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Chemistry of tropospheric fallout and streamflow in a small mountainous water-shed near Vancouver, British… Zeman, Lubomir John 1973

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CHEMISTRY OF TROPOSPHERIC FALLOUT AND STREAMFLOW IN A SMALL MOUNTAINOUS WATERSHED NEAR VANCOUVER, BRITISH COLUMBIA by LUBOMIR JOHN ZEMAN Ing., Czech Technical University i n Prague, 1947 M.Sc., University of B r i t i s h Columbia, 1969 A THESIS SUBMITTED IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY in THE FACULTY OF FORESTRY We accept t h i s thesis as conforming to the required standard THE UNIVERSITY OF BRITISH COLUMBIA August, 1973. In presenting t h i s thesis i n p a r t i a l f u l f i l m e n t of the requirements for an advanced degree at the University of B r i t i s h Columbia, I agree that the Library s h a l l make i t f r e e l y available for reference and study. I further agree that permission fo r extensive copying of t h i s thesis for scholarly purposes may be granted by the Head of my Department or by h i s representatives. It i s understood that copying or publication of t h i s thesis for f i n a n c i a l gain s h a l l not be allowed without my written permission. Department of F o r e s t r y The University of B r i t i s h Columbia Vancouver 8, Canada Date September 13, 197 3 i . ABSTRACT This thesis describes the balance between i o n i c input i n p r e c i p i t a t i o n and output i n streamflow from a small mountainous watershed, and deals with a detailed examination of i o n i c concentrations i n bulk and wet f a l l o u t on a coastal s i t e i n the v i c i n i t y of Vancouver, B r i t i s h Columbia. The Jamieson Creek experimental watershed i n the Greater Vancouver Water D i s t r i c t was chosen as an example of a topographically well-defined watershed with r e l a t i v e l y watertight bedrock and an undisturbed coniferous forest ecosystem. During the period of November 197 0 to October 1971, weekly samples of p r e c i p i t a t i o n and discharge water were analyzed f o r eleven i o n i c constituents. The io n i c input-output budgets show that there were net losses of sodium, potassium, calcium, magnesium, bicarbonate, s u l f a t e , chloride, s i l i c a and phosphate from the watershed i n stream-flow. The exceptions were the n i t r a t e and ammonium loads which showed net gains i n the watershed. The tropospheric f a l l o u t provides most of the i o n i c loads of the following constituents of discharge water: n i t r a t e , ammonium, sulfate and chloride. The t e r r e s t r i a l sources, however, are the major suppliers of s i l i c a , calcium, bicarbonate, magnesium and potassium. Phosphate and sodium are derived equally from tropospheric and t e r r e s t r i a l sources. Continuous d a i l y sampling of bulk f a l l o u t and wet f a l l o u t was carried out on Point Grey, Vancouver, during the period of December 19 71 to A p r i l 1972. Although the i o n i c concentrations i n bulk f a l l o u t were consistently somewhat higher, the differences between i o n i c concentrations i n bulk and wet f a l l o u t were not s t a t i s t i c a l l y s i g n i f i c a n t . The relationships between concentrations and r a i n f a l l were s i g n i -f i c a n t for sodium, potassium, calcium, magnesium, s u l f a t e , chloride, n i t r a t e , s i l i c a and ammonium but there were no s i g n i f i c a n t relationships between snowfall and the concentra-tions of any chemical constituent. Bicarbonate and phosphate do not show any s i g n i f i c a n t r e l a t i o n s h i p with either r a i n or snow. The bulk f a l l o u t on Point Grey was characterized by higher r a t i o s of calcium and potassium to sodium and chloride, and by a lower r a t i o of chloride to sodium than i s found i n sea water. These deviations from sea water r a t i o s are ascribed to the contribution of s o i l dust to the content of calcium, potassium and sodium i n bulk f a l l o u t . Higher r a t i o s of sulfate to sodium and chloride were observed i n the Point Grey re s u l t s and are ascribed to the influence of anthropogenic sources on the composition of bulk f a l l o u t . On the other hand, i n bulk f a l l o u t on the Jamieson Creek water-shed there was a lower deviation of r a t i o s of sulfate to sodium or chloride from the sea water values, suggesting that anthropogenic sources are less i n f l u e n t i a l i n the watershed area. However, much higher r a t i o s of calcium, magnesium and chloride to sodium were observed. These indicate that dry f a l l o u t contributes sub s t a n t i a l l y to the composition of bulk i i i . f a l l o u t on the watershed. ACKNOWLEDGEMENTS The hydrological research on which th i s thesis i s based was made possible i n great part by the f i n a n c i a l support and the f a c i l i t i e s supplied by the Greater Vancouver Water Board. I t i s a pleasure to thank the following advisers for t h e i r u n f a i l i n g kindness i n a s s i s t i n g me during the research work and i n c a r e f u l l y reading the manuscript: Dr. B.C. Goodell, Dr. J.P. Kimmins, and Dr. A. Kozak, Faculty of Forestry, University of B r i t i s h Columbia; Professor T.L. Coulthard and Dr. E.O. Nyborg, A g r i c u l t u r a l Engineering Department, University of B r i t i s h Columbia; Dr. 0. Slaymaker, Department of Geography, University of B r i t i s h Columbia; and Dr. M.A. Tung, Food Science Department, University of B r i t i s h Columbia. I am thankful to D. P a v l i s , chemist i n the laboratory of the A g r i c u l t u r a l Engineering Department, University of B r i t i s h Columbia f o r numerous analyses of water samples. For many suggestions regarding chemical analysis of samples, I am also indebted to S. Brynjolfson, chemist i n the Chemistry Laboratory, Water Resource Service, Department of Lands, Forest and Water Resources. TABLE OF CONTENTS PAGE ABSTRACT i ACKNOWLEDGEMENTS i v TABLE OF CONTENTS v LIST OF FIGURES v i i i LIST OF TABLES X I INTRODUCTION 1 1-1 Objectives of the Study- 2 1-2 Research Approach 2 1-3 Thesis Presentation 3 II LITERATURE REVIEW 4 I I - l Tropospheric Chemistry 6 I I - l . 1 The gases 6 I I - l . 2 Aerosols 15 I I - l . 3 Temporal v a r i a t i o n i n c i r c u l a t o r y chemicals 17 I I - l . 4 Sources of chemicals to troposphere 20 I I - l . 4.1 The sea 20 I I - l . 4.2 The s o i l 20 I I - l . 4.3 Anthropogenic sources. 23 I I - l . 5 Chemical f a l l o u t from troposphere 25 I I - l . 5.1 Wet removal 26 I I - l . 5.2 Dry removal 27 I I - l . 5.3 Reaction with vegetation 28 I I - l . 6 Methods of f a l l o u t measurements and res u l t s 29 I I - l . 6.1 Bulk f a l l o u t 29 I I - l . 6 . 2 Wet f a l l o u t 30 I I - l . 6.3 Comparison of bulk and wet f a l l o u t 33 I I - l . 6.4 Dry f a l l o u t 34 II-2 Stream Water Chemistry 37 II-2 . 1 Forest vegetation 37 II-2. 2 S o i l and rock 38 II-2. 3 Methods and re s u l t s from previous studies 43 I l l STUDY AREA 49 I I I - l Selection of Areas 49 V I , STUDY AREA (Continued) PAGE III-2 Oceanic and Anthropogenic Environ-ments 52 III-3 Climatic Environment 53 III-3.1 A i r masses 53 III-3.2 Wind 54 III-3.3 P r e c i p i t a t i o n 5 5 III-4 T e r r e s t r i a l Environment of the Jamieson Creek Watershed 58 III-4.1 Physiography and hydrology 58 III-4.2 Bedrock geology 62 III-4.3 S u r f i c i a l geology 62 III-4.4 S o i l s 63 III-4.4.1 Physical c h a r a c t e r i s t i c s 64 111-4.4.4.2 Chemical properties 67 I I I - 4.5 Vegetation 67 IV EXPERIMENTAL METHODS 69 I V ^ l Instrumental Network 69 IV- 1.1 Bulk f a l l o u t instrumentation 69. IV-1.2 Wet f a l l o u t instrumentation 71 IV-1.3 Discharge from the watershed 7 5 IV- 1.4 . Chemical analysis 75 V DATA ANALYSIS .' 77 V- l Analysis of Variance 7.7 V-2 Model for Calculation of Input-Output Relationship 80 V-2.1 Input 80 V- 2.2 Output 8 3 VI DATA INTERPRETATION . 8 6 VI- 1 Ionic Concentrations 86 VI-1.1 Ionic concentration r a t i o s 91 VI-2 Ionic Loads 94 VI-2.1 Relationships between f a l l o u t loads and p r e c i p i t a t i o n 99 VI-2.2 Relationships between discharge loads and streamflow 102 VI-2.3 Ionic load balance 105 VI-2.4 Output to input r a t i o s 109 VI-2.5 Sources of calculated i o n i c loads 113 v i i . PAGE SUMMARY AND CONCLUSIONS 117 711 PRECIPITATION CHEMISTRY - POINT GREY 119 VII-1 Comparison of Ionic Concentrations i n Bulk and Wet Fallou t 119 VII-2 Ionic Concentrations i n Bulk Fall o u t 12 6 VII-3 Influence of Snow and Rain on Ionic Concentrations i n Bulk Fallout 131 VII-4 Ionic Ratios i n Bulk Fallout 137 VII-5 Temporal D i s t r i b u t i o n of Wet Fallou t During Rainstorms 140 SUMMARY AND CONCLUSIONS 143 LITERATURE CITED 14 5 v i i i . LIST OF FIGURES FIGURES PAGE 1 World water supply (from Penman, 197 3) 5 2 D e f i n i t i o n of troposphere i n terms of a U.S. standard atmosphere (from COESA, 1962) 5 3 Nomenclature of natural aerosols and the importance of p a r t i c l e sizes for various f i e l d s of meteorology (from Junge, 1963) 16 4 The formation of sea-salt p a r t i c l e s from bursting of bubbles (from Junge, 1963) 21 5 Concentration d i s t r i b u t i o n patterns of inorganic ions i n r a i n water over the United States (from Junge, 1963) 3 2 6 Topographic map showing location of the Jamieson Creek watershed (JC) and the Point Grey s i t e (PG) 50 7 Capilano and Seymour drainage basins showing location of experimental water-sheds and f i e l d instrumental s i t e s (from Goodell, 1972) 51 8 Map of the Jamieson Creek watershed 59 9 A e r i a l photograph showing topographic , boundary surrounding the Jamieson Creek watershed 60 10 Hydrograph of Jamieson Creek, water year 1970-71 61 11 Schematic diagram of soil-landform rela t i o n s h i p 65 12 Bulk f a l l o u t c o l l e c t o r 7 0 13 P r e c i p i t a t i o n and bulk f a l l o u t c o l l e c t o r s 70 14 Bulk and wet f a l l o u t automatic c o l l e c t o r 7 0 15 V-notch weir a f t e r construction 70 1 6 V-notch weir i n operation 7 0 E l e c t r o n i c c i r c u i t r y for automatic c o l l e c t o r for wet f a l l o u t Sensor dry: wet f a l l o u t c o l l e c t o r closed Sensor wet: wet f a l l o u t c o l l e c t o r open Tipping bucket r a i n gauge Tipping bucket recorder C o l l e c t i o n turntable Opened c o l l e c t i o n turntable Schematic diagram for ca l c u l a t i n g the i o n i c input-output balance at the Jamieson Creek watershed Weighted monthly average i o n i c concentra-tions i n bulk f a l l o u t and discharge from the Jamieson Creek watershed, water year 1970-71 (ordinate scale i s logarithmic) Monthly average i o n i c loads i n bulk f a l l o u t and discharge from the Jamieson Creek water-shed, water year 1970-71 (ordinate scale i s logarithmic) Ratios of discharge to p r e c i p i t a t i o n and of io n i c loads i n discharge water to bulk f a l l o u t for the Jamieson Creek watershed (ordinate scale i s logarithmic) Comparison of io n i c concentrations i n bulk f a l l o u t and wet f a l l o u t on Point Grey, winter 1971-72 (axis scales are logarithmic) Daily i o n i c concentrations i n bulk f a l l o u t on Point Grey, winter 1971-7 2 (ordinate scale i s logarithmic) Comparison of regression l i n e s r e l a t i n g i o n i c concentrations i n r a i n f a l l and snow-f a l l to p r e c i p i t a t i o n amount. Point Grey, winter 1971-72 LIST OF TABLES TABLES ' PAGE 1 Summary of Trace Gases i n the Atmosphere. Translated from German o r i g i n a l (Junge, 1971b) 8 2 Concentration of Carbon Monoxide, Sulphur Dioxide, Oxidants and Oxides of Nitrogen. Total Study Period July 19 6 9 to December 19 7 0 (from Lynch and Emslie, 197 2) 11 3 Comparison of Carbon Monoxide Concentra-tions at Vanier Park with Common Objectives and C r i t e r i a for the Entire Study Period of July 1969 to December 1970 (from Lynch and Emslie, 1972) 11 4 Comparison of. Oxidants Concentrations at Vanier Park with Common Objectives and C r i t e r i a for the Entire Study Period of July 19 69 to December 19 7 0 (from Lynch and Emslie, 1972) 13 5 Comparison of Sulphur Dioxide Concentra-tions at Vanier Park with Common Objectives and C r i t e r i a for the Entire Study Period of July 19 6 9 to December 19 7 0 (from Lynch and Emslie, 1972) 13 3 . 6 Model P a r t i c l e Concentrations per cm m Surface A i r (from Junge, 19 63) 16 7 Average Concentrations of Na, CI, and S in Particulate and Gaseous Form i n Hawaii and F l o r i d a (from Junge, 1963) 21 8 Chemical Concentrations of Snowpack Samples from Utah and S i e r r r a Nevada (from Feth et a l . , 1964) 36 9 The Hubbard Brook Experimental Forest, Watershed 2, Water Year 1964-65, Annual Average Input and Output Loads i n Bulk Fallout and Discharge (from Likens et al_. , 1967; Fisher et a l . , 1968) 45 10 Annual Average Input Loads i n Bulk Fallout at Three Scottish Stations (from Holden, 1966) 47 Hutt Valley, New Zealand, Annual Average Input and Output Loads i n Bulk Fallout and i n Discharge (from M i l l e r , 197 0) Temperature and P r e c i p i t a t i o n (from Environment Canada, 197 0) Analysis of Variance, F i e l d Layout, Two-way C l a s s i f i c a t i o n Significance of P r e c i p i t a t i o n D i s t r i b u t i o n (mm) and Ionic Concentrations (mg/1) among Four Elevation Zones and Intervals of Sampling Jamieson Creek Watershed, S t a t i s t i c a l C haracteristics from Monthly Weighted Average Ionic Concentrations i n Bulk F a l l -out, Water Year 1970-71 Jamieson Creek Watershed, Annual Average Concentration Ratios for Major Ions, Water Year 1970-71 Comparison of Ratios to Sodium i n P r e c i p i -t a t i o n and Stream Analysis (from Holden, 1966) Jamieson Creek Watershed, S t a t i s t i c a l C haracteristics of Ionic Loads i n Bulk Fa l l o u t , Water Year 1970-71 Jamieson Creek Watershed, Relationships Between Monthly Ionic Loads i n Bulk Fallout and P r e c i p i t a t i o n Amount Jamieson Creek Watershed, Relationships Between Monthly Ionic Loads i n Discharge and Rate of Flow Jamieson Creek Watershed, Monthly Ionic Balances i n Bulk Fallout and Discharge Water Water Year 1970-71 Jamieson Creek Watershed, S t a t i s t i c a l C haracteristics of Monthly Ionic Balances i n Bulk Fallout and Discharge Water, Water Year 1970-71 x i i . TABLES PAGE 2 3 Jamieson Creek Watershed, Percentage Contribution of Ions i n Water, Water Year 1970- 71 114 24- Point Grey, S t a t i s t i c a l C haracteristics of Daily Differences Between Ionic Concentra-tions i n Bulk and Wet Fall o u t Expressed as Percentage of Bulk F a l l o u t , Winter 1971-7 2 123 25 Point Grey, Test of Differences Between Bulk and Wet Fallout Concentrations, Winter 1971- 72 125 26 Point Grey, S t a t i s t i c a l C haracteristics of Daily Ionic Concentrations i n Bulk F a l l o u t , Winter 1971-72 129 27 Point Grey, Results of Covariance Compari-son of Ionic Concentration Variation with P r e c i p i t a t i o n f o r R a i n f a l l and Snowfall 13 2 2 8 Point Grey, Regression Equations Relating Ionic Concentrations i n R a i n f a l l and Snowfall to P r e c i p i t a t i o n Amount 13 3 29 Comparison Between Ionic Ratios i n Bulk Fallo u t on Point Grey and Jamieson Creek with Ionic Ratios i n Sea Water 139 . 30 Point Grey, Ionic Concentrations i n Wet Fallout During Individual Rainstorms 141 .1. I INTRODUCTION Increasing demands for water and growing environ-mental awareness are causing concern over the qual i t y of fresh water supplies and i t s impairment by human a c t i v i t i e s . There are natural l e v e l s of ions i n fresh drainage water from a l l undisturbed watersheds. It i s therefore necessary to quantify the chemical quality of t h i s fresh surface water so that the degree of human interference i n the hydrochemical cycle and i t s e f f e c t s on the chemical qu a l i t y of water can subsequently be monitored. Very few control watersheds have been estab-li s h e d with t h i s purpose i n the Canadian C o r d i l l e r a . The present study represents the f i r s t r e s u l t s of such a research methodology i n B r i t i s h Columbia. There are many points at which chemical cycles may be strongly related to the hydrologic cycle. For example, a watershed receives various i o n i c constituents as input i n p r e c i p i t a t i o n and as dry f a l l o u t from the troposphere, and the quantity of the input i n p r e c i p i t a t i o n i s strongly influenced by the volume of water f a l l i n g onto the watershed. Uptake of nutrients by standing biomass and release of nutrients by b i o l o g i c a l decomposition are also c l o s e l y related to the hydrologic cycle. S i m i l a r l y , the rate of weathering of s o i l and rocks and the rate of removal of the end products of weathering are influenced by the hydrologic regime. As the water enters the watershed, i t s i o n i c loading experiences various changes. Additional amounts of most io n i c constituents are added to the throughfall as i t passes through the forest canopy by leaching from vegetation. Other biogeochemical a c t i v i t i e s within the forest ecosystem influence 2 . the concentrations of various chemicals i n water passing through the b i o t i c portion of the system. Water moving through s o i l and weathered rocks into streams c o l l e c t s further amounts of i o n i c constituents released by the s o i l and rock minerals. Thus, at each stage of the transfer of water through the watershed system, the concentrations of dissolved matter w i l l be altered to produce an i o n i c output which frequently d i f f e r s from the i o n i c input. The difference between the inputs of i o n i c constituents i n p r e c i p i t a t i o n f a l l i n g on a watershed and i o n i c outputs i n discharge water can be evaluated i f the watershed system has an impermeable geologic substrate and l a t e r a l boundaries which coincide with the topographic divide. I - l ' Objective's' of the Study The purpose of t h i s study was to evaluate the balance of i o n i c input i n tropospheric f a l l o u t and the output i n discharge water from a small mountainous watershed, with special emphasis on processes a f f e c t i n g input components of tropospheric f a l l o u t . 