing utilization in environmental work (Grob and Grob, 1974; Rogers and Mahood, 1974; Lao et al., 1973). The use of SCOT and WCOT columns is discussed by Ettre (1973). The traditional open tubular columns were made of stainless steel due to the difficulty of evenly coating glass. This difficulty was overcome by German and Horning (1973) and the less active glass columns are now in common use. Theoretically, one expects better resolution in a shorter time with a SCOT column as compared to a packed column (Ettre, 1973), however in the study by Lao et al., (1973) fewer peaks were observed with the SCOT column than with the packed column, especially when materials with high retention times are separated. The reasons for this difference have not been determined. One disadvantage of the SCOT column is that only a few tenths of a microlitre of sample may be injected. This means that greater concentration of samples may be required. The most common detectors used for environmental samples are the FID, EC and specific element detectors. The FID is sensitive to most organics and roughly speaking traces of FID response are similar to those of the total ion current produced by coupled GC/EIMS units in terms of sensitivity. The electron captive detector is used for organochlorine pesticide and PCB analysis due to its high sensitivity for electron capturing elements. Karasek et al. (1973) have conducted some studies on the mechanism of electron capture by a 50 series of chlorinated benzenes and biphenyls. They demonstrated that both 63 associative and dissociative electron capture occur. The Ni foil detector is favoured for environmental samples due to its high temperature stability. The problem of the narrow, one decade, linear range of the detector has been overcome through the use of constant current, variable pulsing rate elec tronics. Linearity over four decades has been obtained (Aue and Kapila, 1973). Their publication also discussed some aspects of temperature programmed GC with an EC detector. Essentially quantitation is difficult unless the det ector is operated under conditions where only the mass of the compound is important as opposed to the concentration ratio of electrons to compound. Among the specific element detectors, .thermicroelectrolytic conductivity (MEC) type is the most generally used for halogen detection. The original MEC detector was developed by Coulson (1965). Recent developments by Hall (1974) afford 20 to 50 times greater sensitivity for chlorine due to changes in reaction tube and cell geometry, use of isopropanol/water rather, than water as the circulating solvent and use of an AC rather than DCtbridge circuit for measurement of conductivity. Detection limits of 0.05 - 0.1 ng are reported for organochloride pesticides. Tests by Wilson and Cochrane (1975) revealed only a 4 to 7 fold increase in sensitivity to nitrogen over the Coulson de tector. The recently developed multi-element helium plasma/atomic emission detector offers interesting possibilities and has detection limits of 0.08 ng/sec for carbon, 0.03 ng/sec for hydrogen and 0.06 ng/sec for chlorine (McLean et.ai., 1973). 4. Chemical Analysis This discussion will be limited to a review of the instrumental tech niques of analysis which can be used either after trapping of the separated components from a chromatograph or in some cases by direct coupling or inter facing to the chromatograph. Trapping Techniques Trapping LC effluents is rather facile and will not be discussed. The trapping of GLC effluents, is much more complex. Howlett and Welti (1966), Fowlis and Welti (1967), Milazzo et al. (1968), Armitage . (1969) and Oertel and Myhre (1972) describe cryogenic trapping techniques for IR, NMR and Raman analysis. Losses due to mist or aerosol formation are common Copier and Van der Mass (1967) and Block and Griffiths (1973) used KBr as an absorbent for IR analysis. The GC-trapping-IR methodology has been reviewed by McNiven (1965), and Leathard and Shurlock (1970). It should be kept in mind that one requires 10 - lOO^zg of sample for ordinate expanded IR and capillary tube-time averaged or Fourier Transform NMR. Tandem GC-MS A general overview of GC/MS/computer systems is presented by Karasek (19-7 2) and the available instrumentation and some applications are reviewed by Junk (1972). Identification limits with these instruments vary from 20 - 100 ng. To date, all of the work in the environmental field has been carried out on electron impact sources although preliminary GC-CIMS and GC-FIMS work is reported (Junk, 1972; Blum and Richter, 1974). Environmental samples of organics usually contain a large number of volatile compounds. In the case of incomplete separation of these components or when one is interested in identifying more than one or two of the components computerized data handling facilities are essential. Data handling is a tech nology in its own right and magnetic discs offer a considerable time saving over the tape units during data manipulation (Ward 1972). Hites and Biemann in a series of papers discussed the algorithms and mechanics for the produc tion of reconstructed gas chromatograms (1968a), mass chromatograms or limit ed mass searches (1970) , and background subtraction (1968b). The US EPA has a battery of 23 GC/MS units each equipped with a mini-computer, disk or tape unit, slow.printer and keyboard, slow plotter, CRT with keyboard, CRT hard copy unit and telephone connection to large computer (Heller, McGuire and 52 •Budde, 1975). The identification of an unknown from its mass spectrum is not always a simple task. Various file searching routines have been developed. These can be classified into two groups: a) those programs developed for the in terpretation of the mass spectrum of a new or non-filed compound and b) the identification of an unknown by searching a file for its mass spectrum finger print. The first group of programs was reviewed by Kwok et al., (1973). These are designed primarily for complex polyfunctional compounds of molecular weight greater than 150. While the complete determination of structure by these programs is far from unequivocal, they do provide valuable information as to what functional groupings are present. Work with high resolution spectra, e.g. Venkataraghavan et al., (1969) will not be discussed as one does not generally obtain high resolution spectra by GC - MS due to limit ations of computer storage'space. The programs used to identify an unknown by searching a fingerprint file have been discussed by Hertz, Hites and Biemann (1971). An international mass spectral search system (MSSS) is available and is being constantly up graded. The unknown spectrum is abbreviated by choosing the two most intense peaks in each 14 m/e region beginning from m/e 6 since abbreviation to the five or eight most intense peaks will in many cases result in the loss of too much information. The output consists of a list of best fit compounds and similarity indicies. Filed spectra may also be retrieved by molecular weight or formula, (Heller, 1972). A full list of the options currently available is included in the article by Heller, McGuire and Budde (1975). Although small computer banks have been developed (Wangen et al., 1971) their use is limited. When the spectrum of the unknown contains the spectra of more than one com pound, difficulties arise. Abrahamson (1975) has developed a reverse search program where each spectrum in the reference file is compared to the un-53 known's spectrum. The use of this technique with large libraries will ob viously require some prescreening. In summary GC-MS-Computer instrumentation has become very sophisticated. It must be noted however, that the identification afforded by the MS-Computer is only tentative especially when the molecule is complex and/or has stereo isomers. The possibility of alteration in the GC or interface is always present. Since one may not be able to employ IR and NMR methods due to sample size, chemical workup and subsequent further analysis by GC-MS-Computer, or GC retention time, may be necessary to afford positive identification. Numerous examples of the use of GC/MS/Computer techniques for environ mental samples have already been mentioned. Other studies include those of Hites and Biemann (1972), Hites (1973), Keith (1969, 1972 ), Harris Budde and Eichelberger (1974) and McGuire et al. (1973). 54 CHAPTER III - EXPERIMENTAL A. Outline of the Problems A flow chart of the project is shown in Figure 3.1 and its major facets are summarized below. Extraction - The first problem was to devise an expedient method of recovering trace organics from water. Two systems, a continuous solvent extractor and an adsorption method were developed and tested. Separation -Various methods for the separation of organics were tried. These included filtration, solubility, and liquid, thin layer, and gas chromatograp hic techniques. Effects of Chlorination oh Sewage - These effects were ultimately analyzed by gas chromatography, utilizing electron capture, flame ionization, microelectro-lytic conductivity and mass spectrometric detectors. Identification of Compounds in Sewage- This portion of the work was essentially coincidental with the study of the effects of chlorination. B. Ai ^Apparatus and Techniques 1. General Procedures Those techniques which were routinely used in all facets of this project are described below, while the others will be presented in the appropriate subsequent sections. All organic solvents were of analytical reagent (AR) grade and were glass distilled with at least a 1:1 reflux ratio. Sodium sulphate (AR) and sodium chloride (AR) were heated to 600°C for four hours to remove organics while aqueous reagents were extracted with three twenty ml portions of diethyl ether. Plastic and porcelain vessels and the five gallon glass carboys were cleaned by a detergent wash followed by rinses with dis tilled water and the aqueous sample. All other glassware was cleaned by a detergent wash followed by chromic acid treatment and rinses with distilled water, methanol, acetone and diethyl ether. 55 Primary effluent * Solvent extractor 4 comparison Model compounds 1 Primary effluent XAD resin I Model compounds XAD resin y Breakthrough study Silica gel column Acidity separation GC optimization column & temperature program TLC of acidity fraction TOC study V Selection of Clg levels Estimation of Cl2 Uptake Effects of Cl2 by FID, EC & MEC GC Trapping of GC effluent Retention times of test compounds i GC-MS MS -12 F- 3000 -H GC retention time Mass Spectrum Partial ID Authentic sample of compound Positive ID Figure 3.1 Flowchart of the Project. 56 Prior to extraction, primary effluent samples were filtered with the apparatus shown in Figure;3.3a. Filters of paper (Whatman 541) and glass fibre (Reeve Angel 934) were layered three of each deep in the 11.5 cm l.D. porcelain crucible and sealed by distilled water. They were sequentially removed when the filtration rate dropped below 300 ml/min during vacuum filtra tion at 10 inches water gauge into the five gallon glass carboys. All organic extracts were dried with sodium sulphate and concentrated to 0.5-2.0 ml in a rotary evaporator (Buehler) at 20°C. The concentrated extracts were analyzed on a Hewlett-Packard 5750 GC with a Ni EC or H2/air FI detector. The det ector temperature was 320°C and injector temperature was 260-280°C. Carrier gases were 95/5 Argoni methane for EC and helium for FID. Detector responses of 50 percent of full scale were produced by 1 x 10 g of dieldrin with the —8 EC (50 s pulse interval) and 5 x 10~ g of "isS-octane" with the FID at 1 i 11 attenuations of 32.x 10. All columns were 4'" x y glass fitted with silicone rubber, Supeltex M-l, or lead ©wrings and ferrules (Suprelco). The 5 and 10 yUl GC syringes (Hamilton) were cleaned by aspiration of 5 ml of acetone through the barrel and wiping of the plunger. Chlorination of primary effluent samples involved the use of NaOCl solu tion (Fisher) which was analyzed prior to use by iodometric titation (APHA, 1971). Residual chlorine was determined by the Phenylarsine oxide-Iodine method &APHA>ji X9.7/BX) and a 5 percent excess of solid ^a^S^O^ (Fisher) was added to dechlorinate the sample and control reaction time. All primary effluent sam ples were stirred with a plastic overhead drive propellor to ensure complete mixing in the glass carboy. 2. Sampling and Preservation Sampling Location Lion's Gate Sewage Treatment Plant in North Vancouver was selected as a source of effluent. The plant serves a population (1973) of 108,000 with an average flow of 11.0 MGD of mainly domestic sewage. It provides treatment via primary sedimentation, anaerobic sludge digestion, and effluent chlorination. Supernatant from the digestors is intermittently recycled through the plant. Prechlorination was not practiced during the period of this study. The average composition of the effluent is B0D5 - 100 mg/1, NH -N - 15 mg/1, TK-N - 30 mg/1 and pH 7.2. The average daily chlorine dosage varies seasonally from 7 to 15 mg/1 with a residual of between 2.0 and 5.0 mg/1 as measured by amperometric titration. Sampling and Pretreatment Unchlorinated effluent samples were obtained from the outfall weir of the primary settling tanks. On one occasion a sample of chlorinated effluent was taken from the outfall of the chlorination chamber. Single grab samples were taken between 1000 hr and 1200 hr on Mondays. They were collected in five gallon Nalgene carboys. Work with these samples was commenced within one hour in most cases. Therefore the initial practice of adding 30 mg/1 of sodium azide was discontinued after the second set of samples and subsequently no preservative was added. 3.p Design and Test of Extraction Methods a. Solvent Extractor Apparatus - During preliminary tests of the initial extractor with sewage it was noted that some water overflowed into the solvent chamber, thus the design was modified. The modifications essentially made the flow of water through the extractor unrestricted in a direction opposite to the flow of the solvent. The final extraction system is illustrated in Figure 3.2. It was designed for use with a lighter than water solvent. The solvent, petroleum ether bp 37-47° C is continuously distilled and channeled to the bottom of the extractor flasks. There it is finely dispersed with a Teflon coated magnetic stirring bar. The solvent then rises and overflows back to the distillation chamber. The rate 00 Figure 3.2 Continuous Solvent Extractor 59 of flow of the water sample was controlled by the Teflon valve. Solvent Extraction of Model Compounds (Exp E-l) - In order to test the extrac tor under ideal conditions, two model compounds, 2,4-Dichlorophenol (DCP) and 2,4,6-Trichlorophenol (TCP) (Eastman) were selected. Aqueous solutions of these compounds were prepared by dissolving them in two millilitres of acetone and one litre of distilled water with magnetic stirring overnight, followed by final dilution, to eighteen litres. The solutions were passed through the extractor at flow rates of ten and one hundred ml/min with high and low stirrer speeds. At high stirrer speed the organic solvent was completely emulsified and at low sitrrer speed the solvent was dispersed in discrete droplets. The organic extracts were divided in half, concentrated, diluted to the linear range and analyzed by GC (Hewlett Packard 5750) on 5% DC-11 on Chromosorb W (HP), with an EC detector. Peak areas were measured with a Disc Integrator. Distilled water was run through the extractor between tests without cleaning the tygon tubing and an estimate of memory effects made. After cleanup of the Tygon tubing with detergent and water another blank was run. Solvent Extraction of Primary Effluent (Exp E-2) - In order to further test the performance of the extractor, tests were run with filtered and unfiltered sewage at a flow rate of 100 ml/min and low stirrer speed. Filtered sewage was also extracted at low stirrer speed and 10 ml/min flow rate. Extracts were concentrated to 2 ml and analyzed by GC on 5% DC-11 on Chromosorb W (HP) with an electron capture detector. ib,,. Extraction with XAD-2 Resin Apparatus - Due to problems with the solvent extractor a new method of ex traction was necessary. A styrene-divinyl'benzene macroreticular resin, Am-berlite XAD-2 (Rohm and Haas) was tested. Resin cleanup was accomplished 60 by three washings with distilled water• and decanting-of the .finest- followed by successive Soxhlet extractions with methanol for ten hours, acetone for twenty-four hours, and diethyl-ether for twenty-four hours. The clean resin was then stored as a methanol slurry until it was used. The extraction apparatus is illustrated in Figure 3.3. The resin, as a methanol slurry, was packed into eighteen by one inch glass columns or one hundred millilitre burets to a vol ume of 80 ml. Before extraction of a sample the column was washed with five litres of distilled water to remove the methanol. Desorption was originally accomplished by elution with 200 ml of acetone and drying of the acetone water eluant mixture with sodium sulphate. Extractions of the eluant mixture with petroleum ether and diethyl ether were also tried*. The method finally adopted was elution with 200 mis of diethyl ether. The ether was allowed to run through the ic.o?lumn until two layers were observed in the receiving flask. The flow was stopped for fifteen minutes to allow for complete permeation and then allowed to proceed at 3 - 4 ml/minute. The eluant was dried with sodium sulphate and concentrated. The columns were then washed with 200 ml of acetone and 100 ml of methanol for complete cleanup. XAD-2 Extraction of Model Compounds (Exp.. E-3) - This experiment was run in four parts in order to measure recoveries and determine the sources of losses in the system. The phenols were analyzed by GC-EC detector. The recovery of DCP and TCP from distilled water solutions was tested at neutral pH (Exp. 13a)3a). The effect of detergent on recovery was determined by adding 4.9 mg/1 of LAS standard solution (R. A. Taft, Cincinnati, Ohio) to the aqueous phenol solutions (Exp. E-3b). One fraction was acidified with U^SO^ to pH 1.8 and two litre portions of both fractions were extracted. LAS was analyzed by the Methylene Blue method (APHA 1971). A detailed breakdown of losses in the system was made using distilled 62 water and the chlorophenols (Exp. E3-c). Recoveries and losses at various stages were determined by solvent extraction or sorption. Solvent extraction entailed three ten ml extractions with pet ether after acidification to pH 2 and addition of 20 g/1 of NaCI. Experiment E-3-d was identical to E-3-c except that raw sewage was used in place of distilled water. The solution of DCP was prepared by dissolving the phenol in acetone and water as before. This solution was then added to three or four litres of sewage. Breakthrough Study (Exp E-4). To determine the capacities of the columns eighteen litre portions of filtered primary effluent, at both neutral and acid pH's, were extracted at a flow fhrough rate of 100 ml/min. Column effluent samples were filtered (0.45^ membranes) and analyzed for soluble TOC (Beck-man 915 carbon analyzer). 