1-2 Research Approach F i r s t , the Jamieson Creek watershed was selected as a suitable area for obtaining quantitative data on i o n i c inputs i n bulk f a l l o u t and t h e i r outputs i n discharge water. The watershed which i s characterized by an undisturbed forest ecosystem and located on r e l a t i v e l y water-tight bedrock, i s suitable for the study of chemical cycles. Systematic • sampling of p r e c i p i t a t i o n and discharge water from the water-shed at weekly in t e r v a l s provided a basis for the assessment of i o n i c input-output r e l a t i o n s h i p s . The second part of the study involved d a i l y sampling of p r e c i p i t a t i o n on Point Grey. This part of the study permitt' a detailed examination of the differences between the v a r i a -tions i n the i o n i c concentrations i n two phases of tropospheric f a l l o u t , i n bulk and wet f a l l o u t . 1-3 Thesis Presentation Section I I , a l i t e r a t u r e review, gives a compre-hensive account of the present knowledge of the chemistry of p r e c i p i t a t i o n and fresh surface water. The next section, a description of the study areas, i s followed by a section describing the research techniques. Section V and VI deal with the interpretation of r e s u l t s from the Jamieson Creek watershed and emphasize the balance between i o n i c loads i n bulk f a l l o u t on the entire watershed and i o n i c loads i n discharge water. Section VII presents the r e s u l t s on p r e c i p i t a t i o n chemistry on Point Grey. This section focusses on the input component of the hydrochemical cycle and on a comparison between i o n i c concentrations i n bulk and wet f a l l o u t . F i n a l l y , the data on i o n i c concentrations i n bulk f a l l o u t on Point Grey are compared with the data obtained for bulk f a l l o u t on the Jamieson Creek watershed. II LITERATURE REVIEW The natural waters on the earth are the oceans and seas, the lakes and r i v e r s , snow and i c e , the sub-surface water including both s o i l and ground water, and atmospheric/ water vapor. C o l l e c t i v e l y they form the hydrosphere, the discontinuous s h e l l of water on and about the earth's cpust, Of the t o t a l volume of water in.the hydrosphere, estimated to be approximately 1,50 0 m i l l i o n cubic kilometers, the gr-eater portion of water i s i n the oceans (Fig. 1). Fresh water i n a l l i t s forms represents only about three percent of the t o t a l volume. Of this"' three percent more than three-quarters exists as polar ice caps or g l a c i e r s . The water vapor content i n the atmosphere i s r e l a t i v e l y small but play a very important role i n the world c i r c u l a t i o n of water (Clarke, 1924; Penman, 1970). The concept of the hydrologic cycle encompasses th movement of water through the hydrosphere i n c l u s i v e of i t s atmospheric region. Associated with the hydrologic qycle i s the hydr-ochemical cycle which relates to the chemistry of water as i t ci r c u l a t e s within the hydrologic cycle. The sources of ions i n fresh water are the oceans, s o i l s and rocks,.vegetation, volcanic emissions and man's i n d u s t r i a l and energy-producing a c t i v i t i e s . A major pathway of ions from these sources to fresh water i s through the atmosphere (Hutchinson, 1957; Gorham, 1958; Junge, 1952). 5 . F i g . l . World water supply (from Penman, 19 70) I 40 j-Temperature in Degrees Cenl igrode F i g . 2 . D e f i n i t i o n of troposphere i n terms of a U.S. standard atmosphere (from COESA, 196 2 ) . I I - l Tropospheric Chemistry Conceptually, the atmosphere may be s t r a t i f i e d into troposphere, stratosphere, mesosphere and thermosphere. This s t r a t i f i c a t i o n i s conveniently i d e n t i f i e d by the temperature structure (Fig. 2) but there are associated differences i n chemical composition. The troposphere, the stratum within which man l i v e s and which extends up to about 12 km above the earth's surface (Chapman, 1950; COESA, 1962), w i l l be the focus of attention here. The troposphere i s a well mixed gas consisting primarily of nitrogen, oxygen and! r e l a t i v e l y minor amounts of water vapor, argon, and carbon dioxide. Gases normally present i n trace amounts are helium, krypton, xenon, neon, methane, ammonia, nitrous oxide, sulfur dioxide, iodine, carbon monoxide and ozone. Chemical elements and compounds are also present i n the form of aerosols and larger p a r t i c u l a t e matter. A l l of these elements and compounds are subject to c i r c u l a t i o n and for many of the gases the c i r c u l a t i o n i s i n c l u s i v e of interchanges among the earth's crust (lithosphere), the l i q u i d portion of the hydrosphere, and the biomass of the biosphere. I I - l . l The gases Circulatory behaviour d i f f e r s among atmospheric gases, primarily because of differences i n the nature, pre-valence and strengths of sources and sinks. Junge(1971b) proposed a group c l a s s i f i c a t i o n based on such c h a r a c t e r i s t i c s . The summary of t h i s c l a s s i f i c a t i o n , which includes anthro-7 . pogenic gases, i s given i n Table 1 and i s expanded upon below: Group 1. The noble gases — neon, argon, krypton and xenon — present i n the atmosphere originated i n the protoplanet. These gases do not exhibit atmospheric c i r c u l a -t i o n . Group 2. The gases i n th i s group -- nitrogen and oxygen -- have very long residence times i n the atmosphere. The atmosphere i s constantly acquiring oxygen from chlorophyll-containing plants which take up carbon dioxide and evolve oxygen. At the same time, oxygen i s being removed from the atmosphere by the r e s p i r a t i o n of plants and animals and by the oxidation of the various reducing agents i n the earth's crust such as s u l f u r , iron and manganese. Iron i s the p r i n c i p a l consumer of oxygen during weathering, but manganese i s converted from bivalent to the quadrivalent state, and oxidation converts sulfide s into sulfates or free s u l f u r i c acid. In addition, consumption of free oxygen occurs during the oxidation of volcanic gases, e s p e c i a l l y hydrogen (Goldschmidt, 1933; Mason, 1952). Nitrogen i s removed from a i r by both organic and inorganic processes. The organic processes include nitrogen f i x a t i o n by micro-organisms l i v i n g i n the root nodules of certain plants, by s o i l organisms and some blue-green algae. The amount of organically fixed nitrogen f a r exceeds that fixed by inorganic processes such as f i x a t i o n by lightning (Hutchinson, 1944). TABLE 1 SUMMARY OF TRACE GASES IN THE ATMOSPHERE COMPOSITION, AND DATA ON CIRCULATION, AND CONCENTRATION RESIDENCE SOURCES TIME SINKS PERMANENT Ar GASES Ne Kr Xe ACCUMULATION IN THE EARTH ATMOSPHERE (1)  MAIN COMPONENTS - 1 0 < > Y M S T OF THE ATMOSPHERE (2) - 1 0 4 Y P M, CH CONCENTRATION DUE TO ACCUMULATION o < > o to CIRCULATION EXCLUSIVELY o r PREDOMINANTLY BIOLOGICALLY CONDITIONED CIRCULATION PARTIALLY BIOLOGICALLY o r PHYSICO-CHEMICALLY CONDITIONED CIRCULATION PHYSICO-CHEMICALLY CONDITIONED C 0 2 315 ppm H c o n c e n -t r a t i o n CH r a n g e ' i n ppm CO (3) 15 Y 2 Y 2 Y 1 Y M , B , A M M M, A P M,(CH) M, (CH) M, (CH) NO- c o n c e n -NO t r a t i o n r a n g e NH i n ppm (4) SO. H 0 2 3 He Rn ,Th (5) M? Some c h e m i c a l t r a n s f o r m a t i o n 5 t o i n t o a e r o s o l , 30 D M.CH? some wash-out t h r o u g h M p r e c i p i t a t i o n 10 D - 0.3 10' Evapo-r a t i o n P h o t o -c h e m i c a l P r o d u c e d by r a d i o a c t i v i t y i n s o i l P r e c i p i t a t i o n C h e m . d e s t r u c t i o n on t h e e a r t h ' s s u r f a c e I n t e r p l a n e t a r y space e s c a p e R a d i o a c t i v e decay i n t h e atmosphere HIGHER HYDROCARBONS ( e x c e p t C H 4 ) , C I , I , Hg i n GASEOUS COMPOUNDS LIKELY MANY OTHER TRACE GASES IN VERY LOW CONC. C6) C o n c e n t r a t i o n r a n g e s i n ppb o r l o w e r Y e a r Day M i c r o b i o l o g i c a l A = Anthropogen CH B i o l o g i c a l P = P h o t o s y n t h e s i s (CU) = S i n k not s i g n i f i c a n t C h e m i c a l TRANSLATED FROM GERMAN ORIGINAL (Junge, 1971b) 9. Group 3. The main sources of t h i s group of gases i s also b i o l o g i c a l , but anthropogenic sources are l o c a l l y important. P r i n c i p a l sources are through the oxidation of organic matter which includes combustion, b i o l o g i c a l decay and animal and plant r e s p i r a t i o n . The chemical processes i n which atmospheric CC^ i s involved occur at the earth's surface; the atmosphere acts only as a passive buffer r e s e r v o i r . The rate of exchange with the ocean and biosphere i s r e l a t i v e l y slow, but the ocean represents a huge reservoir f o r CO2 compared to the atmosphere. The other gases of t h i s group, H 2 , CH^ and CO, have r e l a t i v e l y short residence times and low ranges of con-centration . The source of CH^ i s primarily anaerobic b a c t e r i a l decomposition, as, for example, i n flooded paddy areas. In urban areas, CK^ i s a major component of automobile exhaust and other combustion gases. The estimated average concentra-t i o n i n the atmosphere i s 1.5 ppm (Robinson and Robbins, 1968). Carbon monoxide plays an important r o l e i n the chemistry of the contaminated atmosphere. The world-wide emission of carbon monoxide from combustion sources i s second only to that of carbon dioxide ( S e i l e r and Junge, 1969). Automobile exhaust gases are the major source of CO. Besides anthropogenic sources, forest f i r e s of natural o r i g i n con-s t i t u t e a natural source of CO emission (Robinson and Robbins, 1968) . 10. Observations of CO concentrations over Vancouver, B.C., as reported by Lynch and Emslie (1972), are presented i n Table 2. The mean concentration over the study period, July 1969 to December 1970, was 2.1 ppm and the maximum was 28.4 ppm. Table 3 shows, for a central area of Vancouver (Vanier Park), Lynch and Emslie"s comparison of concentration frequency data with established a i r qu a l i t y c r i t e r i a . The authors estimate that the maximum desirable concentration-duration c r i t e r i o n of 13 ppm for one hour may be exceeded from one tenth percent to one percent of the time. Group 4. The gases of group 4 have microbiological sources, although some have anthropogenic sources as well. They have very short residence time i n the atmosphere. Sinks are of physico-chemical character. N i t r i c oxide (NO) and nitrogen dioxide (NO2) are s i g n i f i c a n t pollutants emitted by man's a c t i v i t i e s . They are produced by the combustion of f o s s i l fuels and thus originate from automobile exhausts, furnace stacks and other similar sources. Their importance as pollutants arises mainly from t h e i r p a r t i c i p a t i o n i n photochemical reactions involving organics and SO^• In Vancouver the study of Lynch and Emslie (1972) shows that the mean concentration of the oxides of nitrogen was 0.055 ppm (Table 2). Other chemical reactions involving gaseous nitrogen compounds are oxidation of both NH„ and N 0 9 to form n i t r a t e s o 2 and the ne u t r a l i z a t i o n of NH0 to form ammonium sulfate and TABLE 2 CONCENTRATIONS OF CARBON MONOXIDE, SULPHUR DIOXIDE, OXIDANTS AND OXIDES OF NITROGEN TOTAL STUDY TERIOD -JULY 1969 TO DECEMBER 1970 (ppm) Arithmetic Mean Standard Deviation Maximum Carbon Monoxide 2.1 2.1 28.4 Sulphur Dioxide 0.01 0.01 s 0.17 Oxidants 0.020 0.019 0.244 Oxides of Nitrogen 0.055 0.092 0;335 (from Lynch and Emslie, 197 2) TABLE 3 COMPARISON OF CARBON MONOXIDE CONCENTRATIONS AT VANIER PARK WITH COMMON OBJECTIVES AND CRITERIA FOR THE ENTIRE STUDY PERIOD OF JULY 1969 TO DECEMBER 1970 Objective or C r i t e r i a Number of Times Concentration Exceeded Percent of Time Concentration May Be Exceeded Canada, Maximum Acceptable - 30 ppm for 1 hr. N i l N i l Canada, Maximum Desirable - 13 ppm for 1 hr. 27 0.1% - 1 Z USA, EPA Primary & Secondary - 35 ppm for 1 hr. N i l N i l Impairment In Time Interva'l Discrimination - 50 ppm for 90 min. N i l N i l - 10 - 15 ppm for 8 hr. 0.1% - 12 Physiological Stress i n Patients With Heart Disease - 30 ppm for 8 hr. N i l N i l (from Lynch and Emslie, 19 72 ) 12. ammonium n i t r a t e aerosols. The formation of (NH^) SO^ from NH3 and SO^ i s a s i g n i f i c a n t process i n scavenging SC>2 from the atmosphere. Ammonium n i t r a t e aerosols are removed from the atmosphere by r a i n and snow or as dry f a l l o u t (Robinson and Robbins, 1968). Sulfur dioxide i s one of the p r i n c i p a l a i r pollutants i n i n d u s t r i a l areas. Its main sources are coal combustion and petroleum r e f i n i n g . The most s i g n i f i c a n t reactions for atmospheric SC>2 are photochemical reactions involving SO2, NC>2 and hydrocarbons. According to Lynch and Emslie (1972), the mean concentration of SO2 over Vancouver during the period of t h e i r study was 0.01 ppm (Table 2). Canada maximum desirable concentration l e v e l of 0.06 ppm for 24 hours was exceeded twice (Table 5). Higher values were observed i n winter than i n summer over the central area of Vancouver, B.C. This led to the conclusion that space heating i s the major source of SO2 to the atmosphere of Vancouver, B.C. The decomposition of organic matter i n swamps, bogs and t i d a l f l a t s i s the natural source of H 2S. Various i n d u s t r i a l operations, notably k r a f t paper production and o i l r e f i n i n g , emit H^S into the atmosphere. However, Junge (1963) concluded that the release of H2S from anthropogenic sources i s only of l o c a l importance because ^ S i s e a s i l y converted to SO2 during combustion or i n gas p u r i f i e r s . Group 5. The gases of thi s group are characterized TABLE 4 COMPARISON OF OXIDANTS CONCENTRATIONS AT VANIER PARK WITH COMMON OBJECTIVES AND CRITERIA FOR THE ENTIRE STUDY PERIOD OF JULY 1969 TO DECEMBER 1970 Objective or C r i t e r i a Number of Times Concentration Exceeded Level associated with eye i r r i t a t i o n - 0.1 ppm peak value 24 Aggravation of respitory diseases - asthma - 0.13 ppm max. daily value N i l Leaf Injury Co sensitive plant species - 0.05 ppm for 4 hrs. 6 Canada, Maximum Acceptable - 0.025 ppm for 24 hrs. 80 Canada, Maximum Desirable - 0.015 ppm for 24 hrs. 169 (from Lynch, and Emslie, 1972) • TABLE 5 COMPARISON OF SULPHUR DIOXIDE CONCENTRATIONS AT VANIER PARK WITH COMMON OBJECTIVES AND CRITERIA FOR THE ENTIRE STUDY PERIOD OF JULY 1969 TO DECEMBER 1970 Objective or C r i t e r i a Number of Times Concentration Exceeded Canada, Maximum Acceptable - 0.34 ppm for 1 hr. - 0.11 ppm for 24 hrs. Canada, Maximum Desirable - 0.17 ppm for 1 hr. - 0.06 ppm for 24 hrs. Injury to some species of trees and shrubs - 0.30 ppm for 8 hrs. N i l N i l N i l 2 N i l (from Lynch and Emslie, 19 72) 14. by high v a r i a b i l i t y i n residence time. The occurrence of radon and thorium i n the atmosphere r e s u l t s from radioactive processes on the earth. Ozone i s photochemically formed i n the atmosphere and destroyed on the earth's surface. Evapora-t i o n from the surface of the earth and p r e c i p i t a t i o n are the basic process i n the c i r c u l a t i o n of H^O. Group 6. In t h i s group are the high order hydro-carbons, gaseous compounds of chlorine, iodine, mercury and other trace gases. Mercury i s considered to be a natural component of the atmosphere i n some areas. It has been found i n the P a c i f i c Ocean a i r as a regular component (Junge, 1971b). Hydrocarbons are released to the atmosphere by man's a c t i v i t i e s and by natural sources. A variety of hydro-carbons which are classed as "reactive" are emitted i n the atmosphere from automobiles, petroleum processing plants and gasoline stations. These compounds react photochemically with oxides of nitrogen and y i e l d products which are commonly c a l l e d oxidants (Robinson and Robbins, 19 68). As shown i n Table 2., the mean oxidant content over Vancouver was found by Lynch and Emslie (1972) to be 0.02 ppm. Table 4, taken from the same publication, shows that on many occasions Canada maximum desirable and maximum acceptable concentrations were exceeded. Hydrocarbons of the terpene class are present at concentrations of a few parts per b i l l i o n i n many forest areas (Went, 1960). It has been postulated that they are polymerized i n the atmosphere to form submicron-size p a r t i c l e s . The optica e f f e c t of t h i s reaction r e s u l t s i n the "blue haze" commonly noted over forested areas (Robinson and Robbins, 1968). II-l.2 Aerosols Aerosols have been defined by Lodge (1962) as "Dispersion i n gas of p a r t i c l e s of matter that are larger than single molecules yet small enough to remain dispersed f o r a s i g n i f i c a n t length of time". The p a r t i c l e s may be s o l i d or l i q u i d and are important i n cloud and p r e c i p i t a t i o n formation, atmospheric chemistry, atmospheric e l e c t r i c i t y , r a d i a t i o n balances and v i s i b i l i t y r e s t r i c t i o n s (Junge, 1963; Davies, 1964) . In F i g . 