6. Comparison of XAD-2 and Solvent Extractor -(Exp E-5.') In order to compare the extraction efficiencies of the XAD columns and the solvent extractor, three five gallon aliquots of primary effluent were obtained. One aliquot was dosed with 106 mg/1 Cl^ for one hour. All three aliquots were filtered and the filters from each aliquot were collected damp but without free moisture. One aliquot of the unchlorinated effluent was extracted in the solvent extractor at 100 ml/minute and low stirrer speed. The other aliquots of filtered chlorinated and unchlorinated effluent were extracted by columns of XAD-2 resin. All three organic extracts were concen trated to 5 mis and analyzed by GC. ;d. Extraction of Particulates-(Exp E-6) - The filter pads were cut up into 1" x 2" strips and placed in pre-extracted cellulose Soxhlet Thimbles. Filters from the chlorinated sample were extracted with a 1:1:3 mixture of methanol, acetone and n-hexane. Filters from the unchlorinated samples were extracted with methanol and a 1:1 mixture of chloroform and methanol to determine whe ther or not free chlorine in chloroform is a significant interference. Three 63 porcelain boiling chips (Hengar) were added to the distillation chamber and the extractors were operated at 20 - 25 minutes per cycle for 26 hours. All extracts were dried and concentrated to 5 ml. The pure methanol and chloro-form/methanol extracts were further concentrated to 0.5 ml and rediluted to 5 ml with acetone. The extracts were then analyzed by GC. 4. Separation Experiments a. Preliminary Separation (Exp S-l) Preliminary separation of the organics by silica gel chromatography and acid-base solubility was attempted prior to gas chromatography. Silica Gel Chromatography (Exp S-la) - Silica gel (Fisher Grade 923, 100-200 mesh) was heated at 260°C for five hours and then 5% by weight of water was added in a glass stoppered round bottom flask. The silica gel was gently tumbled until free flowing and allowed to further equilibriate overnight. Glass columns (0.3 by 40 cm) were prepared from soft glass tubing. The col umns were constricted near the bottom and a 2 cm plug of glass wool inserted. The columns were rinsed wi'th methanol, benzene, and pet ether and then filled with pet ether. The silica gel was slurried in pet ether and the flask con taining the slurry was partially evacuated to remove air bubbles. The slurry was then added to the column to a depth of 15 cm. A 0.5 ml aliquot of sample from Exp. E-5 was placed on the column and eluted with 8 ml of pet ether, 8 ml of benzene and 8 ml of 1:1 methanol/benzene (v/v). Acidity Separations (Exp S-l-b) - Four five gallon aliquots of effluent were obtained and chlorinated at levels of 0.0, 15, 100 and 200 mg/1 Cl^ for one hour. They were extracted by XAD-2. The diethyl ether eluant was suc cessively extracted with 3 x 10 ml of 0.1 ,:M NaHC03> and 3 x 10 ml of 0.01 M NaOH to separate strong acids, weak acids and neutral compounds. The aqueous solutionsvwere acidified to pH 2 with aqueous H^SO^ and re-extracted with di ethyl ether after the addition of NaCl. A total operations blank consisting of distilled water and sodium thiosulphate, and a sample of NaOCl/Na9S 0 64 were also analyzed. After concentration to 1 ml, the extracts were stored at -10°C in 2 ml glass stoppered volumetric flasks (Kimax). Subsequently, the bicarbonate extraction step was omitted and 0.05' M NaOH was used, b. GC Optimization (EXp. S-2) An attempt was made to determine the optimum packing and conditions for GC separation. The GC work was performed on a Hewlett Packard 5750 instrum ent with EC and FID detectors. Four column packings were tested. Packings of 3% 0V-1 and of 3% 0V-225 on Chromosorb W (HP) were obtained from Pierce Chem icals. Packings of 3% OV-101 and of 3% 0V-17 on Chromosorb W(HP) 80-100 mesh (Chromatographic Specialities) were prepared by the solution-filtration method (Supina, 1974). The packings were dried at 50°C for twenty minutes before filling the columns with 7.0-7.5 g of material. Packed columns were conditioned by a temperature program of 30° for 20 minutes, a 1° /minute increase, followed by an isothermal period of two days at the maximum temperature. Helium gas and lead ferrules were used during conditioning. i Samples from Exp. S-l-b were analyzed on all four columns using both FID and EC detectors under various temperature programs. The detector res ponses were optimized for the initial of final conditions of the temperature program. c. TLC of Acidity Separated Fractions (Exp S-3) Im an attempt to accomplish more complete preliminary separation of the effluent samples, the neutral and basic fractions of the samples chlorinated at 0 and 120 mg/1 Cl from Exp. Cl-7 were separated by TLC. A preliminary test of the developers was made on commercially prepared plates (Eastman) while final separation was made on plates prepared as follows. Silica gel (Kieselgel) was extracted for 24 hours in.a Soxhlet extractor with methanol. It was oven dried until free flowing and 5% by weight GaSO^ (Fisher AR) was added. Glass TLC plates were washed with detergent and rinsed with water and acetone. Silica gel was applied as an aqueous slurry and the coated plates were oven dried at 103°C for 24.hours and stored over CaSO^ in a dessicator prior to use. Samples were applied as a streak. The plates were developed with pet ether and arbitrarily divided into four or eight fractions. Re covery of the material from the plates was accomplished by the technique devised by Hall (1970) except that the asbestos was omitted. The recovered material was monitored by EC-GC. The fractions showing EC responses were recombined and reseparated by TLC using methanol as a developer. After div ision of the plate and recovery of the material, the fraction showing EC response was then concentrated to 0.1 ml and analyzed by GC-MS. A worst possible blank was obtained from non-soxhlet extracted silica gel and the ' "clean" areas of the second TLC plate which corresponded to the same R^ val ues as the fraction analyzed by GC-MS. 5. Effects of Chlorination a. Mangesiin Soluble TOC Upon Chlorination -(Exp Cl-1) Three fresh effluent samples were chlorinated at levels of 0, 12 and 103 mg/1 C^. The samples were filtered (0.45^membrane) and the TOC of the samples determined on a Beckmann 915 TOC analyzer. b. Effects Detectable by GC with EC and FI Detectors (Exp Cl-2) Extracts were analyzed by GC with EC and FID detectors to determine if changes occur as a result of chlorination and to determine whether changes (Occur.bingaatbhitghilevelsjofclGhlofinatlon'- also"? occurredj&at the levels of chlor ination used in the treatment plants. Experimental conditions used in these experiments were identical to those in Experiment S-2. c. Effects Monitored by MEC Detector and GC Correlations (Exp. Cl-3). Samples were analyzed on a Micro-Tek (Tracor 222) GC equipped with a Tracor 310 detector operating on the Cl mode at 815°C and a 6' x 1/8" glass column containing the packing as used with the GCrMS (Exp Cl-7). The resp onse of the detector was calibrated with a standard mixture of pesticides. 66 An attempt was made to correlate the GC chromatograms from the GC-MS, Microtek GC, and Hewlett-Packard GC. Samples were analyzed on the Hewlett Packard with a 4' x h" glass column of the•packing used with the other in struments. The individual optimum temperature programs were retained for each GC. Three compounds, o-chlorophenol, p-chlorophenol and o,p' - DDT were used as markers. d. GC-MS Studies on the MS 12 (Exp Cl-4) The extracts from experiment Cl-2 were initially used in this experiment. A second set of samples was prepared by extracting, acidity separating and concentrating effluent chlorinated at 0 and 25 mg/1 Cl^. In this second experiment ten gallon aliquots of effluent samples were analyzed by combin ing the extracts of two XAD-2 columns. The GC-MS is a combination of a Pye 104 GC and a Micromass 12 single focussing mass spectrometer interfaced by a differentially pumped porous frdtf-^type separator. Glass columns (1 m x 2 mm OD) with stainless steel Swagelock fittings were packed with the OV-101 and 0V-225 packings previous ly described. Electron energies of 70 and 25 eV were used. They were scanned at a rate of 3 sec/400 amu and recorded on UV chart paper. Low boiling perfluorokerosene was used as a calibrant. Mass spectra were taken at the beginning, maximum and tail of each peak which appeared on the GC. e. Tentative Identification by Retention Time (Exp Cl-5) To tentatively identify some of the organic compounds formed as a result of chlorination, the GC retention times of a number of recrystallized chlor inated compounds were determined under conditions used to analyze the samples of chlorinated effluent. Retention times of composite solutions and individ ual components were determined at 120 and 160°C and .with the temperature programs used for the primary extracts. £. Trapping of GC Peaks (Exp. Cl-6) An attempt was made to trap a specific peak and analyze it by direct probe MS. A new set of samples was chlorinated at 0, 12 and 100 mg/1 of Cl^. A 30:1 stainless steel effluent splitter was installed in the Hewlett Packard GC operating on the EC detector mode. Capillary glass tubes were rinsed with methylene chloride and dried. Attempts were made to trap one specific peak with an air cooled tube, a tube packed with one cm of Tenax GC, and a tube packed with one cm of the 0V-225 material. Eight 3^#1 injections of the neu tral and basic fraction of the sample chlorinated at 100 mg/1 were made with each trapping system. The tubes were handled only with forceps and eluted with 100/^1 of diethyl ether which was allowed to evaporate in the atmosphere down to a volume of 2^1. No peak was discernable upon reinjecting this l/ll aliquot into the GC. g. GC-MS-Computer (Exp Cl-7) A new set of samples was chlorinated at 0, 12 and 120 mg/1 01^, and a sample of plant chlorinated effluent was obtained. A blank of 35 1 of dis tilled water and thiosulphate was run through the collection and extraction systems. The concentrated extracts were analyzed on the Hewlett Packard 5750 by EC and FID on OV-101 and 0V-225. The samples were cooled with dry ice and transported by car to the USEPA lab in Seattle where they were stored in a freezer. The GC-MS-Computer was a Finnigan 3000 consisting of a Finnigan 9500 GC and a Finnigan 3100 D MS interfaced by a jet separator. Auxiliary equipment included a Systems Industry PDP8 computer with magnetic disc and Dec Tape, transfer unit, teleprinter and Houston Instruments slow plotter, Tektronix CRT display/control console with a hard copy unit, and a telephone hookup device. Samples were separated on a 4' x 1/8" glass column containing 6% SE-30/4% OV-210 on Gas Chrom Q. Spectra were obtained at 70 eV ionizing vol tage and scanned at 1 sample /.-amu, integration time of 8, over the mass range 34-450. Numerous limited mass searches were conducted to attempt to locate peaks of interest. Ultimately, each spectrum was manually inspected and appropriate background corrections made. The resultant spectra were compared with the MSSS files or the AWRE••*' = .Aldermaston (1974) and Cornu and Massot (1975) eight peak indices. In addition, spectra not matching those in the file were interpreted by the methods outlined by McLafferty (1973). The/tentatively identified spectra were then compared with those collected by Stenhagen et al..(1974). ^Authentic samples of the compounds whose spec-traa passed these tests were obtained when possible and their GC retention times and mass spectra were obtained on the Finnigan 3000 GC-MS. 4 69 CHAPTER IV RESULTS AND DISCUSSION In this chapter the results from each experiment described in Chapter III will be presented and discussed. In the interest of brevity all of the GC traces and mass spectra will not be reproduced. A selection of chromatograms and mass spectra chosen on the basis of positive importance will be presented while only the salient features of the others will be described. A summary of the chromatograms of effluent samples is presented in Appendix II. The GC conditions for the chromatograms presented in this chapter are described in detail in Appendix III. A. Extraction Experiments 1. Solvent Extractor The recoveries of DCP and TCP from distilled water by the solvent ex tractor (Exp. E-l) are presented in Table 4.1. A test for memory effects indicated residuals of 0.30 mg DCP and 0.35 mg TCP or about 4 percent of the total phenol passed through the Tygon tubing.> No detectable memory effects persisted after cleaning the Tygon. Loss of solvent proved to be somewhat of a problem, primarily due to the entrainment of solvent in the aqueous sample. In order to estimate the im portance of this loss, measurements were made of the solvent needed to re plenish the stock in the distillation flask and of the rate of solvent dis tillation into the extraction flasks. These results presented in Table 4.2 are accurate only to + 10% due to the difficulty of filling the distillation flask exactly, to the calibration mark. From Tables 4.1 and 4.2 it appears that poor recoveries are coupled with large solvent losses. In summary, slightly better recoveries are obtained at low flow rates. In view of the long extraction times required with low flow rates, the op timum operating conditions are a flow rate of 100 ml/minute and a low stirrer Table;4.1 - Recoveries of Phenols by Solvent Extractor Run Compound Concentration Flow Stirrer mg Passed Recovery No. mg/1 Rate "Speed Through mg/min Extractor* mg % 1 DCP 0.48 10 high 8.2 5.8 71 1 TCP 0.48 10 high 8.2 5.8 71 2 DCP 0.41 10 low 7.1 5.8 82 2 TCP 0.33 10 low 5.7 4.3 76 3 DCP 0.51 100 high 8.7 3.2 37 3 TCP 0.46 100 high 7.9 3.4 43 4 DCP 0.39 100 low 6.7 4.6 69 4 TCP 0.26 100 low 4.5 3.2 71 5 DCP 0.50 100 low 8.6 5.8 67 5 TCP 0.43 100 low 7.4 4.9 66 71 Table 4.2 - Solvent Loss Due to Entrainment Run Time of Run Stirrer Solvent Distilled Solvent Lost hrs Speed ml ml % of Solvent Distilled 1 28.5 high 20,500 650 •3.2 2, 28.5 low 20,500 300 1.7 3 3.0 high 2,160 830 38 4 3.0 low 2,160 300 14 5 •3.0 low 2,160 250 12 72 speed. When filtered sewage effluent (Exp E-2) was extracted an emulsion problem developed. At a flow rate of 100 ml/minute and low stirrer speed an emulsion with entrained brownish scum formed at the top of the extractor flask and over flowed into the distillation chamber. The boiling in the distillation chamber then became bumpy. At a reduced flow rate (10 ml/minute) the emulsion and bumping were slower to develop. Discrete bubbles with a brownish scum quickly appeared at the top of the extraction flask and after 15 hours the emulsion in the distillation flask was similar in volume to that obtained in 1 hour with a high flow rate. Examination of the gas chromatograms of the sewage extracts showed a total of 34 peaks detectable by EC. Three of these peaks appeared in.the dis tilled water blank. Although the §xt-ractor.s±sanr.ea-sona&3Jylgrf4e?fierit-,- it was decided to develop an adsorption method for extraction due to the emulsion problem. The alter-nativefssolutions of acidification of the sample to pH 1.8 and addition of 20 g/1 NaCI would probably increase sorption losses. In addition, experience has shown that such practices do not eliminate emulsions with environmental samples. 2. Extraction With XAD-2 Resin The first problems to be solved were the development of a cleanup method, and the development of an efficient method of elution. Since the resin con tains inorganic as well as unknown organic impurities, the approach described in Chapter III was devised. The purpose of the methanol extraction was to remove the water and residual inorganics from the resin. Acetone and diethyl ether were chosen because they were the solvents used for elution of the sorbed organics. The methanol extract was yellow while all of the others were col ourless. Since brittle plastics tend to crack upon drying the cleaned resin 73 was stored as a.methanol slurry. The release of'organics from cleaned resin which was allowed to dry has recently been confirmed by Junk et al. (1974). The eluting solvent must satisfy three requirements. It must be a good general solvent, displace water from the column and be easily removed to allow concentration of the extract. The column contains about 8 ml of water as measured by elution of the column with hexane. When the acetone eluant was dried with Na2SO^ and concentrated, about 0.3 ml of water remained. The pres ence of such a large amount of water will cause large losses of volatile organics during the concentration step. To accomplish a 3 x 10 ml extraction of the acetone - water eluant approximately 120 ml of petroleum ether and 200 ml of diethyl ether were needed. Tests on the recoveries of DCP from a 200:10 mixture of acetone and water yielded recoveries of 77% with pet ether and 64% with diethyl ether. Due to these extraction difficulties the stopped flow method of elution with diethyl ether was adopted. Comparison of the elution efficiencies of acetone and diethyl ether showed recoveries of 93% for acetone and 89% by diethyl ether. Thus the solvents were identical within the 5% error limits and no residual water was noted after drying the diethyl ether. A breakdown of the recoveries of DCP and TCP from the XAD-2 column accor ding to eluant fraction (Exp. E-3) is shown in Table 4.3. The effect of LAS detergent on recoveries of phenols from acidified and non-acidified solutions is shown in Table 4.4. A detailed breakdown of losses is shown in Table 4.5. From Table 4.3 it can be seen that the elution of sorbed phenol is es sentially complete after about 1 bed volume of diethyl ether has passed through the column. Neither the pH of the solution nor the concentrations of the phenols appear to affect the recovery. These results concur with the re cently published work of Vinson et al. (1973) and Junk et al. (1974). Detergents also had no effect uon the recoveries of the phenols. Adsorption of the LAS detergent 74 Table;4.3 Recoveries of Phenols from Distilled Water by XAD-2 Run Sample Initial mg Through Recovery No. Description Concentration Column mg % mg/1 DCP TCP DCP TCP DCP TCP DCP TCP 10. Original Solution 1.1 1.05 18.7 17.8 1 1st 50ml of Eluant \,\. 12.3 10.5 66 58 1 2nd 50 ml of Eluant 9 2.3 10 13 1 3rd 50 ml of Eluant 0.05 0.05 — 1 4th 50 ml of Eluant 0 0 2 Composite of Concentrates 15.0 13.4 80 75 2 Original Solution 0.133 0.189 2.3 3.2 2 1st 50 ml of Eluant 1.6 2.6 70 81 2 2nd 50 ml of Eluant 0.1 0.15 4 5 2 3rd 50 ml of Eluant <C0.01 <-0.01 2 4th 50 ml of Eluant <0.01 CO.01 2 Composite of Concentrates 1.80 2.65 79 83 75 Table 4.4 Effect of LAS on Recoveries of Phenols by XAD-2 Volume of Recovery Run Sample Passed pH Concentration (mg/1) percent Through Column (1) LAS DCP TCP LAS DCP TCP Original Solution 1.8 4.5a 0.55a 1.25a _— ___ 0.0 - 0.5 0.9 20 0.5 - 1.0 2.3 50 1.0 - 1.5 1.8 40 1.5 - 2.0 2.0 55 Total 1.8 0.45 1.05 40 82 84 Original Solution 7.1 4.5a 0.90a 1.35a 0.0 - 0.5 0.0 0 0.5 - 1.0 0.3 7 1.0 - 1.5 0.3 7 1.5 - 2.0 0.2 4 Total 0.4 0.70 1.10 78 82 Original Solution 1.8 0.0a 0.00a 0.00a 0.00 0.00 0.00 a - Original concentration of component asO determined by analysis or from amount of material added and volume of solution. Table 4.5 Breakdown of tosses for XAD-2 System Run Compoundratioa Concentration Loss Due to Loss Due to Loss Due to Non-in Original in Original Solution Filtration Sorption on Adsorption on Solution by weight by solvent mg/1 % Tygon XAD Resin extraction mg/1 % mg/1 % mg/1 % mg/1 mg/1 Distilled DCP O.'S'S 0.52 0.0 0 0.071 14 0.0 0 0 Water-1 TCP i.o 1.0 0.0 0 0.092 9 0.0 0 0 Distilled DCP 0.25 0.24 0.0 0 0.032 13 0.0 0 Water-2 Sewage-1 DCP 0.83 0.74 0.12 16 0.13 18 ©V03 4 Sewage-2 DCP 0.76 0.66 9.08 12 0.14 21 0.03 5 77. occurred only when the sample was acidified. Similar results were obtained by Junk et al., (1974) with volatile acids. Detergents cannot be analyzed by GC-MS and volatile acids are of no interest in this study. From Table 2.3 it can be seen that these compounds are present in high concentrations in sewage. In order to prevent premature saturation of the resin with these compounds, it was decided to extract primary effluent samples at near neutral pH's. From Tables 4.3 and 4.5 it can be, seen that the major source of loss in this method is sorption on the Tygon tubing. The losses during concentration were 7-9 precent. From Table 4.5 it is also evident that the recoveries of DCP are significantly lower when sewage rather than distilled water is extracted. Therefore the recoveries of organics from sewage are affected by sorption and/or precipitation reactions even though LAS in distilled water had no effect. The significant sorption on particulates indicates that quantification will be more difficult by sorptive extraction which required pre-filtration, than by solvent extraction where removal of particulates is unnecessary. In summary, the XAD-2 resin method appears to be slightly more efficient than the solvent extraction method for the recovery of DCP and TCP from neutral distilled water solutions. However the recoveries of DCP from sewage were about 25% lower than those from distilled water. The results of the breakthrough studies of sewage (Exp. E-4) are listed in Table 4.6 and displayed in Figure 4.1. Deviations of up to 6 mg/1 or 13 percent among the TOC values for samples which should have been identical were noted. The stated reproducibility of the instrument is about + 1 per cent while about 1 percent error is expected due to syringe measurements. The deviations are probably due to the solids in the samples. Because of these deviations no comparisons of the TOC of acidified and unacidified 78 Table 4.6 Breakthrough Study for Sewage on XAD-2 Volume Through Column (1) Total Organic Carbon in Effluent pH .2.0 (mg/1) , pH 7.2 Run 1 Run 2 Run 1 Run 2 Raw Sample 67 65 63 64 0.5 43 40 40 1.0 45 45 43 42 2.0 48 46 45 41 2.5 43 43 41 40 3.0 43 48 44 44 4.0 45 45 46 45 5.0 51 53 47 43 6.0 50 45 45 6.5 52 7.0 67 62 56 50 8.0 62 64 55 50 9.0 68 66 54 58 10.0 66 63 60 10.3 69 11.0 65 64 60 63 12.0 66 60 13.0 70 63 65 64 14.0 71 65 64 66 15.0 65 68 62 62 17.0 68 67 66 62 18.Q 64 62 64 Composite 61 60 52 58 Figure 4.1 Recovery of Organics from Primary Effluent by XAD-2 Resin 80 effluent are justified. From the graphs in Figure 4.1 the capacity of the resin in terms of mg TOC/cc resin is 1.7 for both samples. This compares well with the results of Kennedy (1973) who showed that resin capacity can vary over an order of magnitude depending upon the polarity of the compound and quoted a capacity of 3.5-5.2 mg/cc for Vitamin B-12. There was no change in the turbidity of the samples after passage through the column. Turbidity values ranged from 20-25 JTU's as determined by the Jackson Candle (APHA 1971). The breakthrough point could be estimated visually by the movement of the yellowish brown colour down the resin column. The breakthrough volume o"f- the acidified sample appears to be smaller than that of the non-acidified sample. The breakthrough volumes are about 9 and 10 1 or 120 and 133 column volumes respectively for acidified and non-acidified samples. The shift in breakthrough volumes corresponds to an increase in recovery of. TOC upon acidification of about 4 mg/1. From Table 2.3, assuming the volatile acids are primarily acetic and the detergents dodecy1 benzene sulphonates, the volatile acids and detergents contribute 12.1 mg/1 of soluble TOC. In summary, the XAD-2 resin extracts about 30% of the TOC from filtered primary effluent and has a saturation capacity of 130 column volumes. There is some evidence that acidification of samples results in premature satura tion of the resin by volatile acids and detergents. The extraction efficiencies of the solvent extractor and the XAD-2 resin for volatiles in primary effluent were compared by analyzing the con centrates. The GC traces ane shown in Figure 4.2 The reasons for the poor quality of the chromatogram of the unchlorinated XAD-2 extract as compared to those of the solvent extract and chlorinated XAD-2 extract are not known. One likely explanation is the presence of sulphur compounds. Comparison of chromatograms (a) and (b) in Figure 4.2 indicates that the recoveries by the two techniques are very similar in terms of the concentrations of the 81 1—•— » 1 i 11 a 1 * i SO 100 150 200 250 Temp (°C) Figure 4.2 Continuous Solvent and XAD-2 Resin Extraction of Organics from Primary Effluent Monitored by GC. GC conditions in Appendix III. 82 individual components. The XAD-2 resin appears to be slightly better than solvent extraction with pet ether in terms of the number of compounds ex tracted. A cursory examination of the volatiles extractable from the particulates was made to gain some idea as to their complexity. The results of the GC investigation of the extracts are shown in Figure 4.3. The extracts contain twelve to seventeen peaks, two or three of which are extremely large. There are fewer peaks in the chlorinated sample. It must be kept in mind that different solvents were used, however the solubilization of organics through oxidation is also possible. There are also some new peaks in the CHCl^/MeOH extract as compared to the MeOH extract. Although further investigation of these extracts is obviously warranted, due to limitations on time it was decided to concentrate on the soluble fraction. B. Separation Experiments  1. Preliminary Separation GC resolution was not sufficient to adequately separate all of the com ponents of the primary effluent extract (Exp. ;E-5). It is further recognized that the sensitivity of the EC detector for chlorinated and oxygenated compounds is much greater than that of a GC-MS, thus it was decided to con centrate the extracts to 0.2-0.5 ml which would tend to increase the problems of resolution. Therefore it was decided to attempt preliminary separation of the extracts prior to GC analysis. A representative set of results from the Silica Gel column experiments (Exp.S^la) are shown in Figure 4.4. Although the background is considerably reduced, upon close inspection of these GC traces, one finds them remarkably similar. It would appear that channeling occurred in the Silica Gel columns. Furthermore, changing of the eluting solvent resulted in a dramatic change in the consistency of the gel with the result that the flow rate through the 83 / , Time(Mm) Figure A.3 Soxhlet Extracts of Particulates Analyzed by GC. GC conditions in Appendix III. 84 1 •  • ' » 1 : V ,, 50 50 «00 150 200 250 300 Te/np(°C) Figure 4.4 Silica Gel Column Fractionation of Primary Effluent Extracts Analyzed by GC. GC conditions in Appendix III. column was considerably decreased. Flow rates with MeOH/Benzehe were about 0.01 ml/min. In order to speed separation either wide columns with large volumes of eluant and decreases in resolution or some type of pressurization of the column were necessary. Only propipettes were available for the latter purpose and rather than risk the introduction of impurities,the silica gel column method was discontinued in favour of acidity separation. A representative set of GC chromatograms of the acidity separated fractions of the XAD-2 extracts are presented in Figure 4.5 (Exp-. S-lb) . Comparison of the three traces shows that the EC detectable material is al most equally divided between the neutral + basic fraction (N + B) and the weak acid fraction (WA). There were few compounds in "the strong acid fraction which is not surprising since no derivatization was carried out to make the acids volatile enough to be analyzed bj GC. There are an unexpectedly large number of peaks at the low temperature end of the WA fraction. The chromatograms on 0V-17 and 0V-225 also have this feature. This leads one to suspect incomplete separation probably due to the high solubility of diethyl ether in water. The peaks numbered 1 through 7 in Figure 4.5 are.those suspected of being present in both the WA and N + B fractions and which rightly belong in the N + B fraction. The alter native of using pet ether is not attractive since many oxygenated or polar compounds areoonly sparingly soluble in this solvent. It was therefore decided to wash future aqueous extracts with 4 x 10 ml of diethyl ether rather than with just the one 10 ml portion employed in this separation. Since many phenols are.not sufficiently acidic to be completely extracted by the bicarbonate, it was decided to discontinue the bicarbonate extraction and use only the sodium hydroxide extraction. 2. G.C. Optimization The objective of this portion of the project is to determine the best } 30 50 .100 • 150 200 Temp (°C) gure 4.5 Acidity Separation of Primary Effluent Extracts Analyzed by GC. GC conditions in Appendix III. GC phase and the optimum temperature program for separation of the volatiles in sewage (Exp. S-2). The OV series of silicones were chosen for reasons outlined in Chapter II. The basic criteria to>be used for comparison of these phases and temperature programs are the elution of the maximum number of compounds in a reasonable time and the resolution of these compounds. Representative chromatograms tof the N + B and WA fractions of the sample chlorinated at 15 mg/1 Cl^ are shown in Figures 4.6 through 4.9. The SA fractions showed about a dozen fairly well resolved peaks by EC and FID (Figs. 4.17, 4.18). With the OV-101, OV-17 and OV-225 columns, the optimum temperature'program was 30°/10 minutes, 6°/minute, and 200°C/20 minutes for both fractions. Due to the large number of low-boiling compounds in the extracts, OV-1 was of limited use because of its lower temperature limit of 100°C. The other phases provide good separation of the N + B fraction (Figures 4.6 and 4.8) at low temperatures, however all of them have some resolution problems above 100°C. Comparison of the WA fraction on the various phases (Figures 4.7 and 4.9) shows that fewer peaks are observed with the OV-225 phase than with OV-101 or OV-17. This is probably due to the high polarity of the OV-225 phase. No memory effects were observed during these analyses. 3. TLC Separation of Acidity Fractions The main objective of this work was to further separate the acidity fractions so that each peak observable in the GC-MS consisted of only one compound. A sample set of chromatograms as monitored by GC with an EC detector are presented in Figures 4.3-0 and;4^11. A "worst possible" blank and EC trace of the sample before TLC are included in these figures. It is evident that most of the more volatile compounds are lost during TLC manipulations. With pet ether as the developer one can see from Figure 4.10 that most of 30 "~30 50 ~~~ foO 150 200 ^ (100) (100) (150) (200) (250) Temp (°C) OV-I in porentheses Figure 4.6 GC Optimization N + B by EC. GC conditions in Appendix III. (c) 0V-225 30 30 100 Temp (• C) Figure 4.7 GC Optimization WA by EC. GC conditions in Appendix III, •fer Figure 4.8 GC Optimization N + B by FID. GC conditions in Appendix III. the recoverable EC detectable material has an of less than 0.25. This fraction was rechromatographed with methanol as a developer. In this second chromatogram (Figure 4.11) it is extremely surprising that most of the mater ial has an R^ value of less than 0.5. Unfortunately the material from this chromatogram having R^O.O to 0.25 was lost and only the material of R^ 0.25 to 0.50 was analyzed by GC-MS. Figures 4.10 and 4.11 and subsequent GC-MS analysis showed that along with the lo6s of the more volatile components, there was also some removal of the less polar compounds. The data showed however that many of the peaks observable by GC-MS were probably still containing more than one component. In summary, it is suggested that for preliminary separation high speed liquid chromatography rather than the combination of acidity and TLC tech niques should be employed. This would allow a cleaner, less cumbersome sep aration of components without loss of the more volatile ones, and could be expediently complemented with ultimate separation by GC. In any case an outline of the extraction and separation methods finally adopted for this project is shown in Figure 4.12. ;C. Effects of Chlorination oh Primary Effluent 1. Soluble TOC The results presented in Table 4.7 indicate that there is very little change in the soluble organic carbon of sewage as a result of chlorination (Exp. Cl-1). It is also apparent from these results that the 0.45^membrane filters can remove 20 percent of the carbon from primary effluent which has been previously filtered through glass fiber filters of 1.0/tpore size. 2. Effects Monitored by EC and FI Detectors The chromatograms of the various extracts are shown in Figures 4.13 through 4.22 (Exp. Cl-2). These chromatograms were chosen to illustrate Effluent Sample Chlorinate with NaOCI or Take plant chlorinated sample Blank (Distilled H20) NaOCI (pH 7.2) Unchlorinated sample Plastic carboy Dechlorinate with NQ2S2°3 Filter ( l/i) Extract (XAD resin) I Elute column (200ml EtgO) I Extract eluantv (3x10ml 0.05N NoOH) Neutrals & Basics l(N + B) Acids Dry (Na2S04) Acidify, Re extract (3x 10ml Et20) Concentrate to 0.2— 0.5 ml GC (EC, FID) TLC of N +B (Silica gel, pet ether, .methanol) Figure 4.12 Flowchart of Separation Procedure 96 Table 4.7 Effect of Chlorination on Soluble TOC ChlorineCMorine dose TOC TOC mg/1 Cl mg/1 Cl2 (size<V) (size<)0.45>) (mg/1) (mg/1) 0 50 37 12 50 37 103 48 39 97 the effect of various dosages of chlorine upon the acidity separated fractions of the extracts and the reproducibility of these~effects between two differ ent samples of primary effluent. Before discussing these chromatograms in detail some general points should be made. The reproducibility of the chrom atograms is not good particularly in the low temperature region due to the long initial isothermal period at almost ambient temperature. Therefore only changes in patterns of peaks are taken as indications of changes due to chlorination although it is recognized that shifts.^ in the retention time of a series of peaks many not always be an artifact of analysis. It is further noted that there may be differences in concentration among the various extracts. These differences x^hich are most apparent in the FID traces, can be minimized by normalizing peak heights to those of che un changed peaks. Finally, the carrier gas flow rate was significantly higher during the analysis of the sample dated March 8. The higher flow rate resulted from detector response optimization studies carried out on March 10. Since flow rates are never exactly reproducible and pattern recognition techniques could be employed during the comparisons, it was decided to sacrifice flow rate reproducibility in order to standardize the detector response. The peaks whose magnitudes were increased due to chlorination are marked with an "I" and those whose magnitude was decreased are marked with a "D" in each figure. The total number of changes in each extract is summarized in Table 4.8. One of the most striking features of Table 4.8 is that with an EC detector the number of increases far outnumbers the number of decreases. This indicates that the yields of these products of chlorination are small, the products result from non-electron capturing precursors or the precursors are high molecular weight and/or non-solvated molecules. Many more increases are detected by the EC than by the FID whereas the 98 Table 4.8 - Effects of Chlorination by GC Analysis With FID and EC Detectors Figure Sample Date Fraction Detector No. of Increases No. of Decreases 4.13 18/12/74 N + B EC 15 3 4.14 18/12/74 N + B FID 4 2 4.15 18/12/74 WA EC 12 5 4.16 18/12/74 WA EID 4 2 4.17 18/12/74 SA EC 1 0 4.18 18/12/74 SA FID 0 0 4.19 8/03/75 N + B EC 18 5 4.20 8/03/75 N + B FID 5 1 4.21 8/03/75 A EC 2 0 4.22 8/03/75 A FID 0 0 99 30 30 50 100 150 200 Temp (°C) Figure 4.13 Effects of Chlorination by GC - N+B by EC-1. GC conditions in Appendix III. Explanation of Symbols in text. (a) Unchlorlnated 30 30 50 100 Temp (• C) 150 200 Figure 4.14 Effects of Chlorination by GC - N+B by FID-l. GC conditions in Appendix III, of Symbols in text. Explanation 101 Figure 4.15 Effects of Chlorination by GC - WA by EC. GC conditions in Appendix III. Explanation of Symbols in text. 102 (a) Unchlorinated Figure 4.16 Effects of Chlorination by GC - WA by FID'. GC conditions in Appendix III. Explanation of Symbols in text. 103 $0~ 30 50 : 100 ^50 200 Temp (°C) Figure 4.17 Effects of Chlorinat ion by GC - SA by EC. GC conditions in Appendix III. Explanation of Symbols in text. J 1 fl i- I ! 