3 (Junge, 196 3) the nomenclature for categories of natural aerosols i s given along with the importance of each category to atmospheric physics and chemistry. E s s e n t i a l l y three size classes of aerosols are recognized. These are the Aitken p a r t i c l e s (< 0.1 y radius), the large p a r t i c l e s (0.1 to 1.0 y), and the giant p a r t i c l e s (> 1.0 y). The processes which largely determine the proper-t i e s and size of aerosols are sedimentation or g r a v i t a t i o n a l s e t t l i n g and coagulation due to molecular or "Brownian" motion. As the p a r t i c l e radius decreases below a few hundreths of a micron the tendency to coagulate increases. As the radius increases above a few microns g r a v i t a t i o n a l s e t t l i n g becomes pronounced. In general, p a r t i c l e s with r a d i i 16 . NOMENCLATURE / A i t k e n part icles L a r g e particles G i a n t \ p a r t i c l e s / ^ n A i r E l e c t r i c i t y s mo III. i o n s j . / L o r g e ' ' o n s / i Range iportant Fi A t m o s p h e r i c O p t i c s / H o z e N \particles, \ i Range iportant Fi C l o u d P h y s i c s 1 -^—• " Active >s. * £ ^ ~ ~ Condensation ^ f — - — ^ N u c l e i •—M CO A i r C h e m i s t r y - / ' P a r t i c l e s V/hich \ ^ Contain Moin ^ \ j A e r o s o l , M a s s 1 / | 0 - J W* 10"' 10° I01 I01 fi radius Nomenclature of natural aerosols and the importance of particle sizes for various fields of meteorology F i g . 3 (from- Junge, 1963) TABLE 6 MODEL PARTICLE CONCENTRATIONS PER C M 3 IN SURFACE AIR Radius, p <0.0I 0.01- 0.032- 0.10- 0.32- 1.0- >3.2 Total 0.032 0.10 0.32 1.0 3.2 Continent 1600 6800 5800 940 29 0.94 0.029 15,169 Ocean 3 83 105 14 2 0.47 0.29 207 (from Junge, 19 6 3) 17 . larger than 0.1 y are most important as condensation nuclei for cloud droplet formation, (Junge, 1958; 1963). I l l u s t r a t i v e data on p a r t i c l e numbers per volume for each of several classes of p a r t i c l e size are given i n Table 6 from Junge (1963). This author notes that wide deviations from his model can r e s u l t from l o c a l f a c t o r s , e s p e c i a l l y that of man-made p o l l u t i o n . He also states that aerosols have residence times i n the atmosphere of a few days to a few weeks. There are several sources of aerosols. Over the land s o i l dust i s a major source, e s p e c i a l l y i n dry areas. The sea i s a major source of "giant" p a r t i c l e s . I I - l . 3 Temporal v a r i a t i o n i n c i r c u l a t i n g chemicals. The concentrations of c i r c u l a t i n g atmospheric chemicals (groups 2-6 of Table 1) exhibit variations among season, days, hours and even shorter time periods. Variations i n concentrations of anthropogenic chemicals are e s p e c i a l l y large. The variations r e s u l t from interactions between rates of production, dispersion and f a l l o u t . Junge (1963) points out that dispersion i s a complex function of meteorological conditions and l o c a l topography. Transfer and dispersion of chemicals through the atmosphere depends primarily on the thickness of the mixing layer i n which they may be dil u t e d and on d i r e c t i o n and speed of low l e v e l winds, (Munn, 1966; Emslie, 1968; Mosher et a l . 1969; Lynch and Emslie, 1972). The l a t t e r authors report that under conditions of weak atmospheric pressure 18. gradients and clea r skies, the l o c a l and d i u r n a l l y alternating land and sea breezes are strongly i n f l u e n t i a l i n transporting anthropogenic chemicals away from Vancouver, B.C. By them-selves, however, they may not e f f e c t complete clearance of anthropogens from the v i c i n i t y . The authors found that over a period of successive days of stable, land breeze-sea breeze conditions, pollutant concentrations increased from day to day because of the d a i l y return of a portion of the contami-nants to the source area as well as the additions of new quantities. The same authors also found that at sampling stations near the center of Vancouver, the maxima of CO and oxides of nitrogen occurred during the morning and l a t e evening when the land breeze brought i n pollutants from inland, urbanized areas. The minima occur at mid-day when onshore winds carried the pollutants inland. The concentra-ti o n of photochemical oxidants increased during the hours of sunlight while minimum concentrations occurred i n the morning and evening. As i s to be expected, the concentrations of p o l l u -tants of i n d u s t r i a l o r i g i n exhibit a seasonal v a r i a t i o n . The winter increase i n SO2 concentrations i s caused by f u e l combustion for heating purposes and has been referred to previously. Emission of other anthropogenic gases and aerosols are s i m i l a r l y increased. However, Ma g i l l (1956), and Junge (1963) propose a contrary influence, namely, 19. that decreased atmospheric turbulence i n winter leads to a much greater rate of f a l l o u t . Wind speed and d i r e c t i o n can a f f e c t production of atmospheric chemicals as well as t h e i r dispersion. Woodcock (19 53) found that the number and weight of sea s a l t p a r t i c l e s increased with wind speed. He suggested that the abundance of chloride i n r a i n during periods of high winds i s due to the higher production of foam patches on the ocean and increased entrainment of sea s a l t p a r t i c l e s i n incident winds. Gorham (1958b) investigated the e f f e c t of wind speed upon the atmospheric presence of chloride, sulfate and n i t r a t e through measurements and concentrations i n r a i n . His data from the Lake D i s t r i c t , England, show that with high wind speed (about 4-0 km/hr) the supply of sulfate and n i t r a t e was approximately doubled, whereas the chloride supply increased more than tenfold. At low wind speed, on the other hand, the chloride supply was less than that of sulfate and n i t r a t e . The author suggests that the differences probably l i e i n the fact that while entry of the anthropogens sulfate and n i t r a t e into the atmosphere i s continual and larg e l y independent on wind speed, the production of chlorides from the ocean i s dependent on wind speed. Information on the supplies of other ions and t h e i r relationships to wind speeds i s not consistent and does not allow conclusions to be drawn. The evidence that 20. water p r e c i p i t a t i o n from the atmosphere brings down chemicals indicates that the frequency and amount of i t s occurrence must cause temporal variations i n atmospheric concentrations of chemicals. S p e c i f i c information i s absent from the l i t e r a t u r e (Junge, 19 71b). 11-1.4 Sources of chemicals to the troposphere II-1.4.1 The sea. Chloride, sodium, sulfate and most of the magnesium are supplied to the atmosphere from sea spray (Hutchinson, 1957; Gorham, 1961). Examples from Junge (19 63) of sodium, chloride and sulfur concentrations i n the maritime a i r of F l o r i d a and Hawaii are presented i n Table 7. In p a r t i c u l a t e matter, chloride and sodium were found predominantly i n the giant p a r t i c l e s . On the other hand, su l f u r was much more equally represented i n both the large and giant p a r t i c l e s . In the gaseous phase, there were appreciable concentrations of both chlorine and sulphur compounds (Junge, 1956; Eriksson, 1960). Junge (1963) and Woodcock (1953) found that the majority of sea s a l t p a r t i c l e s larger than 1 u r e s u l t from bursting of numerous small a i r bubbles produced by waves at sea ( F ig. 4) and breaking on the shore. These bubbles are swept into the a i r and evaporate there to form s a l t p a r t i c l e s (Gorham, 1961). II-1.4.2 The s o i l . Dust from the s o i l makes important contributions of both soluble and insoluble TABLE 7 Average concentrations of Na, CI and S in particulate and gaseous form in Hawaii and Florida. Values in [zgxm - 3. Large particles Giant particles Gas phase Na CI S Na CI S CI S _ . 0 9 . 1 0 _ 4 . 9 6 . 2 6 1 . 9 2 • 3 7 . 0 6 . 1 0 . 8 5 1 . 4 9 . 1 0 1-57 1 . 0 0 (from Junge, 196 3) o 9 W Water Surface j y The formation of sea-salt par-ticles from the bursting of bubbles. The large droplets IK originate upon disinte-gration of the jet and have been stud-ied by Woodcock and his associates (Kicntzlcr et al. 1951). More numerous and smaller particles M can form from the bursting of the bubble film (Mason, 1954). Fig.4 (from Junge, 196 3) materials to the troposphere. Chemical analyses of rainwater over the i n t e r i o r + 2 of the U.S.A. show considerable quantities of Ca and K + which must have been added from s o i l . The chemical s i m i l a r i t y between K + and Na + suggests that the s o i l may also contribute to the sodium content of the troposphere (Junge, 1958; 1963). According to Pearson and Fisher (1971), s o i l i s the most l i k e l y source of bicarbonate to the tropospheric dust. These authors have also reported very low concentra-tions of phosphate i n p r e c i p i t a t i o n samples co l l e c t e d at nine stations over the Northeastern United States. Generally, the information on phosphate occurrence i n tropospheric dust i s very li m i t e d . Also, low concentrations of s i l i c a have been found i n p r e c i p i t a t i o n over the Hubbard Brook water-shed i n Northern New Hampshire. Presumably the observed phosphate and s i l i c a originated from s o i l dust (Fisher et a l . , 1968). The b a c t e r i a l breakdown of various organic nitrogen compounds i n the s o i l produces NH^, NO3 and some other oxides of nitrogen. The release of ammonia from s o i l s i s a complicated process. The loss of NHg i s a function of pH, and alkaline s o i l s always favor i t s release (Goody and Walshaw, 19 53; Junge, 1963). 23. II-1.4.3 Anthropogenic sources The p r i n c i p a l gaseous chemicals o r i g i n a t i n g from anthropogenic sources are CO, CO25 S 0 2 , NO, N 0 2 and hydro-carbons of which CH4 i s probably the most important. Numerous kinds of atmospheric p a r t i c u l a t e matter also originate as anthropogens. Combustion of f o s s i l fuels i s the p r i n c i p a l generic source of the gases. It has been estimated that the p r i n c i p a l sources of CO i n B r i t i s h Columbia are automobiles, 958 tons per year, and the forest industry, 265,000 tons per year, of which 73,00 0 tons originate from slash burning (B.C. Research, 1970). Coal and o i l combustion are the main anthropogenic sources of SO^. Robinson and Robbins (1968) estimate that of the world-wide annual emission of 220 m i l l i o n tons of sulfu r into the atmosphere, one-third, most as SO2, i s anthropogenic. B.C. Research (197 0) conclude that the pulp and paper industry of B r i t i s h Columbia emits 162,000 tons per year of sulf u r as SO2 and 9,000 tons as reduced sulf u r compounds. The reduced sulf u r compounds, such as hydrogen s u l f i d e , methyl mercaptandimethyl s u l f i d e , and dimethyl d i s u l f i d e are c h a r a c t e r i s t i c features of k r a f t m i l l s . In areas with oxidation-type smog, n i t r i c " o x i d e and nitrogen dioxide are s i g n i f i c a n t constituents of a i r p o l l u t i o n . The anthropogenic sources of these gases are 24 primarily combustion processes i n power plants operating at higher temperatures and automobile exhaust gases. Robinson and Robbins (1968) estimated that the annual world-wide emission of NO2 i s about 53 m i l l i o n tons. In Brdtish Columbia, the 1969 annual emission of nitrogen oxides from automobiles was .43,,500 tons, compared with 25,000 tons emitted from f u e l combustion at pulp and paper m i l l s , and. 2,500 tons from seasonal slash burning (B.C. Research, 1970). Most combustion processes also produce smaller quantities of NH^, but rather higher concentrations of NHg might be expected i n the v i c i n i t y of organic chemical i n d u s t r i e s (Junge, 1963). According to Robinson and Robbins (1968), the estimated world-wide annual t o t a l of atmospheric? emissions of hydrocarbons i s 56 8 m i l l i o n tons. The main sources are automobile exhausts, combustion of f u e l s , rubbish burning and production of gasoline. In B r i t i s h Columbia, the annual t o t a l emission of hydrocarbons was estimated at 181,000 tons f o r automobiles 21 tons from lumber and plywood products, 15,000 tons from slash burning and 3,000 tons from pulp and paper m i l l s (B.C. Research, 1970). In addition to gaseous pollutants, combustipn processes and various i n d u s t r i a l operations produce inorganic and Organic p a r t i c u l a t e matter. The chemical composition of the p a r t i c u l a t e material depends on the nature of the p o l l u t i n g source. The most abundant elements i n dust p a r t i c l e s are s i l i c o n , calcium, magnesium, i r o n , aluminum, lead, zinc and copper. Chemical compounds such as sulfates and n i t r a t e s have also been found as anthropogenic aerosols i n i n d u s t r i a l c i t i e s . Estimates of the amounts of p a r t i c u l a t e matter emitted i n B r i t i s h Columbia were published by B.C. Research (1970). The t o t a l p a r t i c u l a t e emission from pulp and paper m i l l s i n B.C. was 137,000 tons i n 19 69. From t h i s t o t a l , 81,000 tons were emitted from f u e l combustion and the remaining 57 ,000 tons were emitted as Na 2S0 1 + (47 ,000 tons) and CaCOg (9,000 tons). Slash burning emission was 22,000 tons, plywood production 16,000 tons, and automobile emission 6,500 tons of pa r t i c u l a t e matter. Special p o l l u t i o n problems i n Vancouver are caused by bulk shipments of grain, coal, potash, sulf u r and phosphate (rock). In 19 6 9 the annual amount of d u s t f a l l from grain elevators was 13,884 tons, from shipments of potash, 51 tons and of s u l f u r , 12 tons. The most serious p a r t i c u l a t e a i r p o l l u t i o n problem was therefore caused i n the v i c i n i t y of grain elevators i n Vancouver. Potash and sulf u r dust was limited to an area within 1/2 to 3/4 of a mile (0.8 to 1.2 km) of the bulk terminals. I I - l . 5 ' Chemical' f a l l o u t from the troposphere There are several cleaning processes by which natural and anthropogenic substances are removed from the troposphere. Gaseous components are subject to wet removal by p r e c i p i t a t i o n , absorption by the earth's surfaces, or transformation into other gases or aerosols within the atmosphere. For aerosols, the most important mechanisms are wet removal by p r e c i p i t a t i o n and dry removal by sedimentation or impaction on earth surfaces. II-l.5.1 ' Wet removal. This mechanism consists of two d i s t i n c t processes. One i s rainout by which drops receive t h e i r constituents within the clouds. The other i s the washout process which occurs below the clouds when the f a l l i n g droplets pick up p a r t i c l e s on t h e i r way down. Washout i s the most important removal process for sea s a l t p a r t i c l e s and also for aerosols which are concentra-ted below the clouds and contain "giant" p a r t i c l e s (Junge, 1963). Generally, the concentrations of chemicals vary considerably among i n d i v i d u a l rainstorms with respect to duration and in t e n s i t y of r a i n and i t i s therefore d i f f i c u l t to correlate them with meteorological parameters. According to Georgii and Weber (196 0) the v a r i a b i l i t y i n concentration i s larger among small storms and decreases f o r larger storms. The authors ascribe the large v a r i a b i l i t y among small r a i n -f a l l s to the influence of variable quantities of chemicals available to the washout process and to variations i n the potential for raindrop evaporation with attendant increases i n chemical concentration. These authors have found that the r a t i o of maximum to minimum concentrations i s more than 2 0 among storms producing 1 mm of r a i n , about 10 for 10 mm storms, and about 5 f o r 20 mm storms. The decrease of the r a t i o i s caused by decreases i n maximum concentrations while the minima tend to be independent of storm s i z e . On the other hand, Junge (19 63) observed that for larger rainstorms the rainout mechanism i s a c o n t r o l l i n g factor on chemical concentration. During rainy periods i n wet climates chemical concentrations i n r a i n are r e l a t i v e l y low because of the continual operation of rainout processes and the d i l u t i o n e f f e c t of the rainwater. It could be expected that the chemical concentra-t i o n w i l l decrease over time within the period of an i n d i v i d u a l r a i n f a l l , but, l i t t l e relevant information i s available and considerable deviation from such a trend i s probable (Gorham, 1958b; Junge, 1963). Herman and Gorham (1957) have reported that snowfall was not as e f f i c i e n t as r a i n i n the removal of chemical con-stituents from the troposphere. Such findings are not reported i n other l i t e r a t u r e . II-1.5.2 Dry removal. For certain constituents such as sea s a l t , impaction on vegetation, or i n the case of S O 2 5 absorption by vegetation, can be as e f f i c i e n t as p r e c i p i t a t i o n i n the removal process (Junge, 1963). 