30 30 50 100 150 200 Temp (°C) Figure 4.18 Effects of Chlorination by GC - SA by FID. GC conditions in Appendix III. 105 Figure 4.19 Effects of Chlorination by GC -in Appendix III. Explanation of Symbols in N+B by EC-2. GC conditions text. Jl (a) Unchlorinated 200 219 Figure 4.20 Effects of Chlorination by GC -N+B by FID-2. GC conditions in Appendix III. Explanation of Symbols in text. JUL 29 (a) Unchlorinated (b) 12 mg/1 Cl2 (c) 120 mg/1 Cl2 (d) Plant chlorinated 29 50 100 Tomp (°CJ 150 Figure 4.21 Effects of Chlorination by GC - A by EC, Appendix III. Explanation of Symbols in text. 200 219 GC conditions in 108 1 1—: ; « : 1 . t 1 -9 29 50 IOO 150 200 219 Temp (°C) Figure A. 22 Effects of Chlorination by GC - A by FIB. GC conditions in Appendix III. 109 number of decreases are more similar. TKis is not surprising since addition of oxygen or chlorine to a molecule can dramatically increase its response factor for an EC detector. Other aspects of Table 4.8 such as the difference between the two effluent samples can be more precisely discussed during a detailed analysis of the chromatograms. The effects of chlorination upon the N + B fractions are illustrated in Figures 4.13 through 4.16 and 4.19 and 4.20. There are between 50 and 60 peaks present in each of the figures. With the EC detector (Figs. 4.13 and 4.19) one can see that the new peaks marked "I" which appear at a chlorine dosage of 100 mg/1 or 120 mg/1 also appear at a chlorine dosage of 15 mg/1 or 12 mg/1. The effects of chlorination at the plant are generally inter mediate between those of dosages of 12 and 120 mg/1. There is a one to one correspondence between the peaks of chromatograms (rc)i-ahdl (d) in Figure 4.19.1n fact there are some areas where plant chlorination more closely resembles a dosage of 120 mg/1 than 12 mg/1. There are some new peaks which appear near the solvent peak but these are not marked as they cannot be analyzed by GC-MS with the OV-101 column. One can also see that many changes marked "X" appear in the sample dosed with 200 mg/1 of chlorine which are different from those'appearing at lower dosages of chlorine. These changes unique to high dosage levels are prob ably due to the presence of free residual chlorine since the "breakpoint" is expected to lie between 140 and 170 mg/1 C^. In the interest of optimizing the yields of only those produces of chlorination which result from treatment plant dosage levels, it was decided to only chlorinate samples at levels of 0, 12, and 120 mg/1 Cl2. It is evident from Figures 4.14 and 4.20 that most of the peaks in the N + B fraction are much smaller with the FID as compared to the EC detector. Since the changes due to chlorination also occur in areas of poor resolution 110 they are much less spectacular in these chromatograms. Because of the sub stantial differences in detector responses no unequivocal correlations can be made between the EC and FID chromatograms, however it does not appear as though any of the effects of chlorination are visible with both detectors. Judging from the FID one would expect to see about 60 peaks in the N+B fraction by GC-MS, however the effects of chlorination will probably not be very evident. The chromatograms of the acidic fractions are displayed in Figures 4.15 through 4.18 and Figures 4.21 and 4.22. Comparison of Figures 4.17 and 4.21 shows that the NaOH extracts contain one new EC detectable peak resulting from chlorination. The appearance of effects of chlorination unique to high dosage levels is again evident in chromatogram !(d)* in Figure 4.17. The FID chromatograms in Figures 4.18 and 4.22 show the lack of any detectable effects of chlorination. Judging from these chromatograms there should be nine peaks visible in the acid fraction by GC-MS, none of which is due to chlorination. The chromatographic profiles of the various samples of primary effluent collected throughout this study as wellaas the effects of chlorination appeared tolibe remarkably consistent. For example the peaks numbered 1 through 12 in chromatograms Ca)' in Figures 4.13 and.4.19 appear to be iden tical. ?A total of nine new peaks resulting from chlorination obviously pres ent in Figures 4.13 and 4.19, and if for reasons previously discussed some of the peaks in Figure 4.15 are included in Figure 4.13 this number increases from nine to seventeen or eighteen. Only one or two peaks do not appear in both effluent samples. This combination of Figures 4.15 and 4.13 is further jus tified by the analysis of samples taken on July 8, 1974 and Nov. 19, 1974. These extracts (Appendix II), one with bicarbonate extraction and one without produced GC chromatograms similar to either the Dec. 18/74 or March 8/75 Ill extracts on columns of OV-101, OV-17 and OV-225. Evidence for the consistency of the other chromatograms of the extracts is provided by comparison of the appropriate figures. It is noted that the consistency of the FID chromato grams is not as striking as that of the EC chromatograms because of factors previously mentioned. In summary, two major points arise out of these studies. Firstly it was demonstrated that chlorine dosages as high as 120 mg/1 but less than 200 mg/1 can be used to increase the yields of chlorination products without forming products not produced in treatment plants. Secondly it was shown that new EC and FID detectable compounds are consistently produced as a result of chlorination at treatment plant dosage levels. A total of 16 to 18 new peaks were detected in the N + B fraction and 4-6 new peaks in the acidic fraction as a result of this chlorination. 3. MEC Detector This detector was used to study the magnitude of chlorine uptake by the volatile organics (Exp. Cl-3). The chromatograms are presented in Figures 4.23,,f4.24, and 4.25 and the detector calibration curve is shown in Figure 4.26. The chlorine content of each peak was determined and the total chlorine content of each sample calculated assuming a sewage sample volume of 10 1 (Exp. E-4). These results are summarized in Table 4.9. The chlorine up take in each fraction was then expressed as a percentage of the dosage and the total organic chlorine present in the sample. These calculations are presented in Table 4.10. Before discussing the significance of the chlorine uptake data, four points should be made. Firstly, "tixe MEC detector is not specific for chlor ine, although it is specific for halogens. Secondly, even assuming that all peaks were due to chlorine, the response per nanogram of chlorine is not constant for all types'of compounds as can be seen from Figure 4.26. Thus 112 < I : I i I 1 1 1 1 ; I I ' 22 20 18 16 14 12 10 8 6 4 0 Time (min) Figure 4.23 Effects of Chlorination by GC -A by MEC. GC conditions in Appendix III. Explanation of Symbols in text. (a) Unchlorinated J 1 -— • 1 —i il _i i i , . 24 22 20 \BiS 14 12 10 8 6 42 Tim© (min) Figure 4.24 Effects of Chlorination by GC - N+B by MEC-1. GC conditi in Appendix III. Explanation of Symbols in text. 114 24 22 20 18 18 14 12 10 0 6 4 Time ( mlnute» ) Figure 4.25 Effects of Chlorination by GC - N+B by MEC-2. GC conditions in Appendix III. Explanation of Symbols in text. § 2 3 4 5 10 20 30 CHLORINE (NG) Figure 4.26 Calibration Curve for MEC Detector. .116 Table 4.9 - Concentrations of Halogen as Chlorine in Primary Effluent a) Acid Fraction Concentration of Chlorine.(ng.Cl/1) Peak Chlorine Dose (mg /C1./1) N(0) 12 P (12) 120 -1- 60 2 80 70 80 3 40 4 60 60 5 40 40 40 40 6 100 70 100 7 40 60 60 80 8 60 . 60 9 140 10 100 180 240 260 11 90 30 12 60 120 13 40 40 100 117 b) Neutral and Basic Fraction Concentration of Chlorine (ng Cl/1) N (0) Chlorine Dosage (mg 12 P (12) 120 Concentration Factor ,~4 _ ... 4. .. 4 4 4 4 4 10 5 x 10 . 10 5 x 10 10 5 x 10 10 1 OS OS 30 OS 940 2 220 OS 260 OS 200b OS OS 3 500 OS 1050 OS 360 OS OS 4 100 90 60 50 450 5 160 110 50 100 850 6 50 40 25 150 6a 50 50 7 90 8 10 10 10 180 9a 5 90 100 40 600 10 10 0 :9b 5 5 10a 30 35 360 lQa 10 10 10 11 5 5 180 12a 60 15 60 60 60 45 50 12a 40 50 35 Uu 15 15 20 200 13a 15 5 10 1_4 30 45 60 50 50 50 500 1<5* 20 30 30 160 16* 140 95 160 OS 140 100 500 1JZ 40 40 35 300 18 30 25 30 90 m 70 55 60 60 2.0* 15 15 440 21*' 220 205 320 240 260 240 160 22* 90 70 140 60 120 60 420 23 50 80 50 85 90 130 1000 24 65 110 130 120 25* 20 50 40 90 60 120 26* 180 2c7* 20 20 420 280 180 2f8 50 29a 140 •29a 90 100 40 100 60 140 30 40 20 100 360 31 120 OS 120 OS 140 OS 32a 50 . 50 120 . . .. .90 . . 80 50 160 -32a— —: v.:. 60 OS - Off scale 118 Table 4.10 - Chlorine Uptake by Volatiles a) Acid Fraction Cl - Dosage mg/1 Total Chlorine Chlorine Uptake 2 >rg/l //g/1 % Dose % Total Cl-N (0) 0.25 12'; 0.68 0.40 0.0033 59 P (12) 0.67 0.24 0.0020 36 120 1.11 0.70 .0006 63 b) Neutral and Basic Fraction Concen. Cl s Dosage Total Chlorine Chlorine Uptake' Factor . 2 mg/1 /#g/l >Yg/l % Dose % Total Cl —: a b a hi 104 N (0) 1.57a .85 S-r^?' -—— -10* 12 2.83 i.52 0.40 0.0033 14 26 104 P (12) 2.21 1.62 0.53 0.0044 24 33 104 120 -=- 8.05 3.12 0.0026 — 39 5xl04 N (0) 1.18 -— 5x104 12 1.85 0.45 0.0038 24 5xl04 P (12) 2.16 0.59: 0.0049 ... 27 c) Total's Uptake a Cl2 - Dosage Total Cl Cl-Uptake b (mg/1) (Jfe/l) ty/g/D % Dose . % Total N (0) 1.10 12 2.20 0.80 O^QO.7 36 P (12) 2.29 0.87 0^00,6 38 120 9.16 3.82 Q.cO.05 42 a -b -excluding unnumbered peaks at beginning excluding peaks 1, 2, 3 119 an error of plus or minus 25 percent or more is expected in the individual values. Also peak height was used as a response rather than peak area; it was felt that this was a valid substitution mainly because of the large number of shoulders on the peaks. Third, the variability of concentration factors among a set of identically handled extracts is expected to be about 10 percent. Finally, the detection limit for the less concentrated samples was 30 ng/l Cl while the detection limit of the more concentrated samples at lower attenuation was 3 ng/l Cl, assuming a minimum detectable peak of 0.2 cm. From the chromatograms of the acid fraction, Figure 4.23, it is evident that there are six or seven peaks which appear as a result of chlorination. From Table 4.9 it can be seen that all of these peaks are present in concen= trations below the detection limit of the mass spectrometer unless the com pounds are less than twenty percent chlorine by weight. Comparison of the chromatograms of the neutral plus basic fractions in Figures 4.24 and 4.25 shows that there is a one to one correspondence between peaks in identical samples run at different concentrations and attenuations. There are also 10 or 11 new peaks which appear as a result of chlorination as denoted in Table 4.9. Of these, only peaks 4, 5, 9, 10 and 20 will prob ably be detectable with a mass spectrometer. In addition to the 10 or 11 new peaks, there are several others in the sample dosed with 120 mg/1 Cl^ which appear to be enhanced as a result of chlorination. It is unlikely that the hypochlorite contained many chlorinated compounds since both the microelectro-lytic conductivity and electron capture traces of an extract of 50 mis of hypochlorite solution showed no peaks except in the region of the unnumbered peaks at the start of the chromatogram,?. These unnumbered peaks are probably halogenated methane and ethanes. The chlorine uptake summary in Table 4.10 shows that at dosage levels 120 commonly used in primary treatment plants about 0.01 percent of the applied chlorine ends up in the extractable volatile compounds,of this amount about two-thirds is somewhat surprisingly incorporated into neutral and basic compounds rather than acidic compounds. Furthermore, about 40 percent of the extracted - organic chlorine found in primary chlorinated effluent, excluding methanes and ethanes, resulted from chlorination. The use of the term 'extracted'-, in the preceding paragraph to describe the volatiles should be emphasized. It is well known that clays and natural organic matter sorbs organics from water (Weber 1972). On the other hand, dissolved organic matter can increase the solubility of other organic com pounds (Wershaw et al., 1969), although the dissolved organic matter in sew age was shown to have.no effect on the sorption of dieldrin by montmorillinite (Huang 1971). Since clays and organic particulates will be removed during the filtration of the samples between the chlorination and extraction steps, losses due to sorption may be significant. In Table 4.5, the loss of di-chloropheriol due to sorption on particulates was 15 percent. This confirms that sorption is significant however the application of 15 percent as a gen eral estimate is obviously not•justifiable. With these sorptive losses in mind it is possible to make a very rough comparison of the values for total chlorine in Lion's Gate Effluent with those for other sewages. Using unfiltered samples and solvent extraction, Dube et al. (1974) found about 0.2_^f.g/l PCB's in domestic sewage, while McDermott (1974) found about O.S^g/l total identifiable organochlorine pesticides in domestic sewage.• Therefore the total dissolved and sorbed organic chlor ine in these sewages was at least ;0.4/^g/l. No data is available for other volatile chlorinated compounds. Judging from the distribution of chlorine throughout the chromatogram it appears that the 1.4-2.of organic chlorine in the unchlorinated sample of Lion's Gate effluent is in the same range of concentrations,although no PCB'sor pesticides were identifiable by mass spectrometry. The individual concentrations of chlorine containing organics resulting from chlorination on a chlorine basis range from 0.02 to 0.15/Ag/1 while Jolley (1973)reported concentrations of 0.2 to Differences in extraction and analytical procedures as well as the fact that Jolley measured mainly non-volatile compounds may account for these concentra tion differences. 4. GC-MS Studies on the MS-12 The initial experiments with the GC-MS showed some promise. The chrom atograms of all N+B fractions of the extracts were identical. Figures 4.27 presents a typical chromatogram while some of the corresponding mass spectra are shown in Figure 4.28. Only two compounds, a phthalate (Spectrum 34) and caffeine (Spectrum 36) are identifiable. Peaks 9, 11, 14, 17 and 19 in Figure 4.27 have almost identical mass spectra with the major ion series being m/e 45, 59, 73... and 137, and thus appear to be alkyl silanes. There were some differences. but background subtraction was very difficult. It proved difficult to trigger the MS at the precise times for the minor components of the extracts. Fluctuations in accelerating voltage and hysteresis problems were also noted during a GC run. During the course of this project the performance of the MS-12 seriously deteriorated. Negative baseline drift occurred during temperature program ming due to an increase in pressure drop across the column with increasing GC oven temperature. The sensitivity of the instrument decreased to the point —6 where the identification limit of DCP was 1.2 x 10 g. The pressure in the -4 analyzer chamber was about 5 x 10 Torr and the GC detector had to be set at 1 x 10~^ Amps full scale rather than the manufacturer's recommended 1 x 10 ^ Amps. Only one or two rather broad peaks could be detected per run. An at-35 *f* 35 "I* 37 *T* 37 tempt to conduct a search for Cl . H Cl , Cl , and H Cl by a limited so ...;*>,.. /40 , ... 30 , ... 2.0 ,.. [0 ,. . o 300 280 200 120 40 40 Temperature (°C) Figure 4.27 Total Ion Current Plot for N+B Fraction by MS-12. GC conditions in Appendix III. Numbers denote Spectrum. Spectrum 34 149 41 57 JLL 69 111 L 93 _i 105 .J 12i 205 m/e Spectrum 36 28 32 . 42 -iu. m/e 55 67. 82 In I 1 u-109 137 194 165 Figure 4.28 Mass Spectra from MS-12. Spectrum numbers correspond to peaks in Figure 4.27. 124, mass scan showed two peaks. However during this run the hysteresis problem was very evident. In summary, although the initial work with the MS-12 was promising, problems developed which forced the suspension of work with this instrument. Alternative methods of analysis were therefore needed. 5. Tentative Identification by Retention Time The objective of this experiment was to tentatively identify some of the major peaks in the chromatograms of the sewage extracts by comparison of GC retention times. The test compounds, their recrystallization solvents and retention times are listed in'liable ;4.11. The composited GC traces of these compounds along with corresponding GC traces of some chlorinated sewage ex tracts are shown in Figure 4.29. All of the test compounds, with the exceptions of peaks 3 and 4, have corresponding peaks in either of the sewage extracts. However only a few of them, listed in Table 4.12, correspond to major peaks in the sewage extracts. It is also noted that some of the high boiling compounds were not eluted. For example the dihydroxybenzene and the dichloroquinone were not eluted within the temperature program. These negative results are useful in deter mining the limits in terms of volatility of compounds analyzed in this project. Several factors mitigate against pursuing this experiment further by the use of other GC column packings. It is not possible to correlate the chrom atograms of the sewage extracts run on different column packings due to the large number of peaks. Furthermore, since major peaks may contain several components, a change in column packings may cause major peaks to become minor ones while different major peaks may appear. The list of compounds chosen as test compounds is obviously far from comprehensive and one would expect to obtain a list of several possible compounds for each peak in the sewage sample. Notwithstanding the aforementioned problems, it can be said that the 125 Table 4.11 Retention Times of Test Compounds Compound Recrystallization Retention Time Solvent (min) (Temp, prog.) 0- Ghloroberizoic acid Pet ether 29.6 m-Chlorobenzoic acid " N p-Chlorobenzoic acid2- Amino-5-CKlorobenzoic Acid N 4-Chlorometanilic Acidp-Chloro phenol 21.0 p-Bromo phenol 6 2,4-Dichlorophenol Benzene 25.0 2,4,6-Trichlorophenol R^O/MeOH 26.8 Resorcinol Benzene N p-Chloroaniline Pet ether 26.4 2.4- Dichloroaniline " 27.0 2,4,6 Trichloroaniline "= 32.9 4-Chloro-2,6-Dinitroaniline Ethanol 34.2 4.5- Dichloro-2-Nitro Aniline " 35.5 4-Chloro pyridine . HCI N 3- Amino-2-Chloropyridine 17.2,4-Dichloropyrimidine 2 2-Amino-4,6Dichloropyrimidine Pet ether 30.6 1-1- Chloro-2,4-Dinitrobenzene MeOH 32.8 l-Chloromethyl-2 methyl napthalene 34.2 4- Chlorobenzaldehyde 9.5 2,5iDichloro p-quinone N 4,4'-Dichlorobenzophenone 38.6 l-Bromo-4-Chlorobenzene 9.0 Carbontetrachloride 0.8 Chloroform 0.Methylene Chloride 7 Solvent peak 0*7= N - Compound did not elute Figure 4.29 Identity of Numbered Peaks in Chromatogram (a) 1. l-Bromo-4-chlorobenzene 10. 