28. Eriksson (1955; 1960) has pointed out that spruce and pine needles were e f f e c t i v e impaction objects f o r capture of p a r t i c u l a t e C l ~ over Scandinavia. He suggested that the humid climate, morphology of the land, and forest coverage favor dry deposition. Juang and Johnson (1967) have pro-posed that configuration, composition, or e l e c t r o s t a t i c processes occurring on s p e c i f i c vegetation may be important i n the impaction of aerosols. Whenever an airstream i s forced to change d i r e c t i o n , p a r t i c l e s suspended i n i t w i l l tend, due to i n e r t i a l forces, to s e t t l e on the obstacle that has caused the change i n d i r e c t i o n . Thus a be l t of trees w i l l remove a substantial pro-portion of fog from the a i r passing through (Lodge, 1962).. Impaction and g r a v i t a t i o n a l s e t t l i n g i s one of the p r i n c i p a l natural mechanisms of tropospheric removal of dust. Tamm and Troedsson (1955) have drawn attention to the large amount of dust that may be blown on to forests from roads and arable f i e l d s . During dry weather, vegetation captures d r i f t i n g dust p a r t i c l e s which are subsequently washed o f f during r a i n . As postulated by Gorham (1961) dry f a l l o u t may be appreciable i n less humid regions. II-1-5-3 Reaction with vegetation. Reactions of atmospheric SO2 with vegetation provide an additional mechanism for the d i r e c t removal of SO2 from the ambient atmosphere. Sulfur as a plant nutrient i s normally taken up from the s o i l as s u l f a t e . I f the s o i l i s poor i n sulfate supply, gaseous sulfu r dioxide i s absorbed by the plant and rapidly metabolized. There may be a si t u a t i o n where plants improve when exposed to non-damaging leve l s of SO^. How-ever, conifers are p a r t i c u l a r l y sensitive to SC^ and damage occurs i n urban areas where concentration exceeds 0.01-0.0 2 ppm over extended periods of time or 0.04-0.05 ppm for periods of a few days (Katz, 1952; Royal Ministry of Foreign A f f a i r s and Royal Ministry of Agriculture, 1971; Tamm, 1 9 7 2 ) . I I - 1 . 6 Methods' of f a l l o u t measurements and r e s u l t s The measured composition of chemical f a l l o u t i s influenced by the methods used for the c o l l e c t i o n of samples. Based on the c o l l e c t i o n procedures, Whitehead and Feth (1964) divided chemical f a l l o u t into three d i s t i n c t phases: bulk f a l l o u t ( c a l l e d bulk p r e c i p i t a t i o n by Whitehead and Feth), wet f a l l o u t ( c a l l e d r a i n by the above authors), and dry f a l l o u t . Snow-carried f a l l o u t was not mentioned by these authors but w i l l be included i n wet f a l l o u t . I I - 1 . 6 . 1 ' Bulk f a l l o u t . According to Whitehead and Feth ( 1 9 6 4 ) , samples from continuously open c o l l e c t o r s represent bulk f a l l o u t , which-is a solution r e s u l t i n g from r a i n plus dry f a l l o u t . Analysis of such solutions are the most s i g n i f i c a n t for geochemistry because they show the effects of a l l soluble components i n f a l l o u t on the chemical quality of natural water. They also reveal the contribution of airborne components to the mineralization of s o i l water and to the n u t r i t i o n a l status of forest s o i l s . 30 . The most extensive c o l l e c t i o n of data on chemical composition of bulk f a l l o u t i s that reported by Eriksson (19 52, 19 55, 19 58) which i s based on a northern European network of sampling stations. Monthly samples of a l l types of p r e c i p i t a t i o n throughout the year were co l l e c t e d i n polyethylene b o t t l e s , by continuously open c o l l e c t o r s , e l e c t r i c a l l y heated at 5°C. II-1.6.2 Wet f a l l o u t . Sampling of t h i s type of f a l l o u t i s done by means of c o l l e c t o r s that are open only during inte r v a l s of r a i n or snow. This method, which i s preferred by some meteorological investigators, gives informa-t i o n on the solutes i n r a i n or snowfall without any influence from antecedent or subsequent dry f a l l o u t (Lodge et a l . , 1968; Hem, 1970). A c o l l e c t o r provided with an o r i f i c e l i d that i s automatically removed on a signal produced by the f i r s t drops of r a i n i s commonly used"'". Junge and Gustafson (1957), and Junge and Werby (19 58) reported an extensive i n v e s t i g a t i o n of wet f a l l o u t over the United States. These investigators used about 6 0 sampling stations equipped with c o l l e c t o r s which were open only during r a i n f a l l . The samples of each month and s t a t i o n were analyzed for concentrations of ions which represent most of dissolved inorganic matter i n p r e c i p i t a t i o n . Monthly values, for each of several ions were averaged over the 1. Wong Laboratories, Ohio, 45209. 3157 Madison Road, Cin c i n n a t i , 31. period of record, plotted on maps and i s o l i n e s of concentra-tions drawn. Fig. 5 displays the d i s t r i b u t i o n pattern of yearly averages of the concentrations of Na +, K , Ca +^, SO^ , and Cl ~ and three month averages of NOg. Immediately apparent i s the eff e c t of ocean proximity which elevates concentrations of some ions and depresses the concentration of others. Ef f e c t s of i n d u s t r i a l centres and a r i d climates are also v i s i b l e . The average C l ~ concentration rapi d l y decreases from a few mg/1 near the oceans to a f r a c t i o n of a mg/1 inland. It i s apparent that the ocean i s the major source of C l ~ . Concentrations of Na + are also r e l a t i v e l y high among the coasts and low i n inland areas. Junge and Werby (1958) pointed out that, along the coasts, the r a t i o Cl~/Na + i s near to that i n sea water but that i t drops considerably inland. They attributed t h i s to increasing Na + contributions from s o i l dust. The e f f e c t of ocean proximity on K + concentration i s seen to be r e l a t i v e l y small. That s o i l dust i s even more important as a source of K + than of Na + i s shown by r a t i o s of K +/Na + derived by Junge and Werby (1958). They reported that i n sea water t h i s r a t i o i s 0.041 but i n r a i n water i t has a magnitude up to about 1.0. Calcium concentrations are highest over the a r i d zones of the Southwestern U.S., which i s presumably due to supplies CO ----- - - — - • = *• i-j » — "i -.IK-U.I^VJ, . , vuij^wnuci iwo wuiigc, ivooj. (jy courtesy 01 iTanaaawna oj wit AI . . . . . Geophysical Union.) Fig. 5 Concentration d i s t r i b u t i o n patterns of inorganic ions i n rainwater over the Uni ed St es (fr m Junge, 196 3) of dust from s o i l s high i n available calcium. Locally high + 2 coastal concentrations of Ca were ascribed by Junge (1963) + 2 to Ca enrichment from ion exchange processes at the sea surface. Generally, sulfate concentrations along the coasts approximate the 1 to 2 mg/1 concentration that i s estimated to p r e v a i l over sea water. Some of the higher values, both inland and coastal, are att r i b u t a b l e to urban sources. Nitrate and ammonia concentrations were reported by Junge (1958). According to t h i s author, i n less i n d u s t r i a -l i z e d areas maximum concentrations of NO^ were observed i n spring or summer which points to s o i l dust as a source of n i t r a t e . On the other hand the high concentrations over i n d u s t r i a l i z e d areas of the U.S. may be caused by man-made po l l u t i o n . Although the anthropogenic sources of NO3 over the i n d u s t r i a l areas are s i g n i f i c a n t , the author stresses that the earth surface i s the' main source. The highest concentrations of ammonia were also detected over areas with intensive a g r i c u l t u r a l a c t i v i t i e s , p a r t i c u l a r l y over C a l i f o r n i a . As reported by Junge (19 58) the minimum concentrations of ammonia are associated with areas of low s o i l pH, f o r example, i n the Southeastern U.S. II-l.6.3 Comparison of bulk and wet f a l l o u t . Bulk f a l l o u t generally contains more dissolved minerals than wet f a l l o u t . The former tends to r e f l e c t l o c a l sources to a greater degree, both anthropogenic as well as s o i l s and vegetation. According to Whitehead and Feth (1964), bulk f a l l o u t samples from Menlo Park, C a l i f o r n i a , contained 4 to 10 times more mineral solutes than wet f a l l o u t . Junge and Gustafson (1957), i n samples from Boston, found 25 percent more chloride i n samples from continuously open c o l l e c t o r s than from c o l l e c t o r s open only during rainy periods. Although the sampling station i s located i n close proximity to tjie ocean, i t i s also i n t;he range of anthropogenic sources of the i n d u s t r i a l area. II-1.6.4 Dry f a l l o u t . The sampling. of dry f a l l - r out i s effected through the use of a c o l l e c t o r that i s open only between r a i n f a l l or snowfall events. The c o l l e c t e d material i s washed into sampling bottles with d i s t i l l e d water. Whitehead and Feth (19 64) pointed out that the volume of a i r that yielded the sample of p a r t i c u l a t e matter i s unknown. It i s , therefore, d i f f i c u l t to make comparisons between concentrations of chemicals received as dry f a l l o u t and those received as wet f a l l o u t . The method, however, can give some information on the character of p a r t i c u l a t e con-stituents i n the lower levels of the troposphere. Data from Menlo Park as reported by Whitehead and Feth (1964) indicate that the major constituents of dry +2 +2 -2 f a l l o u t are Ca , Mg and SO^ . As pointed out by Viro (1953), dry f a l l o u t can be a very s i g n i f i c a n t contributor to snowpack of mineral constituents, such as s i l i c a , calcium and potassium. Data on the p r i n c i p a l chemical constituents found i n snowpacks i n the Western United States were reported by Feth et_ aJL. , (1964). In t h e i r report analyses of 20 samples from Utah were compared with analyses of 2 0 samples from the Sierra Nevada (Table 8). The higher concentrations of calcium, bicarbonates and sulfates i n Utah samples r e f l e c t influence of dry f a l l o u t from continental sources while higher concentrations of sodium and chlorides i n the Sierra Nevada samples r e f l e c t the influence of oceanic s a l t s . TABLE 8 Chemical Concentrations of Snowpack Samples from Utah and Si e r r a Nevada Utah Si e r r a Nevada E£m P_P_m Ca 2.23 0.79 HCOg 6.3 4.9 SO^ 2.25 0.77 Na 0.60 0.88 CI 0.97 1.02 (from Feth et a l . , 1964) II.2 Stream Water Chemistry Chemical constituents of natural water are derived from tropospheric f a l l o u t , both dry and that contained i n p r e c i p i t a t i o n , and from s o i l and rock weathering. In the presence of vegetation, the "wet" tropospheric f a l l o u t may be either augmented or diminished during passage of r a i n or snow through the vegetation canopy. Thus, chemical inputs to a given stream are conditioned by the regional environment that a f f e c t s the tropospheric chemistry and by l o c a l environ-ment as represented by the vegetation, s o i l s and minerals present on the watershed. The regional influences have been discussed previously. The influences s p e c i f i c to the water-shed of a stream w i l l be discussed here. II-2.1 Forest vegetation P r e c i p i t a t i o n reaching the ground beneath forest canopy contains tropospheric chemicals and, generally, those contributed by the vegetation. The l a t t e r include elements from fo l i a g e surfaces and elements leached by the p r e c i p i t a t i o n from leaves, twigs and bark ( C a r l i s l e et a l . , 1966). Tamm (1951) reported that i n percolating through forest canopies r a i n f a l l i s enriched 18-fold i n potassium as well as 4- and 3-fold i n calcium and sodium respectively. He further con-cluded that trees make a substantial contribution i n nearly a l l nutrients except nitrogen. Apparently tree f o l i a g e may absorb nitrogen from rainwater instead of releasing i t . 38. Nutrients received from the troposphere by a vegetated area are strongly retained within the b i o l o g i c a l cycle and contributions to stream water are diminished thereby. Several investigators ( S t e n l i d , 1958; Ovington, 1965; Bormann' et a l . , 19 71) stated that nutrient inputs may be e n t i r e l y and p a r t i a l l y r e c i r c u l a t e d from the s o i l to the tree and back to the s o i l several times during the growing season. The rate and magnitude of t h i s c i r c u l a t i o n d i f f e r s among the elements. The pattern of flow within the system depends on many fa c t o r s , p a r t i c u l a r l y the nutrient status of the so i l , and the type and age of the f o r e s t . II-2.2 S o i l and rock In the section on tropospheric chemistry consider-able attention has been paid to the troposphere as a source of chemicals to surface waters; however, s o i l and rock weathering i s also an important source (Clarke, 1924; Hutchinson, 19 57; Gorham, 19 61). The several natural pro-cesses which commonly combine to cause d i s i n t e g r a t i o n and decomposition of rock may be c l a s s i f i e d as physical and chemical weathering. Chemical processes are usually more important than physical weathering i n rock decomposition. The rate of chemi-c a l weathering depends upon such factors as the composition and permeability of the rock, the chemistry of incident water and the nature of the f l o r a and fauna i n the immediate environment. The cl i m a t i c factors of temperature, p r e c i p i -t a t i o n and t h e i r temporal variations are also i n f l u e n t i a l . Seasonal differences i n temperature or p r e c i p i t a t i o n favor seasonal differences i n weathering rate (Hem, 1970). The reactions involved i n chemical weathering are , hydrolysis, oxidation and reduction, hydration, carbonation and solution. The unaffected residuals are b a s i c a l l y the res i s t a n t minerals such as quartz,tourmaline, clay minerals and hydrated iron and aluminum oxides (Keller and Frederickson 1952; K e l l e r , 1957; Krauskopf, 1967). As a r e s u l t of soil.and rock weathering, natural water contains many inorganic chemicals both i n solution and suspension. Most water analyses, however, are concerned only with the soluble inorganic matter and there i s almost no information i n the l i t e r a t u r e on the composition of suspended inorganic matter. Although many minor elements may be present i n solution, the dissolved mineral matter i n natural waters i s comprised lar g e l y of.calcium, magnesium, sodium, potassium, bicaronate, carbonate, s u l f a t e , chloride, n i t r a t e , ammonium, phosphate and s i l i c a . The source of each of these constituents to natural water and the processes a f f e c t i n g t h e i r presence w i l l now be .discussed b r i e f l y . Because igneous and meta-morphic rocks are almost exclusively present i n the locale of t h i s study, the discussion i s focussed on these. The weathering of complex calcium-bearing s i l i c a t e s of igneous and metamorphic rocks i s a source of calcium which i s s o l u b i l i z e d by percolating water i n which CO^ from tropo-spheric or s o i l a i r i s dissolved to form weak carbonic acid. In natural stream water the calcium usually exists i n the i o n i c form Ca +^. The concentration i n streams within areas dominated by igneous and metamorphic rocks i s generally low because the rate of mineral decomposition i s low (White" e_t a l . , 1963; Hem, 1970). Magnesium i n igneous rock i s a component of s i l i c a t e minerals, such as o l i v i n e , augite, hornblende, b i o t i t e mica, and other less common minerals. One of the products of chemical weathering i s magnesium carbonate whose s o l u b i l i t y i s controlled by the presence of carbon dioxide i n percolating water. As stated by Hem (197 0) the divalent magnesium ion i s normally the predominant form of magnesium i n natural, water. Sodium i s derived from the weathering of sodium-bearing feldspars of igneous rocks. The products of weather-ing include sodium carbonate which i s soluble i n water. Once the carbonate i s dissolved i t tends to remain so but may be retained by adsorption on mineral surfaces, e s p e c i a l l y on surfaces with high cation exchange capacities such as those of clays (White et a l . , 1963). The p r i n c i p a l potassium minerals i n igneous rocks are potash feldspar, muscovite and b i o t i t e micas, and l e u c i t e . In most natural water, the concentration of potassium i s lower than that of sodium. This i s because of the r e l a t i v e i n s o l u b i l i t y of potassium feldspar and the greater tendency of potassium to be adsorbed on clays and clay minerals (Buckman and Brady, 19 69). The presence of carbonate and bicarbonate i n natural water arises from calcium and magnesium carbonates dissolved i n percolating water. The s o l u b i l i t y of carbonates i s related to the p a r t i a l pressure of carbon dioxide i n the s o i l a i r . Where b i o l o g i c a l decomposition of s o i l organic matter i s active the s o i l water becomes highly charged with carbon dioxide which exists i n equilibrium with carbonic acid. Under the low pH conditions that develop, carbon dioxide attacks the insoluble s o i l carbonates to convert them to soluble bicarbonates (Quastel, 1946; Handbook of Chemistry and Physics, 1966-67). Sulfur exists i n reduced form i n igneous