2,4-Dichloroaniline 2. 4-Chlorobenzaldehyde 11. 2-Chlorobenzoic acid 3. 3-Amino-2-chloropyridine 12. 2-Amino-4,6-dichloropyrimidine 4. 2,4-Dichloropyrimidine 13. l-Chloro-2,4-dinitrobenzene 5. 3-Chlorophenol 14. 2,4,6-Trichloroaniline 6. 3-Bromophenol 15. l-Chloromethyl-2-methylnapthalene 7. 2,4-Dichlorophenol 16. 4-Chloro-2,4-dinitroaniline 8. 2,4,6-Trichlorophenol 17. 4,5-Dichloro-2-nitroaniline 9. 3-Chloroaniline 18. 4,4'-Dichlorobenzophenone Figure 4.29 GC Retention Times of Test Compounds. Numbers in chromatogram (a) are explained on facing page. GC conditions in Appendix III. 128 Table 4.12 Compounds Identified by GC Retention Time Compound Detector Authentic Compound Primary Effluent 4-Chlorophenol MEC, .MS MEC 2,4-Dichlorophenol EC, FID EC 2,4,6-Trichlorophenol EC, FID EC 2-Chlorobenzoie Acid EC, FID EC l-Chloromethyl-2-Methyl Napthalene EC, FID EC or 4-Chloro-2,4-Dinitro-Aniline EC, FID EC 4,4*- Dichlorobenzophenone EC, FID EC a - See Section 7 of this chapter. . 130 identification of five or six chlorinated compounds in chlorinated sewage has been very tentatively established. Further investigations are obviously needed to confirm these identifications. ;6. GC-MS-Computer Studies The objective of this experiment was to identify as many components of the sewage extracts as possible an the basis of mass spectra and GC retention time. A typical set of instrument performance evaluation data is shown in Table 4.13 along with the criteria of Harris,Eichelberger and Budde (undated). The deviations at 365 and 442 are not considered to be serious. A voluminous quantity of information was generated from the manipulation and reduction of data during the analysis of the various extracts and blanks. In the interests of brevity only some illustrative examples of the reconstructed gas chromatograms (RGC) and limited mass searches (LMRGC) will be presented. The mass spectra of the compounds positively identified will be presented graphically in Appendix IV, while the remaining mass spectra will be presented in Appendix V. For convenience, the chromatograms and associated spectra will be referenced by file name. An explanation of these file names is given in Table 4.14. Since the RGC's have been normalized in some cases to the solvent peak, the peak heights do not reflect the relative concentrations of a particular component in the various fractions. However, a problem of loss of volatiles is evident upon comparison of '1CSI202 and C-HALL with 120N1. One would ex pect to find peak heights in CL1202 to be fifteen times those in 120N1. In fact, below spectrum number 20 the ratio is only 2:1, while above spectrum number 150 the ratio is 10 or 12:1. Various temperature programs were employed to optimize reproducibility, and resolution. Of the initial temperatures of 100, 75, 60 and 55°C, 60°C was chosen to be optimum. A deviation of + 3 spectra or 12 seconds persisted 131 Table 4.13 Performance Check of Finnigan 3000 AMU Rel. Int. (%) Criterion Meets Criterion 51 39.42 30-60 % of 19.8 Yes 68 0.62 <2 % of 69 Yes 69 41.04 70 0.33 C2 % of 69 Yes 127 44.49 40-60 % of 198 Yes 197 0.24 <1 % of 198 Yes 198 100.00 100 % Yes 199 6.68 5-9 % of 198 Yes 275 15.66 10-30 % of 198 Yes 365 1.08 >2 % of 198 No* 441 3.32 < 443 Yes 442 22.43 40-60 % of 198 No* 443 4.48 19-21 % of 442 Yes * Criteria are for Finnigan 1015 which has a mass range of 0 Finnigan 3000 has a range of 0 - 500 Amu. - 750 Amuiji the 132 Table 4.14 - File Names for GC-MS-Comp. Studies File Name Extract Fraction Chlorine Dose mg/1 Date of Run ARAWS1 CL12A1 APLCL1 CL12DA BLANKA NBRAW1 CL12N1 NBPLGL 120NB1 CL1202 35LBK1 C-HALL B-HALL RAWNB1 M1XA2 M1XB Acids; Blank-Acidic Neutrals + Bases ii I! II II II II II . II Blank-Neut. + Base Neut. + Base /TLC Blank for C-HALL Same Sample as NBRAW1 Mix of Test Compounds Mix of Test Compounds 0 12 Plant 120 0 0 12 Plant 120 120(30/1 cone, to 2 pX) 0 120 0 May 6-8/75 II II II II it 0 July /75 II Dec. 18/75 133 with this initial temperature. This may be due to slight differences in initial temperature or program rates. When samples were run on different days the reproducibility of retention times was much poorer. Deviations of six spectrum numbers (24 sec) were noted. An unexpected development militated against allowing more than half an hour to cool the GC oven and allow for efequilibration between runs. It was noted that even with no sample injection, two peaks appeared in the chromatogramv, The mass spectra of these peaks (Appendix V) were identical but did not match those of the GC stationary phases. It was therefore con cluded that these peaks were the result of condensation of septum bleed material onto the GC column and subsequent volatilization of this material at higher temperatures. This problem could be ameliorated but not eliminated by changing the septum daily. Although these peaks presented a problem, they also provided a set of reference points for comparison of the RGC's. The RGC's of the acid, neutral plus basic, and TLC separated neutral plus basic fractions are presented in Figures 4.30, 4.31 and 4.32, while the blank is presented in Figure 4.33. Table 4.15 presents, a summary of the total number of peaks in, and the effects of chlorination on each effluent extract. There does not appear to be any noticeable effect of chlorination upon the acidic fraction as predicted by FID studies, although phenolic compounds should appear in this fraction. The RGC's of the neutral plus basic fractions show some changes as a result of chlorination. Some new peaks are apparently produced, however they may have been due to changes in resolution since no different mass spectra could be obtained from these peaks. The LMRGC's provided an invaluable aid in the data reduction process. Searches for septum bleed (m/e 293) , o-phthalate esters (m/e 149), and chlor ine (m/e 35, 36) were routinely made for each chromatogram. Chlorine searches yielded peaks in NBRAW1 at Spectra 7, 11, 62, 83, and 234. These peaks were Table 4.15 Summary of RGC Data File Total Number of Peaks: Peaks Resulting from Chlorination (Spectrum Numbers) Peaks Decreasedby Chlorination (Spectrum No's) ARAWS1 15 None CL12A1 15 None APLCL1 15 None CL120A 15 None BLANK A 4 None NBRAW1 64 None CL12N1 60 43, 145, 167, 257. NBPLCL 60 41, 146, 168, 192, 257 120NB1 63 41, 144, 167, 183, 191 CL1202 62 40, 82, 85, 145, 169, 183, 35LBK1 6 None C-HALL 49 Nc it Determined B-HALL 6 ii i it None None None' None None None ..None 252, 272 252, -157 282, 172 SNone 7 Not Determined n it 0 IS 20 33 13 SO GQ 70 88 30 188 110 120 130 110 ISO 160 170 180 130 ZOO 210 220 230 210 250260270260230300 310 320330310350360 SPECTRA NLK3ER Figure 4.30 RGC's of Acid Fractions. GC conditions in Appendix III, On -i r—i—r-5Q 100 1 ' 150 •»—I— 200 -1— 250 1— 300 -I 1 ' r-40Q. 1— 350 SPECTRUM NUMBER Figure 4.31 RGC's of Neutral and Basic Fractions, GC conditions in Appendix III, ov Figure 4.32 RGC's of TLC Fractions. GC conditions in Appendix III. 139 consistently and uniquely present at all chlorine dosages although the great difference in yields of these ions from aliphatic as opposed to aromatic chlorinated compounds tends to decrease the importance of this search. The septum bleed search showed that these peaks are in some cased most intense peaks in the chromatograms. The LMRGC of m/e 149 shows that the phthalate esters are found in both the^neutral plus basic and acidic fractions although judging from the ratio of peak intensity to average baseline their concentra tions in the neutral plus basic fraction is about 20 times those in the acid fraction. In addition, one additional phthalate appears in the acidic frac tion at spectrum 274 APLCL1. This peak may be due to the saponification of a phthalate ester. A summary of the information contained in the LMRGC's of m/e 149 and 293 is presented in Table 4.163,0 The other very important application of the LMRGC was to pinpoint the spectra of the components. For example in M3LXA2 the phthalate appears at spectrum 214 while the septum bleed occurs at spectrum 213 although these components show up as a single peak in the RGC. The general method involved single or double display of consecutive spectra,- selection of peaks for LMRGC's, construction of the LMRGC, pinpointing of the spectrum or spectra of interest and the libaekground' spectra, background subtraction,, and printing. The CRT console and magnetic disk were invaluable in performing these functions. One complete cycle could be carried out in 4 - 5 minutes. Once a mass spectrum was chosen it was subtracted from the next higher number spectrum to ensure that major peaks found in the chosen spectrum did in fact belong in that spectrum. For example, if spectrum 11-9 was chosen, spectrum 12 - 11 was also retrieved to attempt to ensure that peaks from the compound(s) eluting at spectrum 12 or higher were not included in the spectrum of the compound whose maximum occurred at spectrum 11. The matching of spectra to reference files led to the compilation of a File Table 4.16 Phthalates and Septum Bleed from LMRGC Phthalates (m/e 149) Septum Bleed (m/e 293) Spectrum Numbers Spectrum Numbers ARAWS1 204, 211, 253, 273 210, 257 CL12A1 203, . 210, .252, 274 209, 257 APLCL1 203, 211, 253, 274 - 210, 257 CLI2OA 203, 210, 253, 274 209, 256 BLANK A 203, 210, 252, 338 210, 257 NBRAW1 203, 211, 241, 247, 254, 276, 341, 406 209, 257 CL12N1 202, 210, 2405 246, 252, 273, 336, 409 210, 258 NBPL'CL 203, 211, 241, 247, 253, 339, 403 210, 258 120NB1 203, 211, 241, 247, 253, 341, 423 209, 257 CL1202 195, 204, 211, 242, 248, 254, 277, 342, 425 210, 258 35LBK1 203, 211, 241, 253, 338, 401 210, 258 C-HALL 182, 209, 222, 229, 236, 269, 366, 508 187, 237 3B-HALL 181, 221, 229, 365, 508 187, 237 RAWNB1 211, 219, 251, 257, 265, 291, 369 217, 265 M1XA2* 209, 214, 235, 239, 262 213, 261 M1XB* 179, 201, 206, 226, 233 184, 234 * Spiked with phthalates 141 list of possible compounds for each spectrum. Analysis of a mixture of au thentic samples of these compounds by GC-FID and GC-MS-Com provided spectra and retention times. The comparison of GC-retention times was based on rel ative retention times as follows: • (RB1C " V - (RB1S " V RB1C - RB1S + RS " RC Rr= = : (4.1) SB1C " RB1S RB1C " RB1S where Rr = Retention time of peak in CL<1202 or C-HALL Rg = Retention time of peak in M1XA2 or M1XB R,,..-, = Retention time of ihs.likSeptum bleed in CL1202 or C-HALL DLL R„1C = Retention time of 1st Septum bleed in M1XA2 or M1XB. Bib This method of correlation of the retention times was chosen for the follow ing reasons. First, since relative retention times on a ratio basis are a function of temperature the error limits for these ratios will also be a function of temperature. This would necessitate a rather complex type of analysis to determine the retention time correlations. Second, the phthalate and septum bleed peaks appear to be linearly shifted when comparing C-HALL with M1XB or CL1202 with M1XA2. This implies that the differences in the chromatograms were due either to changes in flow or column deterioration over the four month period between the runs. In any case the linear shift provides a very simple method for correlation of retention times and thus equation 4.1 was adopted. The use of spectrum numbers as a measure of retention time contributes an error of about.0.25 spectrum numbers. Since the maximum deviation in re tention times of identical peaks among the runs on the same day was shown tb be leof»3 spectrum numbers, the maximum allowable deviation in R^ is -1.00 ^R^ <£+1.00 for the retention time correlations. The results of the spectral file searches and retention time checks are summarized in Tables 4.17 and 142 Table.4.17 Results of Spectral Searches and Retention Time Checks for CL1202 Spec. No (CL1202) Possible Compd. from File Search Spec No (M1XA2) R^ within limits 11 19 31 31 31 23 40 44 44 56 56 61 69 69 62 62 66 66 77 ill, 86 98 986 106 106 110.117 117 133 137 137145 145 194 204 211 242 248 C2Cl4 Cl-Benzene Et-Benzene 0- Mie2~ Benzene m-Jle2-Benzene p-Me2~Benzene 2-n-Butoxy ethanol iPr-Benzene 1,2,4-Me3~Benzene lr-Me-3-Et-Benzene 1-Me,2-Et-Benzene P-CI2 Benzene 0- CI2 Benzene P-CI2 Benzene n-Bu-Benzene t-Bu-Benzene Benzaldehyde and C<.-chloro toluene or o-chlorotoluene Benzyl alcohol p-Cresol 2- phenyl ethanol Dihydroheptafulwene Menthol Isomenthol Terpineol Me-Salicylate 1- Me-Nap thaiene 2- iMe^Napthalene Dichlorocresol Indazole Benzimidazole Benzofuran Diethyl phthalate phthalate n-propyl phthalate n~Bu ^phthalate 16 24 31 37 30 28 46 64 70 77 70 80 64 71 72 53 83 92 103 112 115 123 139 139 -0.67 -0.67 +1.00 -1.00 +1.33 -0.67 +0.33 -5.67 -2.00 -1.67 +0.67 -5.00 0.33 -0.67 -1.00 +5.3 -1.00 -1.00 -0.67 -1.00 -0.67 -1.00 -1.00 -1.00 yes yes yes yes (no) <no) yes no no no yes no yes yes yes no yes yes yes yes yes yes yes yes 209 236 263 -0.67 +3.00 -4.00 yes no no 143 Table 4.18 Results of Spectral Searches and Retention Time Checks for C-HALL Spec # Possible Compd. Spec// \ Rj^ within C-HALL From File Search M1XB limits? 39 Benzaldehyde 51 Benzyl alcohol 59 p-Cresol 69 Methyl Benzoate 68 +.67 yes 71 2-?Jhenyl ethanol 81 Menthol Isomenthol 89 Camphor 87 +.33 yes 99 Indazole 121 2,4 or 2,5-Me.2Benzyl-OH 3-Pjhenyl propylamine Benzimidazole' Benzofuran 111 1-M.e Napthalene 110 +.67 yes 2-Mie Napthalene 114 Iso-borneol 72 -13.00 no Bornyl acetate 111 0.00 yes 136 1,3-Dimethylnapthalene 2,7-Dimethylnapthalene 152 Glycerol triacetate 150 +0.33 yes Diacetin 125 -8.00 no 156 1»4,5 Trimethylnapthaiene 159 Dimethyl phthalate 1577 +0.33 yes 164 Coumarin 162 +0.33 yes 168 Cedrol 176 cxVTetrahydrofuryliQH 178 Benzophenone 178 +1.00 yes 182 Diethylphthalate 178 0.00 ye201 Anthracene 200 +0.67 yes Phenanthrene 200 +0.67 yeDiphenylacetylene 176 -7.33 no 209 Propyl phthalate 206 0.00 yes 211 Ppt-Bu phenoxyethanol 222 Phthalate 229 Phthalate 226 236 ,n-Bu phthalate 233 0.00 yes 260 -:ie*;^Stearate 254 -1.00 ye269 Phthalate 366 Benzyl Bu-phthalate 508 Octyl phthalate . 144 4.18. Most of the mass spectral and retention time correlations are straight forward however spectra 31, 61 and 69 in CL1202 present special problems. For spectrum 31 the correlation factor for o-xylene is -1.00 while those for ethyl benzene and the other xylenes range from +1.00 to +2.00. Since almost all of the other positively correlating matches have retention time correla tion factors between +0.33 and -1.00 it was felt that the correlation factors for the meta and para xylenes was sufficiently large to warrant probable rejection. With respect to the dichlorobenzenes the expected order of elu tion is meta, para and ortho (ASTM 1967, Zweig and Sherma 1972). Since the ortho-dichlorobenzene shows a large deviation in relative retention times, it is most probable that the compounds present in C11202 are the meta and para dichlorobenzenes. In some cases authentic samples of the compounds listed in Tables 4.17 and 4.18 were not available. Therefore no retention time correlation times were obtained. In addition, compounds which afforded a reasonable match on the basis of an eight peak index search but for which no reference spectrum or authentic sample was available are not included among those listed in Tables 4.17 and 4.18. A summary of compounds positively identified by mass spectrum and re tention time appears in Table 4.19. For these compounds an estimate of concentration in sewage effluent was made on the basis of peak heights in the unnormalized total ion current traces of the samples. Linearity of the mass spectrometer was assumed along with a zero response for zero sample injected. Since no studies of recovery factors or concentration losses were made, changes in instrumental sensitivity may have occurred and resolution was not always good, these concentrations are stated as order of magnitude ranges. The lower number in the range is the average concentration in 120NB1, 145 Table 4.19 Compounds Positively.Identified by Mass Spectrum and Retention-Time Compound Spec No Spec No Concentration Range in CL1202 C-HALL Primary Effluent (^g/1) GC - MS MEC Tetrachloroethylene 11 5-50 1-10 p-Xylene 23 1-10 o-Xylene 31 1-10 Isopropylbenzehe 44 2-20 Tert-butylbenzene 62 10-100 Chlorobenzene 19 10-100 1-10 m-Dichlorobenzenep-dichior . 61 10-100 0.4-4 p-Dichlorobenzene 69 3-30 1-10 £X-Chloro toluene 66 7-70** 0.4-4 Benzyl alcohol 77 51 10-100 2-Phenylethanol 98 71 5-50 Cresol (p?) 86 . 