and meta-morphic rocks as m e t a l l i c s u l f i d e s . Under weathering i n humid climates the sulfide s are oxidized to y i e l d sulfate ions which are r e a d i l y soluble. M i c r o b i o l o g i c a l breakdown of organic sulf u r compounds may also add sulfate to natural waters. (Gorham, 19 61). Among the chloride-bearing minerals i n igneous rocks are chlorapatite and so d a l i t e . These minerals have a r e l a t i v e l y limited d i s t r i b u t i o n , however. Most geochemists assume that the chloride i n r i v e r water comes e n t i r e l y from tropospheric f a l l o u t (Junge and Werby, 1958; Eriksson, 1960; Gambell and Fisher, 1966). Nearly a l l of the oxidized nitrogen compounds i n s o i l s and natural waters r e s u l t s from microbial a c t i v i t i e s . The n i t r a t e form i s the f i n a l stage i n the mineralization of nitrogenous organic matter. The amount of n i t r a t e i n surface waters shows seasonal v a r i a t i o n , being generally greater i n winter than i n summer because of summer depletion through b i o l o g i c a l mechanisms and a l g a l a s s i m i l a t i o n (Feth, 1966; Morris and Stumm, 1967). Surface water usually contains some trace of ammonia. It may be derived from either natural or anthro-pogenic sources. Clean r a i n and snow always contain a trace of ammonia, the f i r s t f a l l containing most. Upland waters d i r e c t l y derived from r a i n f a l l may contain some free ammonia. Another source of ammonia to s o i l i s the decay of plant and animal.residues. Much of the ammonium ion so produced i s however held i n the s o i l on the exchange complex and t h i s minimizes i t s access to stream water (Russell, 1950; Hem, 1970 ) . The most common mineral i n which phosphorus i s a major component i s apatite which i s p r i n c i p a l l y calcium orthophosphate. This mineral i s widespread both i n igneous rock and i n marine sediments. According to Hem (1970), phosphorus i n soluble form i s l i k e l y to be present i n natural waters as simple phosphate anions and i n complex with metal ions. It may also occur i n c o l l o i d a l form or i n organic material. According to Sawyer and McCarty (1967) the only inorganic compounds of phosphorus of sig n i f i c a n c e to water chemistry are the phosphates or t h e i r molecularly dehydrated forms, usually referred to as polyphosphates. Polyphosphates gradually hydrolyze i n aqueous solution and revert to the orthophosphates, from which they were derived. The content of phosphate i n natural water i s commonly small because of i t s u t i l i z a t i o n by aquatic vegetation and perhaps i t s adsorption by metal oxides, e s p e c i a l l y f e r r i c hydroxide. (White et a l . , 1963). Also, the high f i x a t i o n of phosphate i n s o i l s containing appreciable amounts of hydrated iron and aluminum oxides, t y p i c a l of podzol s o i l s , means that l i t t l e phosphate leaves the s o i l system (Buckman and Brady, 1969). The element s i l i c o n i s second only to oxygen i n abundance i n the earth's crust (Krauskoff, 1967). C r y s t a l l i n e Si02 (quartz) and combined s i l i c a ( i n feldspars, amphiboles, micas, pyroxenes) are major constituents of igneous rocks. According to Hem (1970), most of the dissolved s i l i c a , as the oxide SiC^, i n natural water re s u l t s from the chemical break-down of s i l i c a t e minerals during weathering. He reports that the range of concentrations of dissolved s i l i c a observed i n natural waters i s from 1 to 30 mg/1. H-2.3 ' Methods and r e s u l t s from previous studies The l i t e r a t u r e contains information on the uptake, retention and release of nutrients from smaller segments of watersheds (Ovington, 1962; Cole, 1963; Cole and Gessel, 1968). Less information i s found on quantitative r e l a t i o n -ships between chemical inputs and outputs for entire watersheds 44. Bormann and Likens (1967, 1971) determined the nutrient budget for six small watersheds at the Hubbard Brook Experimental Forest, New Hampshire, from the difference between meteorological input and geological output. They collected samples of p r e c i p i t a t i o n and bulk f a l l o u t using open c o l l e c t o r s located i n forest openings of the watersheds. At the same time they col l e c t e d weekly samples of stream water at points on the streams where the flow was continuously gauged. They calculated the inputs of several chemicals from the product of concentration and volume of r a i n and snow-water col l e c t e d . Outputs were calculated as products of stream water volume and chemical concentration. Inputs and outputs were appropriately t o t a l l e d to give annual values i n kilograms per hectare of the watershed area. From data reported by Likens et al_. , (19 67) and Fisher' et a l . (1968), Table 9 was prepared. It shows average annual inputs and outputs of chemicals from one of the six experimental watersheds i n the water year 1964-65. Bulk f a l l o u t on the watershed provides most of the 3 2.1 kg/ha of sulfate discharged annually by the stream from the watershed 2. On the contrary, the annual input of s i l i c a averaged 2.0 kg/ha while output'in the stream water was 20.7 kg/ha per year. The inputs from the troposphere of both ammonium and n i t r a t e exceeded outputs i n stream water. The climate of Hubbard Brook i s continental (Likens et a l . , .1967). Corresponding information for maritime 45. TABLE' 9 The Hubbard Brook Experimental Forest, Water-shed 2, Water Year 1964-65, Annual Average Input and Output Loads i n Bulk Fallout and Discharge Input Output Balance P r e c i p i t a t i o n (mm) 949.0 Discharge (mm) 487 .0 462 .0 Ca (kg/ha-yr) 2.8 4.3 - 1.5 M g 1.1 1.8 - 0.7 Na " 2.1 4.3 - 2.2 K " 1.8 0.9 0.9 so 4 30.0 32.1 - 2.1 NH4 2.1 0.2 1.9 N0 3 6.7 6.4 0.3 S i 0 2 " 2.0 20.7 -18.7 A l " 0.0 1.0 - 1.0 HC03 " 0.0 2.7 - 2.7 (from Likens et a l . , 1967; Fisher et a l . , 1968) climates i s scarce but data from Scotland (Holden, 1966) suggests that there too, stream water chemistry may be very dependent on bulk f a l l o u t on the respective catchments. Ionic loads of the three Scottish s i t e s reported by Holden (1966) are shown i n Table 10. Strath Bran i s located on the north coast, approximately 45 km from the A t l a n t i c Ocean. Faskally i s located about 110 km and Shelligan about 100 km southerly from the ocean, and i n the proximity of the indus-t r i a l b e l t of Scotland. The loads of chloride, sodium and magnesium were highest at Strath Bran and lowest at Faskally, which i s farthest from the sea. According to the author, the higher loads of sulfate and also n i t r a t e and ammonium at the southerly located s i t e s (Faskally and Shelligan) suggest the possible influence of anthropogenic sources from i n d u s t r i a l areas. Holden (1966) further reported that data from several Scottish s i t e s show that the bulk f a l l o u t of chemicals, p a r t i c u l a r l y sodium and chloride, varies widely with s i t e l o c a t i o n . He noted that the exposed island stations have the highest almost anomalous, quantities. M i l l e r (19 7 0) from his study of the hard beech (Nothofagus truncata) ecosystem at Hutt Valley, near Wellington, New Zealand,reported annual quantities of tropospheric inputs and drainage water outputs (Table 11). Inputs of potassium, phosphorus, nitrogen and sulf u r exceeded outputs to indicate retention i n the ecosystem. Con-tributions of magnesium, calci'um arid s i l i c o n from s o i l and rock weathering are indicated by t h e i r excesses i n outputs. TABLE 10 Annual Average Input Loads i n Bulk Fallout at Three Scottish Stations Strath Bran Faskally Shelligan P r e c i p i t a t i o n (mm) 1352 .0 697 .0 1040.0 Ca (kg/ha-yr) 5 .92 5.49 6.71 Mg 4 .59 1. 21 3 . 52 Na " 47 . 20 11.50 18 . 45 K " 2 . 30 1.44 2.45 S " 7 .54 7.53 18 . 30 CI " 82 .80 19 .90 32.30 NO 3 0 .35 1.02 . 1.97 NH^ 0 .86 1.63 4.73 (from Holden, 1966) TABLE 11 Hutt Valley, New Zealand, Annual Average Input and Output Loads i n Bulk Fallout and i n Discharge Input Output Balance P r e c i p i t a t i o n (mm) 1300.0 Ca (kg/ha-yr) 9.0 26.0 - 17.0 Mg 12.0 22.0 - 10.0 Na 11 68.0 76.0 - 8.0 K 11 7.0 6.0 1.0 S " 10 .0 8.0 2.0 CI 11 134.0 134.0 N " 5.0 2.4 2.6 P " 0.4 0.2 0 . 2 Si " 6.0 49.0 - 43.0 (from M i l l e r , 197 0) 49 . i III STUDY AREAS I I I - l Selection of Areas The objectives of the study and the required instrumentation necessitated the use of two widely separated study areas. A small, watertight and e s s e n t i a l l y undisturbed watershed was required f o r the input-output study, while a r e a d i l y accessible s i t e was needed for the study of temporal v a r i a b i l i t y i n chemical f a l l o u t with i t s requirements of con-tinuous sampling. The Jamieson Creek watershed was chosen for the quantitative study of i o n i c inputs by chemical f a l l o u t and i o n i c outputs i n stream flow. This p r i s t i n e forested water-shed was already instrumented for measurements of p r e c i p i -t a t i o n , streamflow and stream water temperature f o r purposes of a broad program of hydrometeorological research encom-passing the municipal watersheds of Capilano and Seymour Rivers. Its location within the Seymour basin i s shown i n Fig . 6. Its instrumentation i s shown•in Fig.7. To meet the requirement of continuous sampling of f a l l o u t , a s i t e was chosen within the University of B r i t i s h Columbia campus on Point Grey (Fig. 6). This location permitted v i s i t a t i o n as necessary during day or night. It also provided f a c i l i t i e s that permitted the operation of a sophisticated automatic sampler of both bulk f a l l o u t and wet f a l l o u t . B R I T I S H C O L U M B I A Scale 1:250,000 1 Inch to 4 Miles Approximately Mil t I F i g . 6. Topographic map showing-'the l o c a t i o n of" KfrTe Jamieson Creek ' watershed (JC) and the P o i n t Grey s i t e (PG) . 7 . Capilano and Seymour drainage basins showing location of experimental water-sheds and f i e l d instrumented s i t e s (from Goodell, 1972). III-2 Oceanic and Anthropogenic Environments As i l l u s t r a t e d i n F i g . 6, the Point Grey s i t e i s f o r t u i t o u s l y situated i n close proximity to the ocean and p r i n c i p a l l y westward of any i n d u s t r i a l area. The Jamieson Creek watershed i s approximately 2 5 km north of Vancouver, 15 km east from Howe Sound at an average elevation of about 7 50 m. Since the p r e v a i l i n g winds are westerly i n t h i s l a t i t u d e they sweep i n from the ocean to r i s e upward over the urban area and the north shore mountains. One would expect, therefore, that the Jamieson Creek area would be subjected to smoke, fumes and noxious gases from the c i t y . Lynch and Emslie (1972) found SO2 concentrations during winter months over the r e s i d e n t i a l part of the c i t y that they con-sidered attributable to f u e l combustion for heating purposes. They also found high concentrations of f l y ash over Port Moody and New Westminster (Fig. 6). Slash burning i s another p o t e n t i a l source of atmospheric chemicals to the Jamieson Creek watershed. Nikleva (1972) pointed out that high pressure areas characterized by l i g h t winds often stagnate over southern B r i t i s h Columbia i n the autumn. The large scale subsidence accompanying these weather systems produces a v e r t i c a l temperature p r o f i l e which i n h i b i t s the formation of a deep mixing layer. Since most slash burning takes place i n the autumn when the above conditions are most prevalent, a high accumulation of pollutants may be expected to occur. 53. The Point Grey s i t e , on the other hand, may be less subjected to anthropogenic contaminants since the a i r currents sweep over some 30 to 50 km of sea water p r i o r to t h e i r a r r i v a l over i t . One must recognize, however, the p o s s i b i l i t y of some contamination of both sampling s i t e s from pulp m i l l emissions, some of them 30 to 50 km westward, namely at Crofton and Nanaimo on Vancouver Island, and others at Port Mellon and Woodfibre (Fig. 6) to the north of Point Grey. III-3 Climatic Environment III-3.1 A i r masses The climate of southwestern B r i t i s h Columbia i s controlled by the P a c i f i c High and Aleutian Low pressure systems. The former i s a semi-permanent c e l l centered i n the eastern P a c i f i c . The a i r c i r c u l a t e s clockwise around the P a c i f i c High and counter-clockwise around the Low pressure c e l l . The l a t t e r becomes very weak and moves north of the Aleutian Islands during the summer. At the same time the P a c i f i c High i n t e n s i f i e s and spreads over most of the north P a c i f i c Ocean. The clockwise c i r c u l a t i o n brings a north-westerly flow of cool and r e l a t i v e l y dry a i r from the north P a c i f i c to southern B r i t i s h Columbia, and consequently summer in and near Vancouver i s a season of low p r e c i p i t a t i o n . The Aleutian Low i n t e n s i f i e s and moves southward i n the f a l l , reaching i t s maximum in t e n s i t y i n mid-winter, while the P a c i f i c High moves southward and weakens. The res u l t i n g c i r c u l a t i o n brings a southwesterly flow of warm and moist a i r to southwestern B r i t i s h Columbia. This a i r i s warmer than the land surface, thus cooling and condensation take place to cause a rainy season during the l a t e f a l l and winter (Beer and Leopold, 1947; U.S. Department of I n t e r i o r , 1959). The prevalence over southwestern B r i t i s h Columbia i n summer of a i r masses cooler than land surfaces and, i n winter, of a i r masses normally warmer than the land has significance to tropophospheric chemistry, e s p e c i a l l y as affected by l o c a l sources of gaseous and p a r t i c u l a t e matter. Landsberg (19 51) has described the relevant phenomena. A r e l a t i v e l y cold a i r mass warmed from below r e s u l t s i n i n s t a b i l i t y that promotes good atmospheric dispersion of l o c a l l y introduced matter. On the other hand, a r e l a t i v e l y warm mass cooled from below r e s u l t s i n s t a b i l i t y that i n h i b i t s atmospheric dispersion (Beer and Leopold, 1947). III-3.2 Wind. During December and January southwestern B r i t i s h Columbia i s occasionally subjected to strong flows of a i r from a r c t i c high pressure c e l l s . The winds spread towards the coast from the i n t e r i o r through the major v a l l e y s , i n c l u s i v e of the Seymour Valley. Baudat and Wright (19 69) and Environment of Canada (1971) reported that the wind v e l o c i t i e s commonly reach 35 to 45 miles per hour (56.3 to 72.4 km/hr) with gusts of 50 to 70 miles per hour (80.5 to 112.5 km/hr). For most of the winter, however, the coastal area i s under the influence of P a c i f i c storms as previously noted. Frontal disturbances associated with these storms move across the southern coast accompanied by southeasterly winds, often reaching a speed of 30 miles per hour (48.3 km/hr (Environment Canada, 1971). When these gusting winds approach the mountains containing the Seymour and Capilano Valleys they are channelled up these and other narrow, steep valleys (Baudat and Wright, 1969; Schaefer and Nikleva, 1973) . III-3.3 P r e c i p i t a t i o n P r e c i p i t a t i o n i n the Vancouver area shows a pro-nounced seasonal v a r i a t i o n and also, because of topographic e f f e c t s , strong s p a t i a l differences i n annual amounts. Normally, summers are dry with only a few days of r a i n . In winters there are many days of r a i n i n each month. Because most winter p r e c i p i t a t i o n i s brought by P a c i f i c storms, the r e l a t i v e l y f l a t t e r r a i n of Vancouver l i e s i n the r a i n -shadow of the mountains of Vancouver Island and the Olympic Penninsula. This i s r e f l e c t e d i n r e l a t i v e l y low annual p r e c i p i t a t i o n , nearly a l l of which f a l l s as r a i n . Table 12 shows that at the University of B r i t i s h Columbia station on Point Grey, the 3 0-year mean annual p r e c i p i t a t i o n ( r a i n plus snow) i s equivalent to 48.42 inches (12 29.8 mm) of water and the mean r a i n f a l l i s 46.49 inches TABLE 1 2 . TEMPERATURE A N D PRECIPITATION 1941 - 1970 ELEMENT and STATION JAN FEB MAR APR O D D SEYMOUR FALLS LATITUDE 4 9 2 6 N MEAN RAINFALL ( INCHES ) 1 6 . 1 2 1 3 . 5 8 1 1 . 8 0 1 0 . 4 4 MEAN SNOWFALL 3 1 . 3 1 8.6 1 0 . 3 1.0 MEAN TOTAL PRECIPITATION 1 9 . 2 4 1 5 . 5 0 1 2 . 8 2 1 0 . 5 4 GREATEST RAINFALL IN 2 4 HRS 1 2 . 3 7 5 . 7 8 4 . 8 9 4.61 NO. OF YEARS OF RECORD 4 3 4 2 4 2 4 2 GREATEST SNOWFALL IN 2 4 HRS 2 6 . 0 2 3 . 0 1 2 . 0 8 . 0 NO. OF YEARS OF RECORD 4 3 4 3 4 3 4 3 GREATEST PRECIPITATION IN 2 4 HRS 1 2 . 3 7 5 . 7 8 4 . 8 9 4.61 NO. OF YEARS OF KtCURO 4 3 4 2 4 2 4 2 NO. OF DAYS WITH MEASURABLE RAIN 1 4 1 4 1 5 1 6 NO. OF DAYS WITH MEASURABLE SNOW 7 5 4 1 NO. OF DAYS WITH M. PRECIPITATION 1 9 1 6 1 7 1 6 MAY JUN LONGITUDE 122 58 W ELEVATION 660 FT ASL 5.82 4.45 3.18 4.37 8.07 19.62 20.12 20.41 137.98 1 0.0 0.0 0.0 0.0 0.0 0.2 5.9 21.6 88.9 1 5.82 4.45 3.18 4.37 8.07 19.64 20.77 22.57 146.97 1 4.28 3.72 2.40 6.88 6.28 8.36 9.92 9.65 12.37 1 41 43 41 43 43 42 41 44 T 0.0 0.0 0.0 0.0 3.5 14.0 25.0 26.0 1 42 43 43 43 43 42 41 44 4.28 3.72 2.40 6.88 6.28 8.36 9.92 9.65 12.37 1 41 43 41 43 43 42 42 44 13 12 7 9 10 17 19 17 163 1 0 0 0 0 0 & 2 6 25 1 13 12 7 9 10 17 19 20 175 1 ELEMENT and STATION J A N FEB MAR APR MAY JUN JUL A U G SEPT OCT N O V DEC YEAR o g l l non VANCOUVER UBC LATITUOE 49 15 N LONGITUDE 123 15 W ELEVATION 285 i FT ASL MEAN DAILY TEMPERATURE ( DEG F ) 37.0 40.4 42.6 47.5 53.6 58.5 62.7 62 .2 58.1 50.7 43.3 39.4 49. 