59 20^-200 Benzaldehyde 66 39 10-100 Methyl Benzoate 69 0.4-4 Methylsalicylate 117 7-70 Benzophenone 178 1-10 1-Methyl napthalene and/or 133 111 5-50 2-Methylnapthalene 133 Phenanthrene and/or 201 0.8-8 Anthracene 201 Glycerol triacetate 152 0.5-5 Methyl stearate 260 0.7-7 Dimethyl phthalate* 159 0.6-6 Diethyl phthalate* 204 182 0.4-4 Di-n-propyl phthalate* 209 0.3-3 Di-n-butyl phthalate* 236 9-90 Menthol 106 81 15-150 Terpineol 110 20-200 Camphor 89 1-10 Bornylacetate 114 0.8-8 Coumarin 164 2-20 * Possibly from contamination during sampling and analysis. ** Estimate is probably high. 146 CL-1202 and C-HALL if the compound was present in all three chromatograms. The actual concentration may be lower than this due to resolution problems. The higher number is one order of magnitude higher than the lower number and is an estimate of the maximum possible concentrations. A list of those compounds whose spectra can be reasonably identified in the spectra from CL1202 and C-HALL but for which no authentic samples were available is compiled in Table 4.20{ These compounds have been tentatively identified and in many cases several possible identifications were made for the individual spectra from CL1202 and C-HALL. 7. Correlations Among G.C. Chromatograms In order to further study the compounds formed as a result of chlorina tion, a correlation among the GC chromatograms from the various GC instruments was attempted. While some information regarding these compounds can be ob tained from the FID and EC detectors (e.g. Figures 4.24 and 4.10), the most significant information comes from the MEC and mass spectrometric detectors. Therefore correlations among retention time with the MEC detector, spectrum number in CL1202 and spectrum number in C-HALL were made. The MEC detector trace was.first correlated with CL1202 through the use of three compounds and the zero point. CL1202 was then correlated to C-HALL on the basis of identical spectra from Tables 4.16, 4.17 and 4.18. The results of these correlations are displayed in Figure 4.34. It is interesting to note that both correlations are linear. On the basis of Figure 4.34, the spectrum numbers of the halogen con taining compounds were estimated. This data is summarized in Tables 4.21 and 4.22. From these tables it can be seen that seven to nine of the thirty-eight halogenated neutral or basic compounds detectable by MEC are also de tectable by GC-MS, while none of the acidic compounds containing halogen are detectable by GC-MS. In the neutral and basic fraction only three of the 147 Table 4.20 Compounds Tentatively Identified by MS Compound Spectrum No • CL1202 Spectrum No C-HALL Dihydroheptafulvene 98 225 2,3 Bis (4-methoxyphenyl) pent-2-ene 1 -Me-£kyi, 2;rEthylbenzene 56 1 -Meithy 1 ,,3-E thy lb enz ehe 56 1,3,5-Trimethyl-2-n-butylbenzene 127 1,3~Dimethylnapthalene 136 2,7-Dimethylnapthalene 136 1,4,5 Trimethylnapthalene 156 Dichlorocresol (4,6) 137 2,4-Dimethylbenzylalcohol 99 2,5-Dimethylbenzylalcohol 99 2-n-Butoxyethano1 40 p-t-Butylphenoxyethanol 211 Cedrol 168 OC^-Tetrahydrof uf urylalcohol* 176 Dihydrofuran (2,5) 8 Benzofuran 145, 194 . 121 2-Methylazetidine 8 2,2-Dimethylaziridine 8 Indazole' 145, 194 121 Benzemedazole 145, 194 121 Acetanilide 133 3-Phenylpropylamine 99 Caffeine See Figure 4.28 * Retention time is very long and therefore suspect is some type of degradation product. 87T 149 Table 4.21 - Spectrum Numbers of Halogenated. Neutral and Basic Organics MEC Detector Mass Spectrometer Spectrum Compound Peak # Retention Time SPffrum Number sh^s Results (m±n) CL1202 C-HALL Chlorine from Chlorination 1 .1.2 5 No No* 2 1.5 8 No No* 3 1.8 12 Yes No 4 2.3 19 . Yes Yes 5 3.0 25 Yes Yes 6 3.7 36 No Yes 6a 4.6 47 No Yes 7 5.1 53 No Yes 8 5.8 62 32 Yes Yes 9 6.3 68 40 Yes Yes 9a 7.6 83 56 No Yes 9b 8.1 89 62 No Yes 10 8.9 99 72 No Yes 10a 9.6 107 80 No No* 11 9.9 111 85 No Yes 12 10.3 116 90 No No 12a 10.9 124 98 No No 13 11.2 127 101 Yesla No* 13a 11.6 131 106 No No 14a 12.0 136 111 Yes No* 14a 12.3 140 115 No No* 15 12.6 142 117 No No 16 12.9 147 122 No No 13 13.4 153 128 No No* 1"8. 13.7 157 132 No No 19 14.1 162 137 No No 20 14.5 167 142 No Yes 21 14.8 170 146 No No 22 15.3 176 152 No No 23 15.6 179 155 Yes No* 24 15.9 183 159 No No .25 16.2 187 163 No Yes 2"6 16.6 192 169 No Yes* 2Ui 16.9 196 173 No Yes** 28 17.2 199 176 Yes3 No* ;29a 17.6 203 180 No No 29a 18.0 208 185 No No 30 18'. 6 216 193 No No 31 .19.2 222 200 . . No ....... No. 32 —.• —-•• • -• 20...1 -—234-- ..—21-2- • - Yes .: • . : . • • No . * Enhanced at 120 mg/l dosage only. ** Plant chlorinated and 120 mg/1 only a - unsat. HC spectrum 150 Table 4.22 Spectrum Numbers of Halogenated Acidic Compounds MEC Detector Mass Spectrometer Spectrum Compound Spectrum Number Shows Results from Peak Retention Time CL120A Chlorine. Chlorination 1 2.3 19 No Yesa 2 10.2 112 No Yes 3 11.7 133 No Nob 4 12.5 142 No Yesc 5 12.9 149 No No 6 13.3 152 No Yes 7 13.8 158 No No 8 14.5 166 No Yesc 9 15.1 173 No Yesb 10 15.4 177 No No 11 16.7 193 No No 12 19.1 222 No Yesc 13 2.14 250 No Yes a b c - Appears only in plant chlorinated sample. - Appears only in plant sample chlorinated at 120 mg/1. - Appears only in sample chlorinated at 120 and 12 mg/1. 151 fifteen halogenated compounds formed as a result of chlorination could be identified. Peak 5 is an unidentifiable chloroalkyl compound while peak 9 is both p-dichlorobenzene andtX-chloro toluene. Limited mass searches and spectral examinations of NBRAW1, CL12N1, NBPLCL and CL1202 show that p-dichlorobenzene is present in all of the extracts while the mass spectrum of peak 5, chlorobenzene, m-dichloro-benzene and^-chlorotoluene are present only in the chlorinated extracts. It was also found that the mass spectra corresponding to peaks;3, 13, 14, 23, 28 and 32 were present in all extracts. This indicates a good correlation among the peaks resulting from chlorination as monitored by the MEC detector and the mass spectrometer. It is also evident that as expected the MEC detector is much more sensitive than the mass spectrom eter. The fact that the two chlorophenols were used as calibrants allowed a more.unequivocal search for chlorinated phenols. Limited mass searches of 128, 162, 142 and 176 were made in the acid and neutral plus basic fractions run under CL1202 GC conditions. Although the 128 and 162 LMRGC's showed peaks at spectrum 110 in all extracts including the unchlorinated ones and a peak at spectrum 59 only in the chlorinated samples, examination of the back ground subtracted spectra showed little more than tall grass. No isotopic clusters were evident in any of the spectra. It is also noteworthy that m/e 128 is a minor peak in the spectrum of p(-terpineol which is the established identity of spectrum 110. On the other hand the MEC data shows that peak 2 in the acid fractions or peak 11 in the neutral and basic fractions or peak 11 in the neutral and basic fractions may be p-chlorophenol. The search for chlorinated cresols by LMRGC's yielded many peaks for m/e 142 or 176. Only spectrum 137 showed chlorine (m/e 176). In the region of spectra 80 - 140," no new peaks appeared in the LMRGC's (m/e 142) as a result of chlorination. Although peaks appeared at spectrum numbers 87, 91, 99, 110, 118, 125, 134 . 152 and 137, the peaks in the region 83 to 130 were so small that their presence was debatable in many extracts. Since peak 14 (Spectrum 137)• is present in all extracts it appears as though the chlorination does not produce chlorin ated phenols except possibly at chlorine dosages of 120 mg/1. 153 CHAPTER V SUMMARY, IMPLICATIONS AND SUGGESTIONS FOR FURTHER STUDY.• 1. Summary The first part of this work dealt with the analytical methodology neces sary to extract and separate the trace organic components of primary effluent. The work on extraction showed that while both methods gave adequate recoveries . the continuous solvent extractor suffered from emulsion problems while the sorption method suffered from poor recovery of organics sorbed on particulates. The sorption method was chosen because of its compactness and ease of duplica tion. The separation studies indicated that the acid base solvent extraction provided useful preliminary separation but suffered from the high solubility of the organic solvent in water. Thin layer chromatography was valuable only for compounds with volatilities less than benzylalcohol or p-cresol. The GC studies indicated that all the low temperature silicone liquid phases provide good separation although it is evident that they do not give a sep aration of one component per peak even after optimizing the temperature pro grams . The second part of this project centered upon the study of the effects of chlorination upon the volatile organic components of primary effluent and the identification of these components. It was found that with concen tration factors of 5000-10,000 the effects of chlorination were only readily apparent with the microelectrolytic conductivity and electron capture GC detectors. The uptake of chlorine by the volatiles at dosage levels of around 12 mg/1 was in the order of 0.01 percent of the applied dose. With a detection limit of 3 ng/1 about 20 ^ew/jhalogenated compounds were formed as a result of chlorination and those compounds account for about 40 percent of the total organic halogen as chlorine, exclusive of the halogenated methanes . 154 and ethanes, found in chlorinated primary effluent. The EC work showed that these effects were reproducible in different effluent samples. In order to identify the organics in primary effluent a computerized GC-MS was essential. A large number of spectra could not be identified through file searches and the incomplete separation of compounds could be part of the reason for this. A total of 31 compounds were positively iden tified by both their mass spectra and GC retention times (Table 4.19), another 24 compounds were tentatively identified by their mass spectra (Table 4.20) and an additional 7 compounds were very tentatively identified on the basis of GC retention time (Table 4.12). Three of the chlorinated compounds formed by chlorination were positively identified (Tables 4.19 and 4.21). 2. Implications The results of the second part of this study have some implications for the design of treatment plants and the effects of primary effluent upon the aquatic ecosystem. It is obvious that a large number of volatile organic com pounds are present in^g/1 concnetrations in primary effluent. If some of these compounds exhibitedeleterious effects upon the receiving water or gen eral ecosystem, treatment plants will have to be designed to reduce their concentrations to an acceptable level. Since biological oxidation rate is a function of substrate concentration this may necessitate the installation of physical-chemical rather than the biological treatment plants currently used. In order to assess the possible environmental effects of the volatiles in primary effluent Table '5.1 was prepared. Before interpreting the table some general points should be made. The assignments of the possible principal sources were based upon an interpretation of the natural or industrial sources and major uses of a particular compound rather than a waste survey. Street surface runoff is included among the possible sources even though a separate 155 Table 5.1 - Guide to Environmental Effects of Identified Compounds Compound Possible Concen. Toxicity Sourceb mg/1 Acute (mg/1) Sub-acutec Tetrachloroethylene Co 0.005 1,F Orthoxylene Co,SS,H 0.001 1,F i-propylbenzene Co,SS,H 0.002 t-butyl benzene Co,SS 0.01 chlorobenzene Cb,H,Cl 0.01 m-dichlorobenzene Cl 0.01 p-dichlorobenzene Co,H 0.003 1,F Benzyl alcohol Co.H 0.01 l,Da 2-phenyl ethanol 0.005 0( -chlorotoluene Cl.Co 0.007 1,F Benzaldehyde H 0.01 1,M Methyl benzoate H 0.0004 Methyl salicylate H 0.007 Benzophenone H 6.001 Methyl napthalene Co,SS 0.005 .M Phenanthrene Co,SS 0.0008 1,F Anthracene Co,SS 0.0008 Glycerol triacetate H 0.0005 Methyl stearate H 0.0007 Dimethyl phthalate 0.0006 Diethyl phthalate Co,H 0.0004 Di-n-propyl phthalate 0.0003 Di-n-Butyl phthalate Co,H 0.009 Menthol H 0.015 Camphor H,Co 0.02 1,F Terpineol H 0.001 Bornylacetate 0.0008 Coumarin H 0.002 m (5)L (5)L 10 '24 4,Met-Mu,Ca? 2, N? 3 N? 3, Ca? /2.CNS 3,ID t ) 3,Ir 3,Ca? 3,Ca? 3,Ca? 2,Ir 2,Ir 2,N 2,N? a - Effects upon mammals b - References 2,3,5 e;— Lower value Table; 5.1 Cont'd. Symbols Possible Sources - Co - Commercial/Industrial Cl - Chlorination of Primary Effluent H - Household SS - Street Surface Runoff Toxicity - Acute e.s - Sub-acute 1,F - (60) D 1 - Reference Number F - Test Animal 60 - Toxic Concentration D - Type of Toxic Effect 3,C? /2,CNS 3 - Reference Number C - Effect / Next Reference 2 Second Reference Number CNS ,-r.Effect References 1. McKee and Wolf (1971) 2. Merck Index (1968) 3. Sax (1974) 4. Fishbein 1973B 5. Noller 1957 Symbols Ca - Carcinogen or Cocarcinogen CNS - Affects Central Nervous System D - Deleterious but not lethal Da - Daphnia F - Fish ID - Internal Damage Ir - Irritant L - Lethal M - Minnows Met - Metabolic Products Mu - Mutagenic N - Narcotic 157 sewer system is employed in sewage collection area. This was done since groundwater infiltration does occur e.g. during wet weather although the sorption and leaching of organics on soils will affect the input of organics from this source. Regarding the toxicity data it is evident that there is little acute toxicity information available for fish let alone other aquatic organisms, moreover there is practically no data at all available on the subacute effects so those listed are primarily for non-aquatic mammals. From Table 5.1 it appears that no problems of acute toxicity to fish should result from the individual compounds of either unchlorinated or chlorinated /dechlorinated primary effluent, although the cumulative toxicity of all of the components and synergistic effects are difficult to predict. This con clusion is supported by Esvelt j2t al., (1973) who were able to correlate most of the toxicity of primary effluent to concentrations of MBAS and ammonia and Martens and Servizi (1975) who found that chlorination followed by dechlorination of primary effluent might even slightly reduce the toxicity of primary effluent to fish. On the other hand, the acute toxic effects upon aquatic insects, for example, may be important since dichloro benzenes have been used as insecticides (Merck, 1968). Although acute toxicity problems may not result from these compounds sub-lethal effects probably will. Possible effects (McKee and Wolf, 1971; Kemp et al., 1973; Gillet 1970; Walsh and Mitchell 1974) include central nervous system impairment - Brook Trout'-ISO g 0.02 mg/1 DDT, hyperactivity -tadpoles 0.5/Ug DDT residue, survival of fish from eggs exposed to a toxicant -3% survival of steelhead 0.4^g/1 DDT and taste in flesh - oysters l^g/1 chlorophenol. It should be pointed out that DDT is an extremely toxic sub stance and is certainly several orders of magnitude more toxic on a TL^ basis than most organic compounds. On the other hand if the mechanism of the sub-lethal toxicity is independent of that of the acute toxicity, it is . 158 not possible to estimate what concentration of a particular compound will cause sub-lethal toxic effects. Furthermore, the previously stated harmful dosages of DDT and chlorophenol do not take into account bioaccumulation which has been shown to be 3 - 5 orderstof^magnitude with DDT and Daphnia (Kemp et al. 1973). In summary, therefore, it is unlikely that the trace volatile organics identified as originally present in, or resulting from the chlorination and dechlorination of primary effluent will be acutely toxic.to fish. It is possible however that these compounds, particularly those which are recal citrant may be toxic to other organisms or have other deleterious effects upon the aquatic ecosystem. In view of the fact that 1 percent of the chlor ine applied to primary effluent ends up as 'stable' non-volatile organo-chlor-ine compounds (Jolley 1973) while only 0.0(15 percent ends up as stable vol atile organochlorine compounds, it is possible that the most serious effects of chlorination will be manifested in the non-volatile fraction. 3. Recommendations for Further Studies i) Quantification of identified components: It is recommended that recovery studies be carried out using primary effluent as the solvent. Quan tification of the 'identified' compounds can then be conveniently made by unnormalized LMRGC's. ii) Further separation: Since the acidity separation did not prove highly effective it is recommended that fractionation on a HPLC instrument be made prior to final separation by GC. iii) Identification of more constituents: Subsequent to the improvement in separation, more identifications can be made on the basis of mass spectrum and LC and GC retention time. iv) Effects of chlorination: a) Distribution of chlorine uptake. It would be instructive to study the distribution of chlorine uptake in the various molecular weight fractions. This could be done through the use of 36 Cl and gel permeation chromatography, b) It appears from this study that chlorine uptake is related to ammonia content of the sewage effluent. The formation of halogenated benzenes but not halogenated phenols suggests that the major mechanism of chlorine uptake may be other than electrophilic sub stitution. Further work on the mechanisms of chlorine uptake is therefore recommended. v) Environmental Implications of the Resultant Chlorinated Organics. a) Acute toxicity - Bioassays should be conducted to obtain the LC^Q values for each of the compounds identified with a representative set of organisms. b) Sublethal effects - Studies upon the inhibition of bacterial metr abolic rates by these compounds can be easily carried out. 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When a large amount of chlorine is added to a litre of water be tween 9. 5°C and 100°C, the following equilibria are set up: C12(g)^1 C12(aq) K = 0.062, 25°C (1) Cl„, . + HO -ass- H+ + Cl" + H0C1 K =4.2 x 10~4, 25°C (2) 2(aq) 2 This means that a saturated aqueous solution of chlorine at 25°C will have the following composition at pH 4: Total Cl2-0.09.1 moles/1 ^(aq) • °'°01m [HOCl] , [C1~J = 0.090 M When less than one or two grams of Cl2 is dissolved in a litre of water equilibrium (2) is reached in a few seconds. Thus it can be seen that if the total C±2 is less than 1.0 g/1 and the pH is greater than 4 there is a negligible amount of Cl2 ^a<^ present. Hypochlorous acid is a weak acid and exists only in solution. It under goes the following dissociation in aqueous solution. HOCl + H20 ^ H30+ + 0C1~ (pale yellow) (colourless) „ K = 2.5 x 10 @20°C a Thus in the pH range 6.8 to 7.8 a dilute aqueous solution of HOCl contains 75% to 25% HOCl. Below 9.5°C, Cl , . forms a crystalline hydrate with water. HOCl can ^ \§/ o —8 exist at 0 C (K = 1.5 x 10 ) in aqueous solution, a Under ultraviolet light or at high temperatures, chlorine very slowly reacts with water according to the following equation. 180 Cl2 + H20 ^ 2HC1 + lg02 2. Decompositions of HOC1 arid OCl Hypochlorite ions decompose in aqueous solution according to the fol lowing reactions: 20C1" -kj» C10~ + Cl" ' ^ 0C1~ + C10~ -k^ C10~ + Cl" ^ 20Cr-kr 2C1" + 02 (3) k^ 10~6 (g-moles/l)"1 min"1 at 25°C^ k2^10"4 k3-vl0~8 •-I 9 If free H0C1 is present in appreciable amounts, reactions 1,2 and 3 are con siderably accelerated. Thus commercial solutions of hypochlorite usually contain a carbonate stabilizer. Certain metals such as cobalt, nickel and copper catalyze reaction 3 but do not affect the rate of reaction 10(Lister 1965). The reactivities of H0C1 and OCl withiiriorganics are due to the oxidiz ing power of H0C1 and OCl . The half cell equations are: C10~ + H20 + 2e~ = Cl" + 20H~ E° = '+0.89V H0C1 + H30+ + 2e~ = Cl" + 2^0 E° = +1.50V (Cl2 + 2e~ = 2C1~) E° = +1.36V Some reaction times for complete oxidation of inorganics at mg/1 concentra-+2 tion levels are: Fe (pH <7 ~ 9), less than one hour; H2S (pH 7 - 10), 2-4 hrs; Mn+2 (pH 7 - 9), 2-4 hrs; CN" (pH 8.5 - 9), % hr (White 1972). +2 -2 -The chlorine demand of Fe , S and N02 were determined by Taras (1950). It should be noted that these reaction times are for free inorganics. If the inorganics are complexed the reaction times may be considerably longer 181 in the pH ranges cited. 3. Reactions of HOG1 arid 0C1 with Ammonia  Reaction Products The reaction of HOCl and 0C1 .with aqueous solutions of ammonia gives rise to a complex set of equilibria dependent on pH, time, temperature, and concentration. They are compositely referred to as the chlorine break-point reaction. Before discussing this phenomenon, a few definitions are in order. Chlorine residual is divided into two general classifications, free and com bined. Free residual chlorine is the amount of HOCl and 0C1 present ex pressed as mg/1 01^. Combined residual chlorine is the amount of chlorine in the +1 oxidation state which is chemically bound to nitrogen atoms. It is also expressed as mg/1 Cl^. Griffin and Chamberlain (1941a,b) studied the fate of chlorine at var ious Cl^/NH^ ratios and produced what is called the breakpoint curve. The minimum residual chlorine at pH 7 was observed at a Cl^/NH^ - N ratio of 10:1 by weight or 2.0/1.0 on a mole basis. Subsequent work by Isomura (1967) determined more precisely the fate of Cl^ in aqueous NH^ systems. His re sults show that before the breakpoint, the residual chlorine is in the form of chloramines. After the breakpoint, chlorine is in the form of free chlor ine and NCl^. The fate of the NH^ - N during breakpoint chlorination has been a matter of controversy for some time. Mellor (1927, 1928) summarized the work prior to 1923 and presented the following equations: 1) HOCl + NH"!"«= nitrogen chloride, N H , NHo0H 4 2 4 2 2) 3NaOCl + 2NH3~N^;2f (nitrogen chloride, chloramide and chlorates)!;. Reaction (2) is second order overall and never complete in the conversion of NH3 to N2 at 15° - 25°C. It is accelerated^|y--Cu, Hg, Pb, Fe (III), Co, Ni, Ti, Pt, Mn and Cr salts. The tentative identification of the gaseous pro duct as N^, became questionable when it was observed that trace amounts of 182 nitrites and nitrates were also produced. Chapin (1931) when studying the effect of pH on chloramine in formation also found a gas produced at pH 5.0 which matched the 1898 description of N20, but found no N20 at pH 9.0. Following the recording of the UV absorption spectra of the chloramines by Metcalf (1942) and their confirmation by Czech et al. (1961), the develop ment of the OTA, DPD and amperometric titration techniques for residual chlorine (APHA 1971) and the development of gas chromatographic techniques of gas analysis, great advances were made in the determination of the fate of NHg - N during breakpoint chlorination. The reported nitrogenous pro ducts are NH2C1, NHC12 and NC13 (Chapin, 1931; Metcalf, 1942; Palin, 1950; Isomura, 1967; Pressley et al.,,1972, 1973; Bauer and Snoeyink, 1973; Stasiuk et al., 1974), and N2,N0~ + N0~ (Palin, 1950; Pressley et al., 1972, 1973; Stasiuk et al., 1974). The relative amounts of chloramines, N2, N02 + NO^ and other possible products such as hydrazine depend upon many factors which are discussed below. i) C]"2:^ Ratio. If the NH^ is in excess the products are dependent mainly upon pH. If the initial Cl^NH^ - N weight ratio, is between 1 and 5, the major product is NH^Cl. As the initial CltNH^ - N ratio is increased from 5 to 10 increasing quantities of NHC12> NCl^ and free chlorine appear, (Palih?j.s 1950; Pressley et al., 1972). Isomura (1967) also indicates that as the initial amount of NH^ is increased the concentration of HOCl at the breakpoint also increases. ii) pH Effects. In the presence of excess NH^ and with pH values greater than 8.5, monochloramine alone is present. At high pH's, formation of hy drazine by the Rachig synthesis is also expected: NH3 + NH2C1 —> N2H4.HC1. Dichloramine and monochloramine are present in equal quantities at pH 5. At 183 pH 4, NHCI2 predominates while NCl^ predominates below pH 2.8. The preced ing pH values were taken from work by Palin (1950), Metcalf (1942), Chapin (1931) and Corbett et al. (1953). Palin (1950) and Pressley et al. (1972) indicate that at C1:N ratios large enough to produce free residual chlorine, the formation of NO^ + N02 is favoured by higher pH while the formation of NCl^ is favoured by lower pH. The ratio of NC13 - N to N0~ + N0~ - N is 5.7 at pH 6.0, 1.0 at pH 6.4, 0.11 at pH 7.0, and 0.02 at pH 8.0.; ^AthpH 7, NH^ - N is 95-99% oxidized toN2. Reaction Rates Kinetic studies of the various reactions involved in aqueous NH^ - Cl2 systems have been carried out by Weil and Morris (1949a,b), and reviewed by Morris (1965). The following data are presented: 1) NH3 + HOCl > NH2C1 + H20; k reaction order overall is 2, firstoorder in NH3 and HOCl and pH 6 4 dependent k = 8 x 10 at pH 8, 1 x 10 at pH 4 and pH 12 k = 9.7 x 108 exp(-3000/RT) 1 mole"1 sec-1 2) NH2C1 + HOCl -—> NHC12 + H20; k2 reactionoorder overall is 2, first order in NH2C1, HOCl; it exhibits general acid catalysis and is also catalyzed by Cl . k2 =7.6 x 107 exp(-7300/RT) 1 mol"1 sec"1 k2' =3.4 x 10'2'2 (1 + 153 x lO-4 CH*1+ 2 x 102 (HOAc^)) 1 mol"1 sec"1 at 25°C. 3) 2NH2C1 ^NHC12 + NH3; k3 reaction order is 2, second order in NH2C1 k3 = 80 exp(-4300/RT) 1 mol"1 sec"1 k3!" = 5.6 x 10~2(1 + 1.3 x 105 CH+J+ 35 CHOAcj 1 mol-1 sec la) NH„C1 + Ho0 —* HOCl + NH ; k, 2 2 3 la -1 184 reaction order overall is 2, first order in NH^Cl kla = 8.7 x I07 exp(-17,000/RT) sec"1 Gupta et al. (1972) measured the rate of the breakpoint reaction at acid pH Vs. With equal 0.0125 M, Cl2 and NH^ concentrations the rate was first order in each reactant and second order overall. The k , ranged from 0.15 to 1.1 1 obs mole 1 sec 1 between pH 3.5 and 4.5. The rate at pH >5 was too fast to meas ure. They do not state whether residual ammonia was observed at pH 5 as was found by other investigators. Mechanism Morris (1965) favours the nonionic mechanism for the reaction of chlorine and amines to form chloramines in aqueous solution while Soper (Mauger et al., 1946; Edmond et al., 1949; Hurst et al. , 1949; Corbett et. al., 1953) favours the ionic mechanism. Weil and Morris (1949a) found that ionic strength has no effect upon the reaction NH3 + HOCl —» NH2C1 + H20 at pH -1.9. Gupta et al. (1972) observed a negative effect of sulphate and acetate on the overall system at pH 3 - 4. Unfortunately the two mechanisms are not distinguishable since although increasing ionic strength should de crease only the rate of the ionic reaction, consideration of the effect of ionic strength on the hydrolysis of NH^ and HOCl at any given pH will yield identical rate expressions. Both mechanisms are compatible with general acid catalysis. While the formation of chloramines has been mechanistically described the reactions leading to the formation of N2 and NO^ and N02 have not. The most likely mechanism of N2 formation would involve an hydrazine intermediate followed by oxidative degradation. The formation of N0.j + N02 probably involves the intermediate production of an hydroxylamine and/or NO or N20 (Cahn and Powell, 1953; Audrieth and Rowe, 1955; Anbar and Yagil, 1962; Yagil and Anbar, 1962). 185 Chlorinated hydrazines, possibly due to their instability, haveivnot been detected in aqueous NH^ - Cl^ systems. Therefore in considering the inter actions of chlorine with sewage, only the interactions of chloramines will be considered. 4. Thermodynamic Properties of Chloramines Jolly (1956) has estimated the following acidity data from homolgous series. pK of NH0C1 -v 14 + 2 a 2 — pk of NHCl0-v 7 + 3 a 2 -He measured the following oxidation potentials: +1.48 v +1.39 v +1.37 v +0.81 v +0081 v Chloramines are decomposed by activated carbon, (Bauer and Snoeyink, 1973), as well as by the common inorganic reducing agents. 1 M H or 1 M NH,+[NC1, 1 M OH NH2C1 1 M NH3 NHCl" Cl Cl" Cl" Cl" Cl" E o E" = E" = Appendix II Summary of Chromatograms of Effluent Samples Sample Date Experiment & Extraction Method Chlorine Dosages (mg/1) Preliminary Separation Method Fraction Total # # of New Peaks of Peaks Due to Chlorination EC FID EC FID Total 25/06/73 E-2; SE 03/07/73 E-2; SE 10/12/73 E-3-d ; XAD 17/12/73 E-4; XAD 28/01/74 E-5; SE XAD XAD S-la SF, XAD 18/03/74 S-l-6 XAD S-2 Cl-2 29/04/74 Cl-1 XAD Cl-4 Cl-2 08/07/74 Cl-4 XAD Cl-2 19/11/74 Cl-5 XAD Cl-2 18/12/74 Cl-2 XAD 20/01/75 Cl-7 XAD Cl-2 0 0 0 0 0 0 106 0,0,106 0 15 100 200 0 12 103 0 25 0 12 0 15 100 200 0 12 120 F F F F,SG F,ASB F,ASB F,ASB F,AS F,ASB F,AS P(M) So P(MC) So P(MAH) So 1 2 3 N + B WA SA 33 34 18 50 17 50 15 38 42 34 20 52 38 21 51 36 8 17 3 3 } N + B 47 47 18 4 WA 36 32 SA 20 7 i 3 1 N + B 48 — 18 — WA 35 — 3* SA 20 — — N + B 53 60 17 4 A 20 10 2 0 N + B 52 50 13 4 WA 37 31 12 4 SA 20 7 1 0 N + B 50 61 17 5 A 19 10 3 0 17 18 4? 17 2 17 2? 17 3 Appendix II cont'd. 8/03/75 Cl-7 XAD Cl-3 Cl-2 0 12 120 Plant TEC F,AS N + B A 53 63 22 9 18 2 5 0 18 2 •P=3QO0 Yes S-3 JL-3000 Abbreviations A - Acidic Fraction AS - Acidity Separation ASB - Acidity Separation with Bicarbonate Step F - Filtration M - Methanol, Soxhlet MC - Methanol, Chloroform Soxhlet MAH - Methanol, Acetone, Hexane Soxhlet N+B - Neutral and Basic Fraction P - Particulate Fraction SA - Strong Acid Fraction SE - Solvent Extraction SG - Silica Gel Column So - Soluble Fraction TLC - Thin Layer Chromatography XAD - XAD-2 Resin oo 188 Appendix III CG Conditions for Figures Instrument/Column Detector/ Temperature Carrier Gas Flow Atten/Pulse (EC) Program 4.2 HP 5750 EC; 64x10; 5/S 50%C/5 min,10° 65 ml/min 5% DC-11 on min, 300°/30 chromosorb W min (HP) 80-100 mesh 220°C isothermal 4.3 HP 5750 EC; 32x10; 5^S 70 ml/min, 3% SE 30 on chrom W (HP) 80-100 mesh 4.4 Identical to 4. 2 4.5 HP 5750 3% OV-101 on chrom W (HP) 80-100 mesh EC; 64x10;50//S 30°C/10 min 6%/min, 200°/ 20 min 65 ml/min 4.6 HP 5750 Various As in 4.5 As in 4.5 except OV-l 100°C/20 min 6%/min,260° /20 min As in 4.5 4.7 HP 5750 Various As in 4.5 4.8 HP 5750 Various FID; 32x10 As in 4.5 65 ml/min 4.9 As in 4.8 4.10 HP 5750 EC; 64x10; 48°C/10 min, 70 ml/min 6% SE-30, 50^ 10°/min,208° 4% OV-210 on hold Gas Chrom Q, 100-120 mesh 4.11 As in 4.10 48°C/6 min, 8°/ min, 208° hold 70 ml/min 4.13 HP 5750 As in 4.7 4.14 3% 0V-10/on Chrom W (HP), 80-100 mesh As in 4.8 4.15 As in 4.13 4.16 As in 4.14 4.17 As in 4.13 4.18 As in 4.14 70 ml/min 4.19 HP 5750 3% EC: 64x10; 29°/10 min; 6° /min, 219°/20 min OV-101 on 50^S 75 ml/min Chrom W (HP) 80-100 mesh • 4.20 As in 4.19 FID 32x10 As in 4.19 4.21 As in 4.19 4.22 As in 4.20 4.23 Microtek Tracor 310 84°/4 min 10°/min,200°/ 20 min (Tracor 222) 8x10 4.24 As in 4.23 4.25 As in 4.23 Tracor 310 Various As in 4.23 189 Appendix III Cont'd. Figure Instrument/Column Detector/ Temperature Carrier Gas Flow Atten/Pulse (EC) Program 4.27 Pye 104 MS-12 As indicated 3xl58 A full scale 4.29 As in 4.19 4.30 Finn 3000, as in 4.10 F-3000 60°/2.5 min, 10°/min, 200° 32 psi 4.31 As in 4.30 4.32 As in 4.30 80°/2.5 min, 10°/min,200° 32 psi 4.33 As in 4.30 190 APPENDIX IV MASS SPECTRA OF COMPOUNDS POSITIVELY IDENTIFIED IN CHLORINATED PRIMARY EFFLUENT T' I 1 I 1 45 55 75 I " t 1 l 105 CLI202 11-9 135 1 » ' I !65 185 JULMI , I n i 60 CLI202 19-17 70 T >—*T —1 r——5 r*-^ T 100 k 45 55 120 CLI202 23-25 75 95 ^JJ—p 125 ,—8—llliitL-^-i-45 55 -» { 11 g1 p 75 CLI202 31-29 i+LL-y 1 11p i, 95 T"—' 1 r 1 125 4JLL 4 4 54 74 104 CLI202 46-44 (24 191 m 80 lijigiii ii ..h r—r-tu+ CLI202 81-59 r-l 70 100 feo 1 « 1 r*—t r 150 CLI202 62-60 U—,J-J 50 T-^ V 80 i—t •!<! p 100 i-U 120 I; 11 I I |l 11 i ^ 40 50 l»l lli 111 *)•• -|» J( I CLI202 66-64 i 80 100 i—r—r^-r 120 ho ' 1 1 150 CLI202 76-74 A | 1 •"t N' 1 43 53 73 93 I ' I • I ' I ' I • I 123 CLI202 85-80 45 55 75 105 i—•—r n lijnii.ii II II 8i 111li111.. ,i IIi! j j III111.. 11 75 CLI202 98-95 L_I—,..ii—. i—L*i 45 55 35 I, ...I 45 55 u,—1_ i4 CLI202 106-104 . . I.tilli. "» T ' 1 • "» | 95 IE LLLJ jll CLI202 110-108 J_jl 4-50 60 80 CLI202 II7--II3 44 54 74 104 154 i 1111111 CLI202 133-131 nllji i^-.^—Li4—«—, lt»litt 60 70 100 - ! J 'l 140 I V"v f'l—I—r 4 •j—r"» 84 CLI202 204-202 04 fA* 193 4 —L ft,. ,1 ll, ll •j—•—r-l—i1 »i |i "i»—j— 50 60 100 c-MALL 39-42 *±1J , ^—,—r -I I I—r 75 j—.—M! i—I, IL,—1 LL 1 C-HALL 51-49 105 '"|5 1'"' '' ); iii ii C-HALL 59-57 i—1 r 105 ' ' ; . ' I f-Ll-r- J .1. 60 70 1 ' 1E0" 1 «-—1—~* r C-HALL 69-67 T r- i—^^-i—1—»4-—_i—{in 130 •» I » Q rfil t [III II 8 1 |l Ml » • 11 .1 •[ C-HALL 7J-69 50 60 90 LL| ji ll 50 1 r »»11 4 tb ,—Lilll i—f—! <—r 120 C-HALL 81-77 70 HI r 100 T j 1 r" r 120 19.4 C-HALL 69-85 ^ • i 1 '*> { \—'—| 'i " j * i 1 1 r*-'^T 70 80 100 130 150 -C-HALL 111-108 f1 'r—|—r i ro so • 1—r 100 -UL lilt. ..till! 1 r**"f I i IT i • t L )il I f I I \111 LU C-HALL 114-112 4 50 60 7 100 130 ' 155 C-HALL 152-154 ~< T 1 1 • 1 ^ r.—r J r 50 60 -j—L,—|—^—j—r-~-4rj—I 100 120 140 C-HALL 159-157 70 4 ~i—«—r "80 i—L*—r~~>—1—»—r1 > 100 130 i—«—r —r 160 Lu_J C-HALL 164-162 -j T 60 70 j—4 1 100 1 120 "1 140 195 C-HALL 178-176 196 APPENDIX V MASS SPECTRA OF UNIDENTIFIED COMPONENTS OF CHLORINATED PRIMARY EFFLUENT The spectra are organized by file names (see Table 4.14) . They are presented in ascending order of spectrum number within a file. The inter pretation of the structural features of each spectrum is according to McLafferty (1973) and his terminology is used!. Symbols and Abbreviations used are: m/e - mass to charge ratio of a mass spectral peak ' Int. - relative intensity of the specified peak Str. Feat. - structural features of the compound suggested by its mass spectrum File CL1202 Spectrum Number Spectrum and Interpretation 8-5 m/e 92 91 74 73 71 70 69 58 57 56 55 54 53 51 50 46 45 44 43 42 41 40 39 38 Int. 3 7 10 4 72 100 87 45 92 96 99 72 98 52 42 92 98 99 92 96 87 99 93 85 Base W; Parent 120;; Str. Feat.- Cyclic amine, Methyl?. 14 - 15 • m/e 14 - 15 m/e 100 89 87 85 79 71 70 69 59 58 57 56 55 45 43 42 41 39 Int. 3 1 1 8 1 1 1 9 1 15 29 8 9 61 100 26 62 44 Base 43; Parent ? ; Str. Feat.- Thiophene(dihydro), Methyl. 24 - 23 m/e 127 125 109 99 86 82 81 61 60 59 49 47 43 37 36 35 Int. 7 11 5524 16 2475 22 100 9 4 28 Base 43; Parent ? ; Str. Feat.- Propyl, Dichloro, Alkane. 26 - 24 m/e 123 121 113 88 86 85 84 77 71 70 69 57 56 55- 45 43 42 41 40 39 38 37 36 35 Int. 1 1 1 1 1 6 2 2 5 6 16 28 51 37 8 71 41 100 10 32 1 1 2 3 Base 41; Parent ? ; Str. Feat.- Alkenyl, Chloroalkane. 40 - 38 m/e 87 85 75 72 71 58 57 56 55 45 43 42 41 40 39 Int. 11 1 5 2 3 3 100 11 9 85 19 18 10 97 33 Base 41; Parent 87? ; Str. Feat.- 2-nButoxyethanol; ONO ?. 56 - 51 m/e 121 120 119 106 105 104 103 91 79 78 77 65 63 57 51 50 41 39 Int. 2 32 8 8 100 4 9 20 13 11 22 11 12 8 24 11 28 49 Base 105; Parent 120; Str. Feat.- Methyl-ethylbenzene or n-Propylbenzene. 115 - 113 m/e 120 109 108 95 93 91 89 87 81 79 77 75 67 57 55 45 43 41 39 Int. 2 5 8 11 2 2 3 3 10 3 8 10 9 50 12 100 32 82 38 Base 45; Parent 7 ; Str. Feat.- Alkyl, Alkenyl, EtO, Aromatic(weak). 124 - 122 m/e 133 131 123 119 118 103 97 95 94 91 85 83 79 77 69 68 67 66 65 55 48 45 43 41 39 35 Int. 2 4 2 11 12 4 8 10 27 20 21 50 15 21 32 14 28 16 25 25 22 20 47 100 76 3 Base 41; Parent ? ; Str. Feat.- Alkenyl, Aromatic(high, weak), Thiophene(weak). m/e 180 178 177 176 175 160 148 145 143 141 133 121 119 117 105 95 93 91 79 77 59 57 55 53 51 Int. 2 7 3 11 3 3 2 4 8 18 10 12 6 9 17 20 14 17 12 32 23 15 18 16 25 m/e 50 45 43 41 39 Int. 8 28 100 55 25 Base 43(77); Parent 176; Str. Feat.- Aromatic(high), OH, PhCH2, Dichloro. z m/e 160 145 139 130 129 128 124 119 118 115 104 93 91 90 81 79 78 77 76 75 68 67 66 65 64 63 Int. 2 8 13 8 6 7 8 10 86 5 5 8 71 14 8 6 7 6 6 6 16 58 18 30 33 37 m/e 53 52 51 50 43 41 40 39 38 37 Int. 49 45 35 26 95 68 30 100 37 20 Base 39(118); Parent 160? ; Str. Feat.- Indazole or Benzimidazole, Diene, Alkyne or Cyclo-alkene, Aromatic(high and low) , Alkyl side chain. m/e 159 156 155 141 128 115 95 91 89 84 81 79 77 71 69 68 67 59 55 53 51 43 42 41 39 Int. 3 12 5 13 7 7 7 6 4 7 9 8 8 28 12 10 13 51 36 12 11 100 20 64 47 Base 43; Parent 156? ; Str. Feat.-"Alkenyl, Aromatic(weak) , Exo-sulphur aromatic(weak) , Methyl, Carbonyl?. m/e 152 139 121 111 105 97 95 94 93 91 84 83 81 79 77 75 70 69 67 57 55 53 51 43 41 39 Int. 1 1 7 2 2 8 5 4 5 4 5 15 6 10 7 6 18 29 19 36 57 12 2 87 100 32 Base 41; Parent ? ; Str. Feat.- Alkenyl, Aromatic(weak). m/e 123 117 109 101 95 89 87 85 79 77 75 73 71 59 58 57 56 55 45 44 43 41 39 Int. 1 1 2 2 2 7 5 5 2 2 8 3 3 16 7 32 8 8 100 17 45 49 15 Base 45; Parent ? ; Str. Feat.- Alkenyl, Alkyl( alcohol, ether, alkyl-silicon, thia-cycloalkane or substituted unsaturated sulphur compound). m/e 170 169 155 142 141 129 128 115 105 95 93 91 81 79 77 71 69 67 65 63 59 57 55 53 51 50 43 441 Int. 10 5 7 3 8 3 7 15 8 7 5 15 11 12 18 10 13 15 12 12 17 19 30 18 19 10 100 56 Base 43; Parent 170; Str. Feat.- Alkyl, Aromatic, Aldehyde?. m/e 170 156 145 1351103 95 94 93 79 73.71 67 59 55 53 45 44 43 442441 39 Int. 1 1 2 1 6222213284314 100 8 10 7 Base 43; Parent ? ; Str. Feat.- Glycerol acetate like. File CL1202 183 - 181 m/e 194 182 171 170 164 163 155 153 151 135 133 124 116 115 104 99 93 92 91 89 81 77 76 75 74 Int. 1 2 1 2 8 78 9 13 33 9 9 6 11 7 16 16 8 18 16 31 12 47 30 16 21 m/e 71 63 57 55 51 50 45 44 43 441339 Int. 21 27 20 18 22 40 10 20 100 35 40 Base 43(163); Parent 163(164); Str. Feat.- Dimethyl Phthalate, Aromatic(low), Alkyl. 187 - 184 194 - 192 199 197 215 - 213 219 - 216 230 - 228 236 - 233 m/e 147 146 120 119 118 95 94 93 92 91 90 89 83 79 77 71 69 65 63 60 59 58 57 55 53 51 45 43 41 Int. 1 7 3 3 17 77 6 5 5 7 9 8 3 6 3 11 14 10 6 12 51 13 12 24 10 6 16 100 58 Base 43; Parent 146? ; Str. Feat.- Alkyl, Aromatic(weak), Thiophene(weak)?. m/e 146 119 118 117 99 92 91 90 77 76 75 74 65 64 63 62 58 52 51 50 41 40 39 38 37 Int. 6 8 100 9 6 7 82 25 4 P8 10 4 18 48 40 15 10 27 16 18 22 12 46 32 20 Base 118; Parent 118(146); Str. Feat.- Benzofuran, Benzimidazole, Indazole. m/e 135 120 111 105 98 97 93 84 83 82 70 69 68 67 57 56 55 43 42 41 339-Int. 2 7 2 2 2 12 3 8 20 7 20 31 12 7 31 30 67 42 22 100 22 Base 41; Parent ? ; Str. Feat.- Alkenyl. m/e 184 175 139 125 119 111 99 97 95 93 91 89 83 79 77 75 71 70 69 67 57 55 53 51 45 43 41 39 Int. 3 2 1 1 2 2 16 8 7 7 7 7 13 4 2 3 13 10 20 8 38 45 8 3 48 98 100 23 Base 41; Parent ? ; Str. Feat.