7 8 MEAN DAILY MAXIMUM TEMPERATURE 41.5 45.2 48.0 53.6 60. 2 65.2 70.0 69.5 64.7 56.3 4P.0 43.4 55.5 8 MEAN OAILY MINIMUM TEMPERATURE 32.5 35.6 37.1 41 .4 46.9 51.7 55.4 54 .8 51.5 45.0 38.6 35.3 43.8 h EXTREME MAXIMUM TEMPERATURE 58 63 64 71 85 86 B8 91 78 72 60 67 91 5 NO. OF YEARS OF RECORD 13 13 13 13 13 13 13 13 14 14 14 14 EXTREME MINIMUM TEMPERATURE 7 21 23 33 35 44 48 46 33 32 19 - 1 - 1 5 NO. OF YEARS OF RECORD 13 13 13 13 13 13 13 13 14 14 14 14 NO. OF DAYS WITH FROST 12 5 4 0 0 0 0 0 0 # 3 9 33 5 MEAN RAINFALL ( INCHES I 5.91 5. 13 3.86 2.68 2.08 1 .89 1.26 1 .89 2.65 5.90 6.49 6.75 46.49 8 MEAN SNOWFALL 7.5 0.5 1.3 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.7 9.3 19.3 5 MEAN TOTAL PRECIPITATION 6.66 5.18 3.99 2.68 2.08 1.89 1.26 1 .89 2.65 5.90 6.56 7.68 48.42 B GREATESI RAINFALL IN 24 HRS 3.47 2.01 1.68 1.13 0.95 0.82 1 .22 1 .49 1.73 1.81 2.18 1.96 3.47 5 NO. OF YEARS OF RECORD 13 13 13 13 13 13 1 3 13 14 14 14 14 GREATEST SNOWFALL IN 24 HRS 7.8 1.7 5.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 3 .0 9.3 9.3 5 .NO. OF YEARS OF RECORD 13 13 13 13 13 13 13 13 14 14 14 14 GREATEST PRECIPITATION IN 24 HRS 3.47 2.01 1.68 1.13 0.95 0.82 1.22 1 .49 1.73 1.81 2.18 2. 16 3.47 5 NO. OF YEARS OF RECORD 13 13 13 13 13 13 13 13 14 14 14 14 NO. OF DAYS WITH MEASURABLE RAIN 18 16 16 14 10 9 6 9 10 16 19 20 163 5 NO. OF OAYS WITH MEASURABLE SNOW 4 1 1 0 0 0 0 0 0 0 <= 3 9 5 NO. OF DAYS WITH M. PRECIPITATION 20 16 17 14 10 9 6 9 10 16 19 22 168 5 The actual period of record used to compute the means of temperature and precipi tat ion may be determined through the use of code numbers which appear in the column label led "Type of N o r m a l " . The code is as fol lows: 1 30 years between 1941 and 1970 2 25 to 29 years between 1941 and 1970 3 20 to 24 years between 1941 and 1970 4 15 to 19 years between 1941 and 1970 5 10 to 14 years between 1941 and 1970 6 less than 10 years 7 combined data from 2 cr more stations 8 adjusted 9 estimated (from Environment Canada, 197 0) (1180.8 mm). Snow i s occasional from November through February with a 10-14 year mean of 19.3 inches (490.2 mm) of snow depth. The greatest r a i n f a l l i n 24 hours was 3.47 inches (88.1 mm) and the greatest 24 hour snowfall was 9 .'3 inches (232.2 mm). As the P a c i f i c storms move eastward and approach the coastal mountains the orographic e f f e c t causes increased p r e c i p i t a t i o n and a greater proportion of snowfall. Accord-ing to Schaefer and Nikleva (1973), the ordinary orographic l i f t i n g of a i r masses by mountain slopes i s augmented i n narrow, steep-walled v a l l e y s , such as that of Seymour, by forced convergence. The 3 0-year record of p r e c i p i t a t i o n at Seymour F a l l s , the lowermost v a l l e y gauge, at an elevation of 660 feet (201.1 m), i s also shown i n Table 12. (Environment of Canada, 1970). The mean annual t o t a l p r e c i p i t a t i o n i s equi-valent to 146.97 inches (3733 mm) of water with r a i n f a l l accounting for 137.98 inches (3504.7 mm). Total snow depth averages 88.9 inches (2258 mm). The greatest r a i n f a l l i n 24 hours has been 12.37 inches (314.2 mm) and the greatest 24-hour snowfall depth was 2 6.0 inches (660.4 mm). From October through A p r i l , p r e c i p i t a t i o n may be either r a i n or snow. The snow depth i n some years can reach 6 meters at the upper 2 elevation of the Jamieson Creek watershed . Data from these 2. F i l e s of the Faculty of Forestry, The University of B r i t i s h Columbia, Vancouver 8, B.C. same records indicate that at the lower end of the Jamieson Creek watershed, the average annual p r e c i p i t a t i o n for 19 7 0 to 1972 was 146.8 inches (3720.3 mm) and for the upper end of the watershed was 163.2 inches (4145.3 mm). III-4 T e r r e s t r i a l Environment of the Jamieson Creek. Watershed III-4.1 Physiography and hydrology The Jamieson Creek watershed has an area of 2.9 9 km . The elevation range i s from 3 04.8 m at the stream gauging station to 1280.2 m at the highest point of the divide. The topography i s shown i n d e t a i l i n Fig.8. The a e r i a l photograph i n Fig. 9 shows that the topographic boundary of.the watershed i s well defined, but that the c l i m a t i c climax coniferous forest cover of the watershed f i t s into the matrix of surrounding vegetation without marked discontinuity. The watershed i s underlain by g r a n i t i c bedrock and i s considered to be watertight. Drainage of the area i s by Jamieson Creek and i t s t r i b u t a r i e s to the Seymour River. The watershed stream channels are characterized by boulders, occasional bedrock exposures and numerous dams of debris from the over-mature f o r e s t . Streamflow i n Jamieson Creek i s rapid, the channel gradient averaging some 2 0 percent and exceeding 10 0 percent over short reaches. There i s a pronounced seasonal v a r i a t i o n in stream discharge, which i s demonstrated on the hydrograph of Jamieson Creek for the water year 197 0-71, shown i n F i g . 10. 59. o Bulk Fa l l - o u t Collectors Elevation Height (m) Fig.8. Map of the Jamieson Creek Watershed. The flow ranges from several cubic meters per second during the spring and f a l l runoff to a few hundredths of a cubic meter per second i n summer months and during cold periods of winter. III-4.2 Bedrock geology A number of authors have investigated aspects of the geology of the Coast Mountains within which the Jamieson Creek watershed l i e s . Mathews (1951; 197 2) and Roddick (1965.) indicate that the rock mantle of about 80% of the Coast Mountains i s plutonic, with the remainder consisting of pendants of sedimentary volcanic and metamorphic rocks. The plutonic rocks consist of some or a l l of f i v e major s i l i c a t e minerals, namely, plagioclase, hornblende, b i o t i t e , quartz, and potassium feldspar. According to Roddick (1965) most of the rock i n the upper Seymour River area i s a mediums-grained quartz d i o r i t e with more hornblende than b i o t i t e . 111-4.3 S u r f i c i a l geology The Pleistocene glaciations mantled almost the entire area (Armstrong, 1954, 1960; Holland, 1964) with g l a c i a l deposits i n which g l a c i a l t i l l of various depths pre-dominates. A tough, r e l a t i v e l y impervious basal or lodgement t i l l i s commonly encountered at 0.5 to 1.2 m below the ground surface. Above t h i s l i e s a mixture of loose ablation t i l l and weathered basal t i l l . The mineralogy of these deposits r e f l e c t s t h e i r plutonic rock derivation. Gravelly loamy sands with a high stone content predominate i n the t i l l s . The texture i n the solum or B horizon i s f i n e r as a re s u l t of weathering; generally gravelly sandy loams are predominant (Lewis, 1973). Depth of the s u r f i c i a l materials to bedrock i s largely controlled by topography. The t i l l has mostly been removed by c o l l u v i a l action from the steep upper valley slopes whereas i t remains on the gentler slopes of the lower v a l l e y walls. The c o l l u v i a l materials, which p i l e up below steep slopes consist of a mixture of g l a c i a l t i l l and angular stony and bouldery colluvium which was ph y s i c a l l y weathered from the exposed bedrock,. These c o l l u v i a l deposits cover a considerable portion of upper slopes, but each deposit covers a r e l a t i v e l y small area. The end r e s u l t i s a highly complex, random pattern of shallow t i l l over bedrock, exposed bedrock, shallow forest f l o o r over bedrock, and deep colluvium (op_. c i t . ) . 111-4.4 Soils The following description of the s o i l of the Jamieson Creek watershed i s based on s o i l mapping by D.Parsons 3 . . . . and L.M. Lavkulich , and mapping and c l a s s i f i c a t i o n c a r r i e d out i n 1969 by T. Lewis (1973). A l l terms for s o i l c l a s s i f i -cation are from The System of S o i l C l a s s i f i c a t i o n f o r Canada (Canada Department of Agriculture, 1970). 3. F i l e s of the Department of S o i l Science, University of B r i t i s h Columbia, Vancouver 8, B.C. III-4.4.1 Physical c h a r a c t e r i s t i c s . Large v a r i a -tions i n s o i l c h a r a c t e r i s t i c s occur i n d i f f e r e n t parts of the watershed. For the purpose of the present study, three broad categories of s o i l s are distinguished, primarily on the basis of parent materials, depth over bedrock, p r o f i l e development and drainage pattern. From a hydrologic point of view three groups of , s o i l s may be recognized: a) In the upper part of the watershed, shallow well drained s o i l s developing on bedrock are dominated by poorly to well decomposed organic matter horizons. They may have thin mineral Ae and Bfh horizons but often the organic L, F and H horizons are i n d i r e c t contact with the bed-rock. These s o i l s belong to the category of L i t h i c F o l i s o l s and L i t h i c Podzols, (Lewis and Lavkulich, 1972). According to Lewis (1973) the series Cannell, Dennett, Sayres, and Hollyburn are included. Their t y p i c a l topographic locations are indicated on the sketch of Fig.11. b) The second group of s o i l s are those which developed on imperfectly drained s i t e s . These s o i l s have formed i n ablation and weathered basal t i l l mixtures overlying unweathered basal t i l l or bedrock, under the influence of seepage water. Lower slopes and midslope benches and drainage depressions are usually characterized by these ,HOLLYBURN organs / „ »DENNETT Soil Pattern on. Ridge Tops LIONS DENNETT ROCK OUTCROP PALISADE DENNETT ROCK OUTCROP PALISADE Soil Pattern on Steep Upper Slopes STRACHAN CANNELL STRACHAN BURWELL Soil Pattern on Lower Slopes Fig. 11. Schematic diagram of s o i l - l a n d form relationship. 66 . wetter, p e r i o d i c a l l y waterlogged s o i l s which have shallow L, F and H horizons underlain by a gleyed and stony Bhf horizon. These s o i l s belong to the category of Gleyed Ferro-humic Podzols, Burwell s e r i e s , (op. c i t . ) . F i g . 11 shows t h e i r t y p i c a l l o cation on lower slopes, c) The t h i r d category comprises moderately well drained s o i l s developed i n t i l l and/or colluvium. These s o i l s show good horizon development with substantial develop-ment of Ae horizons overlying strong podzolic Bfh and Bhf horizons. They have been c l a s s i f i e d as the Strachan and Palisade s o i l s (op. c i t . ) . Their normal slope positions are indicated i n F i g . 11. Because of the protection of the mineral s o i l by the developed organic horizons, the high permeability of the mineral s o i l (Chamberlin, 1972), low i n t e n s i t i e s of r a i n f a l l and n e g l i g i b l e presence of frozen s o i l , surface runoff r a r e l y , i f ever, occurs on the Jamieson Creek watershed. E s s e n t i a l l y , a l l r a i n f a l l and snowmelt water undergoes percolation through the s o i l to stream channels. Thus the y i e l d of p a r t i c u l a t e matter from the s o i l i s r e l a t i v e l y low. A large po t e n t i a l exists for the y i e l d of solutes from the s o i l and rock materials because of the very wet climate over much of the year. However, the very permeable s o i l s , steep slopes and great annual p r e c i p i t a t i o n r e s u l t s i n frequent, rapid flushing of the s o i l and should favor low concentration of solutes i n the drainage waters delivered to stream channels. 67 . III-4.4.2 Chemical properties Information on chemical properties of s o i l s s p e c i f i c to the Jamieson Creek watershed are not available. However, the majority of s o i l s i n the watershed are podzols which t y p i c a l l y occur i n Coastal B r i t i s h Columbia (Canada Department of Agriculture, 1972). The podzols are very acid and base unsaturated. The cation exchange complex i s largely pH dependent since organic matter and iron and aluminum oxides provide more exchange s i t e s than the s i l i c a t e clays. Also nitrogen and phosphorus levels are low i n the s o i l . The podzols are characterized by thin and discon-tinuous Ae horizons underlain by strong podzol B horizons. According to the study ca r r i e d out by Lewis (1973) the B horizons commonly have higher iron and aluminum content than parent material. Whereas iron and aluminum are immobilized i n the s o i l , large amounts of s i l i c a are l o s t from the parent material by a combination of weathering and leaching. Other elements such as calcium, potassium and magnesium are l o s t to drainage water i n si m i l a r fashion and may influence the quality of stream water from the watershed. III-4.5 Vegetation The Jamieson Creek watershed i s e n t i r e l y covered by mature and over-mature coniferous f o r e s t . Based on the forest c l a s s i f i c a t i o n .of B r i t i s h Columbia proposed by Krajina (1965) the vegetation may be described as follows: Below an eleva-68. t i o n of 3,0 00 feet (914.4 m) the Jamieson Creek watershed, which extends to 4,200 feet (1280.2 m) l i e s within the wetter sub-zone of the Coastal Western Hemlock Zone. The most productive trees i n t h i s zone are Douglas f i r (Pseudotsuga menziesii var. menziesii), western hemlock (Tsuga hetero-£hylla) } western redcedar (Thuja EliQ&Jcp , Sitka spruce (Picea s i t c h e n s i s ) , and P a c i f i c s i l v e r f i r (Abies amabilis). Associated shrubs are s a l a l CGaultheria shallon), Alaska blueberry (Vaccinium alaskaense), red huckleberry (Vaccinium parvifolium), and western mountain ash (Sorbus s i t c h e n s i s ) . Above approximately 3,000 feet (914.4 m) the sub-alpine Mountain Hemlock Zone begins. According to Krajina (1965) the cl i m a t i c climax plant community of the zone i s represented by mountain hemlock (Tsuga. mertensiana), P a c i f i c s i l v e r f i r , Alaska blueberry, thin-leaved huckleberry (Vaccinium membranaceum), and strawberry dwarf bramble (Rubus gedatus). The great depth of snow accumulation and i t s long duration influences the d i s t r i b u t i o n of epiphytic species on tree trunks. The snow pack as i t melts provides an extended moisture supply to hygrophytic bryophyte and lush herb communities downslope from the retr e a t i n g snow banks. IV EXPERIMENTAL METHODS IV-1 Instrumentalion Network The instrumentation used for f i e l d measurement i s i l l u s t r a t e d i n Figures 12 and 16-. It included c o l l e c t o r s for bulk f a l l o u t on the Jamieson Creek watershed (Figs. 12 and 13), an automatic c o l l e c t o r of wet f a l l o u t at the Point Grey s i t e (Fig. 14-) and a V-notch weir for measurement of d i s -charge from the Jamieson Creek watershed (Figs. 15 and 16). This instrumentation i s described i n d e t a i l i n the following pages. IV-1.1 Bulk f a l l o u t instrumentation Jamieson Creek watershed was instrumented with twelve bulk f a l l o u t c o l l e c t o r s , located i n four elevation , zones as shown i n F i g . 8. These c o l l e c t o r s (Figs. 12 and 13) were used during the rainy season. They were fabricated from 152 mm diameter polyethylene funnels, tygon tubing and 3 - l i t e r r e servoirs. The uncovered funnels were fix e d two meters above the s o i l surface. A renewable nylon screen was inserted 3 0 mm above the throat of each funnel to prevent debris and insects from entering the reservoir. The loop i n the tygon tubing formed a water b a r r i e r to i s o l a t e the reservoir from the atmosphere thereby minimizing evapora-t i o n . This i s o l a t i o n was completed by forcing a i r discharge from the reservoir into a water f i l l e d b o t t l e . Beginning i n November 1970, the reservoirs were Fig.12. Fig.13. Fig.14. Bulk f a l l o u t P r e c i p i t a t i o n and Bulk and wet f a l l o u t c o l l e c t o r . bulk f a l l o u t automatic c o l l e c t o r , c o l l e c t o r s . emptied at weekly i n t e r v a l s . The volume of p r e c i p i t a t i o n was. measured i n a calibrated cylinder and subsamples taken for analyses. During the winter, January to A p r i l 1971, the s i t e s located at the higher elevations of the watershed were inaccessible. P r e c i p i t a t i o n i n the form of freshly f a l l e n snow was collected i n two open, polyethylene containers placed approximately three meters above the s o i l surface i n the lowest elevation zone. The sampling i n t e r v a l for snow c o l l e c t i o n varied, but i n most cases was weekly, depending upon a c c e s s i b i l i t y of the s i t e , IV-1. 2 Wet 'fallout' instrumentation A special r a i n f a l l c o l l e c t o r (Fig. 14) to allow comparison of wet and bulk f a l l o u t , was designed and fabricated. This c o l l e c t o r also had the c a p a b i l i t y of automatic sampling of r a i n f a l l within i n d i v i d u a l . r a i n storms. The el e c t r o n i c c i r c u i t r y , associated with a l i q u i d water sensor on the automatic c o l l e c t o r i s shown i n F i g . 