- Alkenyl, Alkyl, Thiophene?. m/e 185 171 157 1431124 115 105 97 87 85 83 77 74 73 71 69 61 60 59 57 55 45 43 41 39 Int. 3 1 1 1 7 3 4 3 . 6 5 7 6 4 42 5 14 8 60 10 27 55 12 73 100 22 Base 41(60); Parent 185; Str. Feat.- Alkenyl, Alkyl, 'Retro-Diels-Alder'. m/e 180 179 149 135 134 125 119 117 115 107 97 93 83 77 71 70 69 57 56 55 45 43 41 39 Int. 2 21 1 18 2 1 2 2 3 12 10 7 13 6 5 10 24 42 22 53 15 75 100 18 Base 41; Parent 179(180); Str. Feat.- Alkenyl, Alkyl, OCO,or CS, CO or.N2. m/e 221 220 219 218 184 183 182 181 166 165 155 154 153 152 142 140 115 114 113 112 102 101 99 Int. 1 17 8 52 6 43 9 13 8 39 8 8 23 37 16 49 18 20 10 57 8 6 8 m/e 91 89 78 77 76 75 74 73 65 63 58 52 51 50 39 Int. 32 20 34 87 26 32 18 32 33 51 22 18 100 41 52 Base 51; Parent 218(219); Str. Feat.- Aromatic(high and low), Ph, Monochloro, OH?, possibly is a Chlorophenyl-benzyl alcohol. m/e 213 209 185 171 157 143 129 115 111 101 98 97 87 85 84 83 74 73 72 71 70 69 61 60 59 57 55 Int. 2 1 1 1 1 1 8 4 2 3 4 8 11 10 6 13 8 77 8 22 8 32 20 100 12 63 83 m/e 45 43 42 41 Int. 28 71 33 72 Base 60; Parent ? ; Str. Feat.- Alkenyl, Alkyl, Aliphatic acid or ester. m/e 133 127 125 124 123 121 119 115 114 112 111 110 109 107 98 97 96 95 93 91 84 83 82 81 79 77 Int. 11112111213331 5 12 8 10 2 2 8 22 10 22 12 5 m/e 73 71 70 69 68 67 60 57 56 55 54 53 45 43 42 41 39 Int. 12 8 12 42 18 41 27 27 23 100 32 15 22 79 23 93 29 Base 55(41); Parent ? ; Str. Feat.- Alkenyl, Alkyl. m/e 292 290 289 288 220 219 218 202 195 191 189 182 162 155 154 148 147 146 145 143 126 116 115 Int. 23 62 15 54 31 15 92 23 15 23 15 38 23 23 15 38 15 46 38 38 15 23 85 m/e 114 111 110 109 105 99 96 95 86 83 82 81 73 71 69 68 67 63 62 61 60 52 51 38 Int. 46 38 23 85 38 23323 38 77 15 23 46 46 61 100 31 31 77 31 31 46 15 84 15 Base 69; Parent 288; Str. Feat.- Trichloro, Exo-sulphur aromatic, Diphenyl thio-ether?. m/e 201 200 183 140 130 128 126 117 116 114 112 109 103 99 98 95 88 86 85 75 73 72 71 70 69 62 Int. 1 9 4 1 1 11 1 9 2 3 1 26 5 12 3 3 11 27 2 3 7 5 11 6 12 m/e 60 57 55 53 45 44 43 42 41 39 Int. 30 25 45 3 23 30 82 28 100 20 Base 41; Parent 200(201); Str. Feat.- Alkenyl, Alkyl, Acid. m/e 237 160 149 143 141 139 131 126 114 105 104 99 98 96 95 89 88 85 83 77 75 74 71 70 69 67 59 Int. 4 4 4 4 4 10 4 4 32 15 10 16568 5 8 12 8 10 12 18 10 100 28 22 38 12 18 m/e 57 56 55 45 44 43 42 41 39 Int. 50 30 58 85 22 91 37 91 22 Base 74; Parent ? ; Str. Feat.- Alkenyl, Alkyl, Methyl ester?. m/e 268 267 237 215 208 198 190 189 175 161 159 151 147 137 135 133 131 119 117 114 107 103 92 Int. 17111131133126 12 44333 573 m/e 89 87 78 77 73 71 59 57 45 43 41 39 Int. 16 8 8 18 3 8 27 28 100 22 15 10 Base 45; Parent ? ; Str. Feat.- AlkyKSi, S or O) , Aromatic (weak) . File CL1202 424 - 411 m/e 256 227 168 167 160 150 149 142 137 132 126 124 122 115 114 113 112 104 99 88 87 86 85 83 77 Int. 1 1 1 10 1 7 69 2 3 2 2 1 2 1 16 3 4 16 4534365 m/e 76 74 71 70 69 65 58 57 56 55 50 45 44 43 41 39 Int. 7 100 16 26 12 3 5 59 30 45 2 14 16 83 94 17 Base 74;- Parent ? ; Str. Feat.- Alkyl, Alkenyl, Phthalate ester?. File C-HALL 41 - 39 m/e 123 122 121 112 98 90 84 83 82 80 79 70 69 68 58 57 56 55 54 53 45 44 43 42 41 Int. 2 41 18 1 11 1 1 1 1 4 18 >2 1 2-100 20 12 1 1 1 2 10 7 46 Base 57; Parent 122? ; Str. FeatAlkenyl, t-Butyl?. 64-61 - m/e 144 143 142 140 136 134 125 123 121 120 119 111 95 91 85 84 83 82 81 80 73 72 69 67 57 43 41 Int. 1 1 6 8 6 18 1 4 27 8. 38 12 6 62 4 20 10 17 100 32 32 32 19 14 22 85 30 Base 81; Parent ? ; Str. Feat.- Alkyl, Polyunsat or cyclic alcohol or ether?, Polychloro?. 94 - 91 m/e 135 134 133 120 119 118 117 116 105 104 103 91 90 89 85 82 79 78 77 71 65 63 57 51 50 43 Int. 12 28 35 7 12 9 100 45 20 3 3 20065 38 10 8 7 10 18 12 12 24 28 30 18 36 Base 117; Parent 135? ; . Str. Feat.- Alkyl, Aromatic. 99 - 103 m/e 162 156 154 152 150 147 139 137 136 135 121 120 119 118 117 116 115 107 105 103 95 93 92 91 Int. 1 2 5 4 3 1 6 14 31 8 40 8 72 92 57 10 14 22 9 12 10 22 10 100 m/e 90 89 85 83 79 78 77 67 65 63 51 50 44 Int. 9 10 20 31 31 9 32 15 30 20 23 12 18 Base 91; Parent 156? ; Str. Feat.- Aromatic, OH, Methyl. 101 - 99 m/e 162 161 159 147 127 125 123 111 108 104 96 94 81 73 71 70 69 68 59 57 55 54 45 43 42 41 Int. 7 4 7 10 2 4 4 11 13 2 22 2 7 18 42 8 77 12 7 18 20 7 44 65 7 100 Base 41; Parent 162? ; Str. Feat.- Alkenyl, Alkyl(alcohol, ether or sulphur). 105 - 108 m/e 162 160 156 152 146 145 137 136 134* 133* 132 131 121* 118 117 111 99 97 86 85* 84 71* 70 Int. 35 4 4 15 62 45 25 65 92 42 33 100 41 58 36 8 29 29 64 13 35 100 79 File C-HALL 105 - 108 (continued) 109 - 107 116 - 113 119 - 117 121 - 119 127 - 125 130 - 128 136 - 132 m/e 69* 57 56 55 51 44 43 41 Int. 31 80 90 35 40 35 70 7 Peaks marked with an asterisk two spectra are similar. Base 71(131) ; Parent 162? ; (*) are not found in spectrum 105 - 103, relative intensities in the Str. Feat.- Alkyl. m/e 160 142 141 118 115 108 106 104 95 93 91 82 80 79 77 65 58 54 53 41 Int. 10 32 29 6 8 23 9 21 26 40 50 100 3 5 4 10 17 72 18 22 Base 82; Parent 160; Str. Feat.- Cycloalkyl?, Cyclic ketone?, Alcohol?, Methyl. m/e 163 160 147 145 135 131 119 118 117 112 109 97 87 85 83 82 79 73 71 59 58 57 55 44 43 41 Int. 8 28 13 33 13 20 24 40 30 10 7 10 10 100 93 20 10 28 22 28 50 21 30 10 32 40 Base 85; Parent 163? ; Str. Feat.- Cycloalkanol, Propyl, Sulphide?. m/e Int. m/e Int. 187 174 173 159 152 150 140 139 138 132 124 120 118 108 107 92 91 85 79 78 68 67 65 64 63 5 1 6 2 28 2 18 4 4 42 10 9 60 100 3 2 2 12 36 18 5 2 1112 53 52 51 50 45 21 8 7 2 10 Base.91; Parent Str. Feat.- Cycloalkene, diene.or alkyne, Alkyl-Ph.?. m/e 174 173 159 132 130 125 120 119 118 104 91 90 78 76 75 71 64 63 62 52 50 Int. 2 1 4 2 1 13 4 100 6 20 8 1 2 1 10 18 10 2 8 2 Base 118; Parent ? ; Str. Feat.- Benzimidazole, Indazole or Benzofuran. m/e Int m/e Int. 190 188 186 184 176 175 171 170 169 161 147 142 141 134 133 113 111 103 98 87 85 83 72 70 111 1 12 2 5 27 7 4 7 5 10 12 100 2 6 2 2 7 60 62 1 1 57 55 48 38 10 11 Base 133; Parent 176? ; Str. Feat.- Alkyl-trimethylbenzene, Dichlorocarbene?, Butyl?. m/e 173 160 158 157 156 148 147 145 141 121 119 115 91 89 87 71 57 56 55 45 43 41 Int. 3 4 4 4 31 7 14 6 33 22 13 6 8 13 25 33 50 30 10 20 100 30 Base 43; Parent 156? ; Str. Feat.- Alkyl(alcohol, ether, Si or S). m/e 159 157 156 155 153 152 142 141 128 115 85 77 76 75 64 63 58 57 51 50 Int. 9 12 100 32 13 11 10 83 12 14 20 6 11 6 5 6 5 8 4 1 Base 156: Parent 156? ; Str. Feat.- Bicyclo aromatic, Methyl, 1,3 or 2,7 Dimethylnapthalene. to o m/e 182 168 167 154 153 152 140 125 113 112 111 98 97 84 83 82 70 69 68 57 56 55 43 42 41 Int. 1 13 8 2 4 5 3 2 2 5 10 10 26 25 47 20 57 73 22 49 73 95 100 32 95 Base 43; Parent ? ; Str. Feat.- Alkenyl. m/e 168 150 135 133 123 107 91 85 82 81 69 59 58 57 53 41 Int. 33 24 42 11 9 21 11 100 10 10 8 11 10 20 8 18 Base 85; Parent 168? ; Str. Feat.- Alkenyl, Thiophene?, Alcohol, Methyl, Carbonyl. m/e 171 170 169 156 155 154 153 152 137 127 110 109 99 98 97 95 87 83 82 81 74 71 70 69 67 59 Int. 7 50 8 3 41 4 10 8 5 3 8 7 9 100 15 18 10 28 14 16 18 13 25220 27 28 m/e 58 57 55 53 41 Int. 13 16 30 8 60 Base 98; Parent 170? ; Str. Feat.- Alkenyl, Cyclic ether or alcohol, contains spectrum of .1,4,5-Trimethylnapthalene. m/e 208 207 206 192 191 189 187 184 Hi81 169 155 153 150 138 137 135 133 131 125 121 120 117 111 Int. 9 9 13 13 88 13 18 56 13 22 32 20 20 37 28 23 23 37 22 45 100 28 22 m/e 109 108 107 105 95 93 92 91 88 84 81 79 78 77 67 65 59 58 55 53 52 45 43 41 Int. 22 13 28 28 33236327 45 12 12 37 19 12 38 37 22 31 40 37 10 5 19 100 72 Base 43(120) ; Parent 206? ; Str. Feat.- Diene or cycloalkene, Aromatic (high)), OH?. m/e 209 207 204 189 184 169 161 155 151 150 149 138 135 121 119 111 109 107 95 93 91 85 81 79 78 Int. 2 2 2 2 10 10 5 19 24 30 11 7 42 12 18 13 18 23 60 21 8 8 30 18 5 m/e 77 71 69 67 65 57 55 53 45 43 41 Int. 8 11 11 30 7 8 28 14 20 100 68 Base 43; Parent ? ; Str. Feat.- similar to 167 - 166, contains spectrum of Cedrol. m/e 224 209 196 181 161 159 151 150 149 138 135 122 119 109 108 107 99 96 95 91 81 73 72 69 67 Int. 11 8 8 20 8 8 20 35 11 11 98 12 8 14 14 19 30 11 100 21 7 7 7 26 10 m/e 57 55 41 Int. 10\ 7 57 Base 95; Parent 224? ; Str. Feat.- Diene or cycloalkene, Propyl, Cyclic ketone. m/e 185 184 183 182 177 169 160 157 154 153 152 141 130 128 118 117 100 91 90 87 85 76 75 74 64 Int. 6 40 6 40 6 70 4 6 8 16 3 6 2 3 52 3 3 13 3 5 100 7 3 10 13 File C-HALL 172 - 170 m/e 63 59 58 56 52 51 (continued) Int. 8 28 36 10 3 7 Base 85; Parent ? ; Str. Feat.- fQyfcllJi'c<&x-.JaU'cdfroUTi 173 - 172 m/e 209 153 137 125 124 111 110 109 97 96 95 "87 83 82 81 74 71 70 69 68 67 59 58 57 56 55 44 43 41 Int. 3 8 8 1 5 3 3 4 10 20 11 7 20 31 18 11 38 13 23 22 21 27 38 51 17 41 22 100 52 Base 43; Parent ? ; Str. Feat.- Cycloalkenyl(alcohol, Si or S), Alkyl, Carbonyl?. 176 - 174 m/e 169 155 120 111 98 83 73 72 71 69 56 55 43 41 Int. 5 1 1 11115 100 7 5 3 62 12 Base 71; Parent ? ; Str. Feat.- Similar to 2-Hydroxy-3-methyltetrahydrofuran. 177 - 176 m/e 222 204 189 162 161 147 138 137 134 125 122 121 120 119 117 109 107 105 104 98 95 93 92 91 83 Int. 23 17 17 17 35 23 78 30 41 35 23 36 36 23 30 41 60 41 23 41 39 60 23 23 35 m/e 82 81 80 79 77 68 67 65 59 54 53 51 50 Int. 35 100 23 48 30 18 71 30 60 23 12 6 42 Base 81; Parent 222? ; Str. Feat.- Aromatic, Diene or cycloalkene, possibly Methyl ester of an aromatic acid with an ortho hydroxyl. (177 - 176) - m/e 222 204 189 161 147 138 137 132 125 122 121 120 119 109 108 107 98 95 94993 83 82 81 80 79 67 (178 - 177) Int. 31 23 23 46 15 100 40 15 48 31 47 47 31 53 22 78 55 55 23 55 30 30 100 30 60 70 m/e 65 57 53 50 Int. 39 78 15 55 Base 81(138); Parent 222? ; Str. Feat.- Similar to 177 - 176 except that m/e 77, 91, 92, 104 and 105 are missing. 187 - 185 m/e 293 237 220 219 216 215 198 195 184 183 180 179 169 165 159 138 137 109 107 82 81 78 77 59 54 Int. 4 31 3 14 5 35 5 5 9 8 20 9 12 134 38 10 95 13 8 11 20 41 52 100 5 Base 59; Parent ? ; Str. Feat.- Aromatic, Silicon, Septum bleed peak. 190 i 189 m/e 196 146 124 111 110 99 98 97 96 95 84 83 82 80 74 71 69 68 67 57 56 55 44 43 41 Int. 3 1 4 8 5 10 8 18 26 13 8 28 30 7 13 18 31 28 29 92 25 64 22 100 91 Base 43; Parent 196? ; Str. Feat.- Cyclic alcohol or ether. K5 o File C-HALL 192 - 190 m/e :-253 244 230 229 197 196 195 181 175 173 155 135 131 119 107 99 92 91 Int. 7 18 9 52 8 42 41 13 48 22 11 13 11 21 8 100 5 17 Base 99; Parent ? ; Str. Feat.- Alkylsulphur. 195 - 193 m/e 237 221 219 215 210 198 187 186 185 184 183 179 168 159 153 147 145 139 138 137 117 109 104 Int. 7 7 7 12 7 7 10 15 7 78 15 12 16 16 100 7 7 12 9 38 7 10 6 m/e 92 91 77 67 59 Int. 20 26 10 17 20 Base 153; Parent ? Str. Feat.- Similar to 2-Methoxymethyl-3-methoxycarbonyl-5-methylfuran. 196 - 194 m/e Int. m/e Int. 237 216 215 196 195 187 184 159 153 145 140 139 137 131 125 117 116 115 112 111 109 98 97 92 2 3 3 10 5 5 23 9 32 8 5 9 18 6 7 10 10 9 10 30 8 11 38 10 91 84 83 77 71 70 69 68 65 63 57 56 55 53 51 50 45 43 41; 65 24 57 15 73 33 57 22 8 2 50 40 66 5 5 2 20 100 60 Base 43; Parent ? Str. Feat.- Alkyl, Alkenyl, Aromatic(weak), Alcohol or Fluoride?, iso-Propyl. 198 - 196 m/e 212 194 180 177 175 161 159 137 129 117 115 111 109 105 97 95 91 85 83 79 77 71 69 59 57 55 Int. 5 6 2 3 3 2 2 10 6 4 6 21 8 45 11 5 23 14 25 5 15 30 32 22 35 53 m/e 51 43 441 Int. 5 100 63 Base 43; Parent 212? ; Str. Feat.- Alkenyl, similar to 196 - 194 except m/e 105 and top end. 205 - 203 m/e 243 231 229 228 218 216 215 195 194 185 179 161 143 137 129 119 102 100 97 91 87 85 74 73 71 Int. 6 1 3 7 3 5 2 3 7 5 8 8 3 3 8 3 19 357 18 49 23 12 12 m/e 69 60 59 57 55 43 '41 Int. 16 30 15 28 28 100 37 Base 43; Parent ? ; Str. Feat.- Alkenyl, Ester?, Amide?, Methyl?, Chloro?. 206 - 204 m/e 263 243 228 211 185 171 159 143 129 115 102 97 96 87 83 82 74 73 71 69 60 57 55 43 41 Int. 2 10 3 1 2 1 1 1 6 2 13 6 4 9 7 6 12 11 14 13 30 32 23 100 40 Base 43; Parent ? ; Str. Feat.- Similar to 205 - 203 except m/e 161, 179, 194, 195 and 216. 208 - 206 m/e 237 230 229 227 226 219 216 215 202 177 149 137 114 52 Int. 7 100 28 13 21 7 10 62 10 7 38 24 13 10 Base 230; Parent 230? ; Str. Feat.- Polycyclic aromatic hydrocarbon, Methyl?. ho o File C-HALL 209 - 208 m/e 256 210 209 198 197 158 157 150 149 137 114 81 62 59 54 Int. 12 12 12 42 31 12 25 12 100 43 12 12 12 19 12 Base 149; Parent ? ; Str. Feat.- Phthalate ester, possibly n-Propyl. 210 - 209 m/e 237 210 209 199 198 197 195 180 179 165 137 135 99 Int. 12 30 12 12 75 50 32 12 100 20 17 50 17 Base 179; Parent 237? ; Str. Feat.- Hydroxyl or carbonyl, Chloro?, Aromatic?. 211 - 210 m/e 250 219 210 198 196 180 179 159 137 136 135 119 111 107 97 95 91 83 78 77 71 59 57 55 45 43 41 Int. 2 2 2 2 2 12 100 2 3 3 51 3 3 117 11 3 3 14 3 7 14 9 30 17 10 13 21 Base 179; Parent ? ; Str. Feat.- Similar to p-t-Butylphenoxyethahol except no m/e 194. 213 - 211 m/e 137 125 117 112 111 104 97 85 84 83 82 78 77 70 69 57 56 55 43 41 Int. 5 4 4 4 12 7 30 12 18 45 20 3 4 31 52 70 40 72 100 70 Base 43; Parent ? ; Str. Feat.- Alkyl, Alkenyl, Aromatic(weak). 218 - 216 222 - 218 225 - 223 m/e 257 237 221 220 219 218 217 215 208 193 192 191 190 189 184 183 165 159 155 153 152 142 140 Int. 7 15 7 18 21 46 9 37 10 9 30 18 9 12 18 52 24 37 25 12 15 27 78 m/e 138 137 128 114 112 109 108 95 93 91 82 79 78 77 76 73 69 67t65 63 59 55 53 51 50 43 41 Int. 15 100 12 9 37 33 12 12 12 40 16 38 19 62 91 24 18 33 10 25 80 10 12 40 15 12 10 Base 137; Parent 257? ; Str. Feat.- Aromatic(high and low), Chloro, appears to be a mixture of spectrum 236 - 234 in CL1202 with those of some other compounds. m/e 223 205 192 167 150 149 137 132 121 105 104 93 87 76 75 74 71 65 57 56 55 50 43 41 Int. 2 1 1 1 9 100 1 1 2 2 62352853 33 722 10 23 Base 149; Parent ? ; Str. Feat.- Phthalate ester, possibly t-Butyl. m/e 297 283 282 268 253 242 237 212 211 170 163 160 159 147 141 137 133 130 128 127 117 115 91 58 Int. 10 13 100 13 37 13 13 31 20 10 13 18 49 8 18 45 13 13 35 21 52 31 25 14 Base 282; Parent 297? ; Str. Feat.- Cyclic or Aromatic, Methyl, Ketone or ester?. 226 - 225 m/e Int. m/e Int. 268 254 253 240 237 220 218 179 178 161 159 146 145 141 137 136 135 128 127 120 117 115 109 13 6 42 7 .7 .1 13 13 20 10 12 12 12 16 30 20 15 23 30 16 22 32 22 108 105 103 92 91 81 79 78 77 69 67 65 58 53 52 51 45 43 32 20 20 20052 30 31 26 70 100 30 22 32 30 12 30 12 55 Base 69; Parent 268? ; Str. Feat.- Aromatic(high), Methyl, Carbonyl. ISO O as m/e 280 257 237 223 215 212 205 185 150 149 137 104 87 76 59 51 Int. 111141117 100 10 1117 3 Base 149; Parent ? ; Str. Feat.- Phthalate ester. m/e 268 237 236 227 219 216 215 208 191 177 164 163 161 159 145 138 137 121 117 109 107 101 95 93 Int. 7 13 11 .1 7 7 29 7 7 7 28 7 7 21 10 13 100 18 23 18 10 13 28 13 m/e 92 91 88 81 79 78 77 74 73 69 67 59 55 54 53 43 42 41 Int. 13 70 23 49 22 28 35 18 25 31 28 60 46 10 10 48 31 22 Base 137; Parent ? ; Str. Feat.- Aromatic(high), Nitro?, Methyl?. m/e 256 237 219 215 159 150 148 137 122 121 105 104 93 87 85 84 77 76 65 60 59 57 56 55 50 43 41 Int. 1 2 1 5 2 3 2 27 3 3 7 12 12 7 3 4 17 28 22 8 22 53 40 13 13 18 100 Base 41; Parent ? ; Str. Feat.- Aromatic(low), Alkyl. m/e 236 222 207 206 202 193 191 190 189 180 179 178 168 167 165 154 152 134 133 123 119 109 107 Int. 47 10 12 36 10 20 30 12 16 40 17 40 30 32 32 17 17 10 10 10 13 22 30 m/e 101 96 95 94 91 82 81 80 79 71 69 67 55 43 Int. 10 16 80 22 26 35 88 26 40 42 100 55 65 45 Base 69; Parent 236? ; Str. Feat.- Diene or cycloalkene, Diunsat. cyclic alcohol or ether, or Alkenyl carbonyl. m/e 234 197 184 183 177 167 166 140 139 135 134 131 127 121 108 107 106 93 91 85 79 77 57 53 52 41 Int. 8 1 1 2 4 10 15 2 12 2 100 2 7 3 3 31 3 4 6 12 22 3 22 7 ] 5 Base 134; Parent ? ; Str. Feat.- contains spectrum of 2,4-Dimethyl-6-ethylpyridine (mw 135), t-Butyl, o-Methyl ester?. m/e 354 250 247 228 209 175 167 151 150 149.98 93 83 76 70 69 67 65 55 41 Int. 2 2 2 2 8 2 5 2 10 100 4 4 22 4 18 4 4 4 12 13 Base 149; Parent ? ; Str. Feat.- Phthalate ester. m/e 199 112 97 84 83 81 71 70 69 57 55 43 41 Int. 50 25 17 18 25 18 58 50 33 100 50 50 32 Base 57; Parent L? ; Str. Feat.- similar to Di-2-ethylhexylfumarate except for m/e 199. File C-HALL 366 -360 m/e 238 206 205 178 165 150 149 135 133 132 123 122 105 104 92 91 77 76 65 57 56 51 50 41 Int. 1 15 2 2 1 11 100 4 2 12 12 8 10 15 5 71 5 10 18 4 5 2 4 15 Base 149; Parent ? ; Str. Feat.- similar to Benzyl-butylphthalate. 506 - 498 m/e 299 279 253 243 231 229 222 220 217 203 198 191 188 186.178 168 167 150 149 113 112 104 83 Int. 1 31 1 1 1 1 1 1 1 1 1 1 1 1 1 3 32 11 100 8 6 77 m/e 76 71 70 57 55 43 41 Int. 4 25 23 40 18 31 28 Base 149; Parent ? ; Str. Feat.- Phthalate ester. File APLCL1 83 - 88 114 - 111 152 - 145 187 - 182 243 - 240 m/e 109 108 107 91 90 89 80 79 78 77 63 62 55 53 52 51 50 39 Int. 7 88 100 7 12 7 20 43 13 61 17 9 10 30 20 40 31 42 Base 107; Parent 108? ; Str. Feat.- Methylphenol, probably p-Cresol. m/e 187 115 101 87 85 84 74 73 69 61 60 555445443441339 Int. 1 3 11 7 7 6 6 57 10 10 100 40 52 54 82 39 Base 60; Parent ? ; Str. Feat.- Aliphatic acid. m/e 129 115 104 101 Int. 10 3 1 1 Base 41; Parent ? 97 91 87 83 73 71 69 61 60 57 55 45 43 41 39 1 6 9 9 60 13 13 8 80 22 47 45 60 100 40 Str. Feat.- Aliphatic acid. m/e 185 171 158 157 143 130 129 115 111 101 99 98 97 87 85 83 73 71 69 60 57 55 45 43 41 39 Int. 1 2 1 5 2 1 8 5 2 5 2 3 5 8 8 8 61 11 11 100 20 40 50 59 80 40 Base 60; Parent ? ; Str. Feat.- Aliphatic acid. m/e 129 123 115 111 110 109 101 98 97 96 Int. 12153415 10 8 m/e 43 41 39 Int. 59 3100430 Base 41; Parent ? ; Str. Feat.- Aliphatic acid. 95 87 84 83 81 79 77 73 69 67 60 57 56 55 54 53 45 8 2 10 18 16 10 7 12 32 24 18 17 18 71 19 10 20 ho o oo File APLCL1 274 m/e 137 125 123 (unsubtracted) Int. 2 12 Base 41; Parent 111 109 97 95 83 82 81 79 77 73 69 3 3 9 10 17 10 21 12 8 8 30 ? ; Str. Feat.- Aliphatic acid. 68 67 60 57 55 54 45 43 41 39 13 33 21 16 69 22 18 51 100 24 File 35LBK1 146 - 143 193 - 189 211 - 205 also 257 - 253 330 - 320 m/e 241 239 237 215 201 195 161 160 159 141 137 109 81 79 78 77 59 51 39 Int. 7 7 33 40 8 8 8 8 40 7 33 10 21 6 51 96 100 18 80 Base 59; Parent ? ; Str. Feat.- Aromatic, similar to septum bleed. m/e 237 219 215 167 159 155 154 139 137 113 112 99 883 82 78 77 65 59 57 55 43 41 Int. 1111121745 10 100 3 3 2 4 1 5 28 7 25 50 Base 99; Parent ? ; Str. Feat.- Cyclic alcohol or ether. m/e 297 295 294 293 277 273 * spectrum 146 - 143 Int. 1113 11 Base 59; Parent ? ; Str. Feat.- Aromatic, Septum bleed peaks. 

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