17. The sensor, which i s placed i n one arm of a Wheatstone bridge was fabricated by imbedding s i l v e r plated copper pins i n a plexiglass easting. The presence of water (one drop of rain) on the sensor surface, causes an input voltage to be fed to the operational amplifier while a dry sensor surface re s u l t s i n no input voltage. The output of the operational amplifier i s fed to a relay which, together with two microswitches, o + 12 V NORMALLY ^CLOSED NORMALLY oQPEN AUTOMATIC RAIN DETECTOR PARTS LIST: RESISTORS j 10 kn. R1 R2 R3 R4 R5 =1kst '/4W I R6 ,R8 =10 kiL 220ks>- }jW 1.5ks\. l.w 4 :1ksi \w h R7,R10 =1MSL R9 =360JL  J/4W R11 =470 SL 1/4w CAPACITORS CI =200pf-DIODES D1,D2 = 1N 4004 TRANSISTORS TI =2N4124 T2 = MPS 3638 AMPLIFIER AMP = MC 143966 (MOTOROLA) SENSOR SILVER PLATED COPPER PINS RELAY 6V DC DPST CONTACTS BATTERIES 2 x12V Fig.17. Electronic c i r c u i t r y for automatic c o l l e c t o r of wet f a l l o u t . Fig.18. Sensor dry: wet f a l l - F i g . 20 out c o l l e c t o r closed. Fig.19 . Sensor wet: wet f a l l -out c o l l e c t o r open. Tipping bucket r a i n gauge. Fig.22. C o l l e c t i o n t u r n t a b l e . Tipping bucket recorder. Fig.23. Opened c o l l e c t i o n t u r n t a b l 74. controls a servo motor which opens or closes the wet f a l l o u t c o l l e c t o r (Fig. 18 and 19). A bulk f a l l o u t c o l l e c t o r (Figs. 18 and 19) i s located adjacent to the wet f a l l o u t c o l l e c t o r . The former i s always open while the l a t t e r opens only during r a i n . A l l of the materials used i n c o l l e c t o r f a b r i c a t i o n were either of stainless s t e e l or p l a s t i c . The c o l l e c t i o n funnels on the automatic sampler were heated to permit snow c o l l e c t i o n . P r e c i p i t a t i o n water caught ^n the bulk f a l l o u t c o l l e c t o r was fed through an OTA-SEIKI tipping bucket r a i n . gauge (Fig. 20) while that caught i n the wet f a l l o u t c o l l e c t o r was fed to a collector"-bottle turntable (Figs. 22 and 23). The signals from the r a i n gauge were fed to a modified QTA-SEIKI tipping bucket recorder (Fig. 21). The pen mechanism on the recorder was modified by i n s t a l l a t i o n of a four-lobed cam and a microswiteh. The microswitch closed at the 25, 50, 75 and 100 percent of chart scale position and the recording pen. This microswitch, which was i n series with a control solenoid on the c o l l e c t o r turntable (Figs. 2 2 and 23), caused the turntable to advance and move into position a new c o l l e c t i o n bottle to receive discharge from the wet f a l l o u t c o l l e c t o r . This resulted i n the c o l l e c t i o n of a continuous series of discrete 50 ml samples of wet f a l l o u t throughout a storm. Each sample was large enough for the required chemical analyses. IV- 1.3 Discharge from the watershed Continuous records of the discharge of Jamieson Creek over the weir of F i g . 15 and 16 have been obtained by the Faculty of Forestry, University of B r i t i s h Columbia, since November 1970. Samples f o r stream water chemistry determination were co l l e c t e d approximately 100 meters upstream from the V- notch weir, i n a s i t e outside the influence of the weir s t i l l i n g basin, but not i n a zone of excessive turbulence. Samples of discharge water were obtained on each of the days that samples of bulk f a l l o u t accumulation were co l l e c t e d . IV-1.4 Chemical analyses The samples of bulk f a l l o u t and stream water were analyzed for sodium, potassium, calcium, magnesium, bicarbonate, s u l f a t e , chloride, n i t r a t e , s i l i c a , ammonium, orthophosphate, and pH. The samples were stored at 5°C p r i o r to analyses. Cations were measured with a J a r r e l l Ash No.800, atomic absorption spectrophotometer. In the water year 1970-71, the concentrations of anions and s i l i c a were determined by manual wet chemical methods which are des-cribed below. The samples of snow and r a i n from the Point Grey s i t e were analyzed with a Technicon Auto Analyzer II by methods described i n Technicon Industrial. Methods AAII . 4. Technicon Instruments Corporation, Tarryton, N .Y. 10591 . The manual method used for bicarbonate analysis was the " t i t r a t i o n method" (Black,e_t a l . 1965). Sulfate was determined by the ''spectrophotometric t i t r a t i o n method" (Rainwater and Thatcher, 1960). The,method employed for chloride analysis was the "mercuric n i t r i t e method" (APHA, 1965). S i l i c a was determined by the colorimetric molybdo^ s i l i c a t e method, method B, (APHA, 1965). The method employed for ammonium analysis i s presented i n Strickland and Parsons (1965). Nitrate was evaluated by the "phenoldisulfonic acid method", method A, (APHA, 1965). Orthophosphate was determined by the "aminonaptholsulfonic acid method" (APHA, 1965). The pH was measured with a Corning meter, model 10. V. DATA ANALYSIS A goal of the study was to design a mathematical model to accommodate tropospheric f a l l o u t data, measured at various elevations of the watershed and discharge data obtained at the outlet from the watershed. In order to select the method f o r determining areal averages of p r e c i p i -tation and i o n i c concentrations which would be congruous with values of i o n i c discharge, bulk f a l l o u t data were subjected to an analysis of variance. V - l Analysis of Variance P r e c i p i t a t i o n data and the 11-variable i o n i c con-centrations i n bulk f a l l o u t f o r November 19 70 and May 19 71 were used f o r s t a t i s t i c a l a nalysis. Table 13 shows the f i e l d layout for the two way c l a s s i f i c a t i o n of the analysis of variance. Rows are the numbers of weeks of sampling and columns represent the elevations. The entries i n row-column c e l l s are the numbers of r e p l i c a t i o n s of sampling c o l l e c t o r s i n each elevation zone. To obtain the same c e l l numbers data from two c o l l e c t o r s at each elevation zone with s i m i l a r aspects were used f o r the analysis. Inspection of raw data, i n the form of scatter diagrams, indicated that logarithmic data transformation should be used. Gorham (19 5 8b) and Junge (1963) show that t h i s type of transformation i s most l i k e l y to be appropriate f o r data on p r e c i p i t a t i o n chemistry. TABLE 13 Analysis of Variance F i e l d Layout Two-way C l a s s i f i c a t i o n Elevations Weeks 1 2 3 4 Number of Replications 1 2 2 2 2 2 2 2 2 2 3 2 2 2 2 4 2 2 2 2 TABLE 14 Significance of P r e c i p i t a t i o n D i s t r i b u t i o n (mm) and Ionic Concentrations (mg/1) among Four Elevation Zones and Intervals of Sampling November 19 70 May 1971 Variable Elevation Weeks Elevation Weeks PTN ftft ftft ft ft ft ft Na ftft ft* NS ftft K * ft NS NS Ca NS ft NS NS Mg NS NS NS NS HCOo NS NS ft ft ftft s c V NS ft NS NS CI NS ft A A ftft N0 3 NS NS NS NS S i 0 2 ftft ft ft ft ft NHn ft ft NS ft P O 4 NS NS ftft ft ft * S i g n i f i c a n t at P < 0.0 5 ** S i g n i f i c a n t at P < 0.01 NS Not s i g n i f i c a n t The mathematical model for the two-way c l a s s i f i c a -t i o n of analysis of variance (Snedecor and Cochran, 1967) was : X.. = u + a. + 3« + £••, i = l . . . a , j = l...t>, (1) ID i D ID where X.. = measurement obtained for the unit that i s i n 1-' the i t h row and j t h column u = the o v e r a l l mean a. = elevation effects l 8 • = week effects 3 e. . = error term i l a = the number of elevation zones b = the number of weeks. Program MFAV, U.B.C. Computer Center Library, was used to execute the analysis of variance. Results are summarized i n Table 14. In both the month of November and May, the majority of variables varied s i g n i f i c a n t l y with time of sampling. Differences among elevations varied very s i g n i f i c a n t l y for p r e c i p i t a t i o n amount i n both months. Concentrations of sodium and s i l i c a varied very s i g n i f i c a n t l y i n November as did chloride, bicarbonate and phosphate i n May. S i g n i f i c a n t differences among elevations were also observed f o r potassium and ammonium concentrations i n November and f o r s i l i c a i n May. The r e s u l t s show that time of sampling i s a very s i g n i f i c a n t factor i n c a l c u l a t i o n of i o n i c input i n bulk f a l l o u t over the entire watershed. Elevation i s a very s i g n i f i c a n t f a c t o r , p a r t i c u l a r l y for d i s t r i b u t i o n of p r e c i p i -t a t i o n and also f o r some chemical constituents. Accordingly, i n order to obtain the best possible estimations of i o n i c inputs to the entire watershed, the elevational s t r a t i f i c a -t ion of i o n i c concentrations and volumes of p r e c i p i t a t i o n was retained i n the calculations of i o n i c inputs presented below. V-2 Model for Calculation of Input-Output Relationship V-2.1 Input The c a l c u l a t i o n of i o n i c input i n bulk f a l l o u t on the Jamieson Creek watershed and i o n i c output i n discharge i s schematically outlined i n Fig. 24. It i s b r i e f l y summarized as follows: The average p r e c i p i t a t i o n of an elevation zone during a sampling i n t e r v a l was determined by the equation n i = 1 i A f (2) where the volume of p r e c i p i t a t i o n i n an elevational zone ( l i t e r s ) n the number of sampling si t e s (replicates) i n each elevational zone P. 1 the volume of p r e c i p i t a t i o n c o l l e c t e d by i n d i v i d u a l bulk f a l l o u t c o l l e c t o r s i n l i t e r s area of an elevation zone area of an i n d i v i d u a l c o l l e c t i o n funnel (consistent set of units for c a l c u l a t i o n of a l l areas i s assumed). 81. WEEKLY SAMPLING PRECIPITATION P k liters o N Z o r -< > 1x1 BULK FALLOUT C k mg/1 AREA km 2 A, _ J PRECIPITATION P k liters O M Z . o CM I U J BULK FALLOUT C mg/1 k 2 AREA km 2 A k 2 U J o M z O 10 I LU PRECIPITATION P k. liters BULK FALLOUT C k , mg/1 AREA km 2 PRECIPITATION P k liters o ISl > U J BULK FALLOUT C k mg/1 ;4 --, AREA km 2 WATERSHED INPUT FOR SAMPLING PERIOD PRECIPITATION * liters mm BULK FALLOUT > mg/1 kg/ha WATERSHED OUTPUT FOR SAMPLING PERIOD DISCHARGE Q f liters mm CONCENTRATIONS C f mg/1 kg/ha MONTHLY INPUT AND OUTPUT PRECIPITATION P w DISCHARGE Q, liters liters mm mm BULK FALLOUT mg/ I kg/ha  CONCENTRATIONS D w mg/1 kg/ha  MONTHLY AND ANNUAL BALANCE QUANTITY PRECIPITATION-DISCHARGE mm QUALITY BULK FALLOUT-DISCHARGE kg/ha Fig.24. Schematic diagram for calcu l a t i n g the chemical input-output balance at the Jamieson Creek watershed. 82. The average i o n i c concentrations i n the bulk f a l l -out from the same elevation zone was calculated from laboratory r e s u l t s . 1 n C. = - Z C. (3) k n i = l where C-u- = average i o n i c concentration (mg/1) of a s p e c i f i c constituent for an elevation zone C. = concentration (mg/1) i n subsamples 1 collected at each s i t e during the sampling i n t e r v a l , and n i s as previously defined. The volume of p r e c i p i t a t i o n (P-^) i n each eleva-t i o n a l zone was used to determine the p r e c i p i t a t i o n over the watershed during one sampling i n t e r v a l as follows: m Z A P Pj - 7^ (»0 where P. s the weighted p r e c i p i t a t i o n ( l i t e r s ) f or 3 the t o t a l watershed during one sampling i n t e r v a l 2 A^ = the area i n km of each elevation zone P^ . - the average p r e c i p i t a t i o n ( l i t e r s ) f or each elevation zone as determined by equation (2) 2 A = the t o t a l area i n km of the watershed m = the number of elevational zones. The weighted i o n i c concentration i n the bulk f a l l -out on the t o t a l watershed during one sampling i n t e r v a l was s i m i l a r l y determined. 83. m E P C C - k = 1 k k (5) j ~ P : where C = the weighted i o n i c concentration of a s p e c i f i c constituent (mg/1) i n the bulk f a l l o u t on the t o t a l watershed during one sampling i n t e r v a l P , C , and P. are as used i n equations (2) to (4) and m as previously defined. The monthly watershed p r e c i p i t a t i o n P w was determined by summing the weighted p r e c i p i t a t i o n from equation (4), f o r a l l sampling i n t e r v a l s i n a month. The monthly weighted average i o n i c concentration of a s p e c i f i c constituent was determined as follows: I Z C P C S 3-1 J 3 w p w where (6) C w = the monthly weighted average concentra-t i o n (mg/1) of a s p e c i f i c constituent i n bulk f a l l o u t on the t o t a l watershed P., C- are as defined by equation (4) and (5) -* J and I i s the number of sampling i n t e r v a l s i n a month. For the c a l c u l a t i o n of io n i c loads, the p r e c i p i t a -t i o n values are converted to a millimeter basis f o r the t o t a l watershed and the io n i c concentrations to a load basis i n kilograms per hectare per month. V-2.2 Output The c a l c u l a t i o n of the outputs of water and 84 dissolved chemicals from the watershed i s also outlined i n Fig. 24. Instantaneous rates of water discharge were 5 determined through conversion of water l e v e l records by formula: where 4.43 H 2' 5 (7) Q = the discharge i n cubic feet per second H = the head of water on the weir crest as measured i n feet. The r e s u l t s were converted into cubic meters per second, and used to plot the annual hydrograph of Jamieson Creek for water year 1970-71 shown i n F i g . 10. The arithmetic integration of t h i s curve over time i n t e r v a l s between water samplings f o r i o n i c concentration provided data f o r the derivation for each ion of i t s monthly weighted average by the following equation: q E C Q D w = P f l _ P P (8) where k t D w = the monthly weighted average i o n i c concen-t r a t i o n (mg/1) for a s p e c i f i c constituent i n the discharge water C = the concentration i n each subsample of P discharge water i n a sampling i n t e r v a l (mg/1) 5. F i l e s of the Faculty of Forestry, The University of B r i t i s h Columbia, Vancouver 8, B.C. 85. Q = cumulative stream discharge i n l i t e r s P during each time i n t e r v a l between samplings Q =. t o t a l monthly stream discharge i n l i t e r s , T and q = the number of sampling i n t e r v a l s per month. • The cumulative discharge was also converted to millimeters per watershed area i n order to obtain a figure comparable with p r e c i p i t a t i o n . Monthly loads, expressed i n kg/ha, were determined by multiplying the monthly weighted i o n i c concentration by monthly discharge and dividing by watershed area. 86. VI DATA INTERPRETATION VI-1 Ionic Concentrations For the purpose of d i r e c t comparison of the con-centrations of i n d i v i d u a l ions i n bulk f a l l o u t and discharge water, a bar graph i s presented i n F i g . 25. In t h i s procedure each phase of the hydrological cycle i s represented by a v e r t i c a l bar whose t o t a l height i s proportional to the monthly weighted average concentration i n milligrams per l i t e r . S t a t i s t i c a l c h a r a c t e r i s t i c s of the data for each ion i n the water year are tabulated for bulk f a l l o u t and for discharge water i n Table 15. Generally the i o n i c concentrations i n bulk f a l l o u t were very low. Of the cations, sodium and calcium had the highest weighted mean concentrations i n the water year. The monthly weighted average concentrations of sodium, calcium, magnesium and ammonium were higher i n summer than i n winter. Monthly weighted average concentrations of potassium were very low, p a r t i c u l a r l y i n summer. Of the anions, chloride had the highest mean concentrations, followed by sulfate and bicarbonate. Nit r a t e , phosphate and s i l i c a concentrations were very low. Seasonal d i s t r i b u t i o n of anion concentrations, p a r t i c u l a r l y chloride, sulfate and n i t r a t e i s characterized by higher concentration i n spring and summer than i n winter. The mean pH i n bulk f a l l o u t f or the water year was 5.29. Previous data from various parts of the world (Junge, NA o BULK FALLOUT t DISCHARGE 0.0 2Jt 4.0 6.0 B.O 10.0 13.1 N 0 J f H fl H J J f l S O % 10.0_ 1.0 _ 0.5 Z o BULK FALLOUT + DISCHARGE IULILI III H 0 J t M n o BULK FALLOUT t DISCHARGE 0.0 2 A 4.0 i.o fi.o o.p ig.o f M fl M J J fl HC03 o BULK FALLOUT . DISCHARGE 2.0 4.0 6.0 6 N 0 J ? H A M tO.O 13.0 J J fl S 0 CO 1^ Fig.25. Weighted monthly average ionic concentrations i n bulk f a l l o u t and discharge from the Jamieson Creek watershed, water year 1970-71 (ordinate scale i s logarithmic) en CONCENTRATION IMG/U I I " i n i r i i i miiF i i i hmi" I l l Mill CONCENTRATION (MG/LI _ - J £ B K g i i i r mi i i 11• 111r* i i i nun i i CONCENTRATION (MG/LJ : ! s 8 5 6 I I 11riir* I I I h i m  CONCENTRATION (MG/L) i i i n i n f i i i i i i n i i i r i i i r i i 11 i n i r CONCENTRATION tHG/VJ CONCENTRATION IMG/L) i i i Fi inT i i i "1111° 1 1 1 Minr 1 1 1 h i m 1 1 1 1 m i •88 89. TABLE 15 Jamieson Creek Watershed S t a t i s t i c a l Characteristics from Monthly Weighted Average Ionic Concentrations i n Bulk Fallout Water Year 1970-71 Mean S. ,p. • C.V. .Max. Min. Max/Min. Na 0. 32 0. ,18 55 , i < • • 1 • .85 0. , 81 0. ,13 6 , .23 K 0, 02 0 , 01 34, . 8 8 0 , 03- 0. ,01 3, .00 Ca 0. 21 ' 0. 41 66 , .82 0 ,  52 0 , 05 10, .40 Mg 0 . 06 0. .04 66 , . 54 0 , .18 • 0, ,03 6 , .00 HCOo 0. 12 0 . 16 129 , .26 0 . ,58 0 , 01 58. .00 SO4 0. 20 0, .10 50, .61 0. ,35 0 , 09 3, . 89 CI 0. 63 0. ,41 65 , .05 1, ,35 0. , 23 5, , 87 N 0 3 0. 05 0. ,05 3,03. ,61 0. ,18 ' 0. , 01 30. .00 S i 0 2 0. 03 0 , 03 91. .96 0 , 10 0. ,01 10, .00 0. 02 0 . 03 112. ,48 0. .10 0. ,005 19, .60 POLL 0. 01 0, .0 04 41. , 33 . 0, .02 0 . ,002 8. , 50 pH 5. 29 • 0. .40 7. ,49 5. ,93 4, . 54 1, .31 S t a t i s t i c a l Characteristics from Monthly Weighted Average Ionic Concentrations i n Discharge Water Year 1970-71 Na K Ca Mg HCOq SOM ' CI NOo S i 0 9 NiV POj P H Mean S . D . . C.V. Max. Min.. Max/Min. 0. 73 0 . 23 31.36 1.11 0 . 37 3 .00 0. 07 0 . 03 44.85, 0.15 0.04 3 .75 1. 12 0, 45 40.44 '2.42 0. 82 2 .95 0. 34 0. 36 105.14 1.48 0 .18 8 . 22 1. 19 1. 30 109.75 4f 30 0.30 143 .33 o f 25 0. 05 21.44 0. 34 0.14 2 .43 1. 13 0. 40 35.64 1.74 0 . 61 2 .85 0. 03 0 . 03 88.17 0.11 0. 01 12 .11 2. 95 1. 27 43.04 5.08 0. 54 9 .41 0. 02 0 . 02 78.75 0 .05 0.001 54 . 00 Q. 03 0. 04 124.99 "0.16 0,01 27 .33 6. 39 0 . 46 7,17 6.92 5 , 34 1 . 30 Ionic concentrations are i n mg/1 90. 19 63) show that the range of pH i s between •+ and 6. From the l i s t of cations i n discharge water, calcium has the highest annual mean concentration, followed by sodium, magnesium, potassium and ammonium. The monthly average concentrations'of calcium, sodium and magnesium were higher in summer than i n winter, whereas the concentrations of potassium and ammonium were di s t r i b u t e d rather uniformly throughout the year. From the analyses of anions i n discharge water, bicarbonate and chloride show the highest weighted mean con-centrations . Chloride concentrations were higher i n summer with a maximum i n July while minimum concentration of chloride was observed i n spring. The concentration of bicarbonate i n the discharge fluctuated considerably during the water year. The estimate of bicarbonate i s also li m i t e d by the low s e n s i t i v i t y of the a n a l y t i c a l method. The fact that bicarbon-ate was barely detectable i n fresh water drainage from undisturbed watersheds by the use of routine methods was stressed by Fisher e t a l . (1968) and Likens et a l . (1970). The weighted mean concentration of sulfate i n the discharge water was not much d i f f e r e n t from that i n bulk f a l l o u t (Table 15). The seasonal v a r i a t i o n i n sulfate con-centration i s characterized by a gradual r i s e i n the autumn reaching a maximum i n January and a minimum i n March. Concentrations of n i t r a t e and phosphate were generally very low. Maximum concentrations of these con-stituents were observed i n la t e summer. S i l i c a was one of the major constituents i n discharge water from the Jamieson Creek watershed. The highest concentrations were observed i n summer with a maximum i n August and minimum i n May. The annual pH i n discharge water was 6.39 i n d i c a -t i n g that discharge water from the watershed was s l i g h t l y acid. VI-1.1 Ionic 'concentration r a t i o s It has been found that i n sea water the r a t i o s among i o n i c concentrations i s rather constant a l l over the world (Junge, 1963). Thus, comparisons among i o n i c r a t i o s i n bulk f a l l o u t with those observed i n sea water are useful i n assessing the o r i g i n of some ions. It i s generally believed that sea s a l t aerosols are the major source of chloride i n the tropospheric f a l l o u t and also an important source of sodium. Therefore, the r a t i o s of major ions i n bulk f a l l o u t to sodium and chloride are used for the com-parison with i o n i c r a t i o s i n sea water (Junge, 1963; Holden, 1966). Ionic r a t i o s are also used to compare concentrations of major ions i n discharge water. In general, the concept of i o n i c r a t i o s provides a means for comparison of chemical composition of bulk f a l l o u t or discharge water with data from previous studies. The i o n i c concentration r a t i o s as calculated from data on bulk f a l l o u t and discharge water from the Jamieson Creek watershed, and comparable r a t i o s i n sea water are given i n Table 16. As shown i n t h i s t a b l e , a l l i o n i c r a t i o s i n bulk f a l l o u t indicate an excess of a l l ions when compared with sea water. There i s always some deviation from the t h e o r e t i c a l r a t i o s of sea water. This deviation i s caused by the influence of dry f a l l o u t from t e r r e s t r i a l sources or by anthropogenic sources. Thus the higher r a t i o s of calcium, magnesium and potassium to sodium and chloride observed i n bulk f a l l o u t on the watershed (Table 16) can be ascribed to the influence of s o i l dust. On the other hand, the higher sulfate r a t i o s to sodium and chloride are presumably caused by man-made po l l u t i o n such as the burning of fuels and refuse. The higher chloride-to-sodium r a t i o i n bulk f a l l -out can very l i k e l y be accounted for by the deposition of chloride aerosols on the p r e c i p i t a t i o n c o l l e c t o r s during dry periods. As mentioned i n section II-1.5.2 the significance of dry deposition of chloride aerosol p a r t i c l e s by g r a v i t a t i o n a l s e t t l i n g and by impact on vegetation and other obstacles was observed by Eriksson (1955; 1960) i n the coastal areas of Sweden. The concentration r a t i o s of major ions to sodium TABLE 16 Jamieson Creek Watershed Annual Average Concentration Ratios for Major Ions, Water Year 1970-71 Ratio Bulk Fallout Discharge Sea Water K/Na 0.062 0.095 0 . 036 Ca/Na 0.656 1.534 0.038 Mg/Na 0 .187 0 .465 0.121 SO^/Na 0.625 0.342 0.250 Cl/Na 1.970 1. 540 1.800 Na/Cl 0.507 0 .646 0.555 K/Cl 0 .031 0.061 0.020 Ca/Cl 0.333 0.991 0.021 Mg/Cl 0.095 0. 300 0.067 s o 4 / c i 0.317 0.221 0.140 (Values of the r a t i o s for sea water are from Junge, 1963; and Holden, 1966). and chloride are also shown for discharge water from the Jamieson Creek watershed (Table 16). The r a t i o of 1.5M- of chloride to sodium was lower than i n sea water i n d i c a t i n g the excess of sodium over chloride i n discharge water. The other i o n i c r a t i o s to sodium and chloride i n discharge water are higher than those i n sea water. The higher calcium potassium and magnesium r a t i o s , i n p a r t i c u l a r , suggest the influence of t e r r e s t r i a l sources on the concentrations of these constituents. The r e s u l t s from the Jamieson Creek watershed are comparable with data reported by Holden for two s i t e s i n Scotland (Table 17). VI-2 Ionic Loads The calculated i o n i c loads i n kg/ha per month for both bulk f a l l o u t and stream discharge are graphically shown i n F i g . 26. S t a t i s t i c a l data for each constituent i n bulk f a l l o u t and discharge water are summarized i n Table 18. There were pronounced seasonal changes i n monthly ion i c loads i n the bulk f a l l o u t and i n discharge from the watershed Because of extremely high p r e c i p i t a t i o n i n the winter period the i o n i c loads of chloride, sodium and sulfate i n bulk f a l l o u t exceeded the loads of these constituents i n discharge water. In January the potassium input was also' higher than i t s output load (Fig. 26). In summer, on the other hand, the monthly discharge loads were consistently greater than loads i n bulk f a l l o u t TABLE 17 Comparison of Ratios to Sodium i n P r e c i p i t a t i o n and Stream Analyses CI K Mg Ca Strath Bran Shelligan Summer Rain 0 .20 1. 7 3 0 .05 0 .11 0 .16 Stream 0 .23 1. 74 0 .06 0 .15 0 . 28 Winter Rain 0 .13 1. 77 0 .05 0 .09 0 .10 Stream 0 .28 1. 63 0 .08 0 .16 0 . 32 Summer Rain 1 .33 1. 36 0 . 24 0 . 24 0 .72 Stream 0 .69 1. 41 0 .07 0 . 52 2 .13 Winter Rain 0 .88 1. 88 0 .10 0 .18 0 . 25 Stream 0 .60 1. 45 0 .08 0 .47 2 .16 Comparison of Ratios to Chloride i n P r e c i p i t a t i o n and Stream Analyses Na K Mg Ca Strath Bran Shelligan Summer Rain 0 .12 0 .58 0 .03 0 .06 0. 10 Stream 0 .13 0 .57 0 .03 0 .09 0. 16 Winter Rain 0 .07 0 .57 0 .03 0 .05 0. 06 Stream 0 .17 0 .61 0 .05 0 .10 0. 20 Summer Rain 0 .98 0 .74 0 .17 0 .17 0. 53 Stream 0 .49 0 .71 0 .05 0 .37 1. 51 Winter Rain 0 .47 0 .52 0 .05 0 .09 0. 13 Stream 0 .41 0 .69 0 .05 0 .32 1. 49 (from Holden, 19 66) O PRECIPITATION t 015CKRRGE H 0 J F H A .a a.a lo.e N J J A O BULK FALLOUT + DISCHARGE O BULK FALLOUT + DISCHARGE o.i _ O BULK FALLOUT + DISCHARGE c BULK FALLOUT + DISCHARGE N D J F M A H J J O J F H A " M J J g -a BULK FALLOUT + DISCHARGE N D J F M A H J J F i g . 26. Monthly average i o n i c loads in bulk f a l l o u t and discharge from the Jamieson Creek watershed, water year 1970-71 (ordinate scale i s logarithmic). CO CD LOAD (KG/HA) LORD (KG/HA) - T i ° H -OP r o «-C O 2 •D*--O O 1 <-b" r+ j_ H« -cfi-C (A a OH-I I 11 i i 11 i n i i n i r i i i n u n i i 11 i n r LORD CKG/KRJ ; i l l PIMM" I I I "1111° 1 1 1 ~i 1 nf* 1 1 1 hi 111 1 1 1 11111 LOBO IKG/HBJ 1 1 1 rum" 1 1 1 Minr 8 § S | r * LORD (KG/HHI I I I °l lllf •Z.6 TABLE 18 Jamieson Creek Watershed S t a t i s t i c a l C haracteristics of Ionic Loads i n Bulk F a l l o u t , Water Year 1970-71 Annual Total Mean S M .D. o n C t h • V. i y Max. Min. Max/Min. PTN 4541.46 378.46 293 . 23 77 .48 946.15 61.13 15.48 Na 13.17 1.10 0 .70 63 .77 2 .16 0.11 19.64 K 0.86 0.07 0 .06 81 .11 0.18 0.01 18.00 Ca 7.25 0.60 0 . 34 55 . 89 1.07 0 . 06 17.83 Mg 2 . 21 0.81 0 .09 48 .65 0 . 31 0.03 10.33 HCOo 7 .55 0.63 1 . 27 202 .01 4. 51 0.02 225.50 s o u d 6.70 0.56 0 . 39 70 .48 1.20 0.04 30.00 CI 23.11 1.93 1 . 54 79 .72 5.10 0. 29 17 . 59 N0 3 1.13 0.09 0 .02 19 .45 0.11 0.05 2. 20 S i 0 2 0.75 0.06 0 .03 55 .90 0 .15 0.01 15. 00 0 . 57 0.05 0 .02 38 . 22 0.08 0.02 4.00 P 0 4 0 , 40 0.03 0 .02 74 .95 0.09 0.01 9.00 PTN i s p r e c i p i t a t i o n i n mm S t a t i s t i c a l Characteristics of Ionic Loads i n Discharge, Water Year 1970-71 Annual Total Mean S.D. M o n t h l y C.V, Max, Min. Max/Min, DIS Na K Ca Mg HCO-S C V CI NOo Sid, NH 4' P O 4 3668 . 33 305 .69 183 . 27 59 .95 658 . 74 18. 24 36. 12 25. 61 2 .13 1. 37 64 .32 4. 74 0. 20 23 . 70 2. 56 0 . 21 0. 14 66 .90 0. 51 0 . 02 25 . 50 41. 66 3 .47 2. 30 66 . 30 8 . 29 0. 15 55 . 27 8. 82 0 .73 0. 36 48 .94 1. 24 0. 27 4. 59 37. 24 3 .10 3 . 38 108 . 80 10 . 23 0 . 02 511. 50 9. 04 0 .75 0. 41 54 .74 1. 43 0. 05 28. 60 38. 06 3 .17 1. 83 57 .64 5. 96 0 . 30 19. 87 0. 82 0 .07 0. 03 50 .63 0. 12 0 . 02 6 . 00 92 . 01 7 .67 4. 66 60 . 84 16 . 07 0. 93 17 . 28 0. 54 0 .04 0 . 03 56 .46 0. 09 0 . 01 9. 00 0. 73 0 .06 0. 03 45 .13 0. 11 0. 03 3. 66 Monthly i o n i c loads are i n kg/ha DIS i s discharge i n mm for a l l components except for n i t r a t e and ammonium. The examination of r e s u l t s on the annual basis indicates that the f a l l o u t loads of chloride (2 3.11 kg/ha), sodium (13.17 kg/ha), bicarbonate (7.55 kg/ha), calcium 7.25 kg/ha), and sulfate (6.70 kg/ha) were substantially greater than of the other ions. In the discharge data, loads of s i l i c a , calcium, chloride, bicarbonate and sodium were the greatest, being sub s t a n t i a l l y greater than those of the other ions and released i n the given order from 92.01 kg/ha to 25.61 kg/ha per year (Table 18). Inspection of this table also suggests that calcium and s i l i c a are primarily of t e r r e s t r i a l o r i g i n because of the large difference between input and output load. VI-2.1 ' Relationships between' fallout' loads and p r e c i p i t a t i o n Regression analyses were used to t e s t the r e l a t i o n -ships between monthly values of i o n i c f a l l o u t load (dependent variable) and p r e c i p i t a t i o n amount (independent v a r i a b l e ) . Testing of l i n e a r and logarithmic models indicated that the logarithmic form was more accurate i n the majority of cases. The data on monthly loads were therefore transformed logarithmically to f a c i l i t a t e l i n e a r analysis (Gorham, 1958). The mathematical model i s as follows: L± = a(PTN) b (9) where 100 . = i o n i c load of a p a r t i c u l a r constituent i n bulk f a l l o u t i n kg/ha per month PTN = monthly p r e c i p i t a t i o n i n mm a,b = the regression parameters. The l i n e a r model of equation (9) i s : In L i = In a + b (In PTN) (10) The U.B.C. Computing Center, Library Program TRIP was used for the c a l c u l a t i o n s . The r e s u l t i n g regression equations are presented i n Table 19. This table shows that sodium, potassium, magnesium, s u l f a t e , chloride, calcium and phosphate loads were s i g n i f i c a n t l y r e l a t e d to p r e c i p i t a t i o n amount. On the other hand, loads of nitr-ate, s i l i c a and ammonium were not s i g n i f i c a n t l y related to p r e c i p i t a t i o n amounts; these constituents are apparently not strongly dependent on p r e c i p i t a t i o n . . Further examination of the slopes of regression lines indicates that constituents with a predominantly marine o r i g i n , such as sodium and chloride, show rapid increases i n chemical load as p r e c i p i t a t i o n increases. Others, such as calcium and s u l f a t e , show slower increases i n load, while potassium, magnesium and phosphate have very small increases i n load as p r e c i p i t a t i o n increases. The c o r r e l a t i o n of bicarbonate with p r e c i p i t a t i o n , though s t a t i s t i c a l l y s i g n i f i c a n t , i s much weaker than the above ions, but the general trend i s that bicarbonate load increases rather quickly as p r e c i p i t a t i o n increases. The explanation i s , however, not immediately 101. TABLE 19 Jamieson Creek Watershed Relationships Between Monthly Ionic Loads i n Bulk Fall o u t and P r e c i p i t a t i o n Amount Constituent Regression Equation S.E. (In units) Correlation C o e f f i c i e n t S i g n i -ficance In Na = -5.897+1.008 In PTN 0.481 0.89 ft& In K = -8.899+1.046 .In PTN 0.395 0.93 ft ft In Ca -4.898+0.735 In PTN 0.677 0.72 ft ft In Mg -5.857+0.709 In PTN 0.414 0.85 In HC03 = -8.414+1.186 In PTN 1.301 0.66 * In s o 4 = -5.536+0.824 In PTN 0.669 0.76 «f* •*» In CI = -3.547+0.696 In PTN 0.573 0.76 A . * • In N0 3 = -1.881-0.089 In PTN 0.226 0.35 NS In S i 0 2 = -3.567+0.113 In PTN 0.674 0.16 NS In NH4 = -4.351+0.220 In PTN 0.369 0. 49 NS In P O 4 = -6.948+0.592 In PTN 0.458 0.78 * ft Monthly i o n i c loads are i n kg/ha PTN i s p r e c i p i t a t i o n i n mm Number of degrees of freedom i s 11 * S i g n i f i c a n t at P < 0.05 ** S i g n i f i c a n t at P < 0.01 NS Not s i g n i f i c a n t S.E. i s standard error of estimate f o r the dependent variable. 102 . obvious from th i s study. Comparable correlations between chemical substances i n bulk f a l l o u t and p r e c i p i t a t i o n amount are given by Pearson and Fisher (1970) fo r the northeastern United States. Although the authors used only graphical techniques, they showed that sodium, chloride and sulfate loads were strongly related to pr e c i p i t a t i o n amount. The authors suggested that chemical substances which have loads varying with p r e c i p i t a t i o n may be present i n f a l l o u t as gases, soluble sa l t s or t h e i r derivatives while substances which have loads independent of p r e c i p i t a t i o n amount may enter the f a l l o u t as pa r t i c u l a t e matter. This material may consist of a considerable f r a c t i o n of insoluble mineral and organic compounds. Pearson and Fisher also found that loads of n i t r a t e and ammonium did not show any load-precipitation r e l a t i o n s h i p . However, some nitrogen compounds are believed to have a gaseous o r i g i n (Gambell and Fisher, 1966) and should therefore have loads varying with the p r e c i p i t a t i o n amount. The above authors explain t h e i r contrary finding by the large scatter i n n i t r a t e , ammonium and p r e c i p i t a t i o n data. VI-2.2 • Relationships between' discharge' loads' and st'reamflow A second series of regression analyses was used to assess the relationships of i n d i v i d u a l i o n i c loads i n d i s -charge to streamflow. Ionic load and discharge data were logarithmically transformed and regression parameters evaluated 103 . i n the manner described for the relationships between bulk f a l l o u t loads and p r e c i p i t a t i o n . The following equation was chosen for the regression analysis: L. = a(DIS) b (11) where L. = i o n i c load of a p a r t i c u l a r constituent ^ i n discharge water i n kg/ha per month DIS = monthly discharge i n mm a,b = the regression parameters The l i n e a r model of equation (11) i s : In Lj• = In a + b (In DIS) (12) The r e s u l t i n g equations are presented i n Table 20. The relationships between i o n i c loads and quantity of discharge were s i g n i f i c a n t (P < 0.01) for a l l i o n i c constituents except bicarbonate, n i t r a t e , ammonium and phosphate. Generally, slopes of regression lines are p o s i t i v e , that i s i o n i c loads tend to increase with increasing discharge. Comparison of regression equations obtained for the relationships between i o n i c loads i n bulk f a l l o u t and p r e c i p i -tation (Table 19) with regressions obtained for i o n i c load-discharge relationships indicate that both calcium and s i l i c a have higher c o r r e l a t i o n i n the load-discharge r e l a t i o n s h i p than i n the load-precipitation r e l a t i o n s h i p . The rate of increase of sulfate load with discharge, however, remains similar to the increasing rate of this constituent i n p r e c i p i -t a t i o n . Phosphate load which i s closely related (P < 0.01) 104 . TABLE 20 Jamieson Creek Watershed Relationships Between Monthly Ionic Loads i n Discharge and Rate of Flow Constituent Regression Equation ,, S ' E * , Correlation Sjzni & ^ (In units) C o e f f i c i e n t fican In Na =-4.250+0.869 In DIS 0.305 0.94 ftft In K =-6.354+0.832 In DIS 0.384 0.90 ftft In Ca =-4.984+1.081 In DIS 0.318 0.96 ftft In Mg =-3.048+0.478 In DIS 0. 336 0.81 ftft In HC03 =-3.292+0.667 In DIS 1.430 0.41 NS In s o 4 =-5.894+0.979 In DIS 0.237 0.97 A A In CI =-3.600+0.827 In DIS 0.341 0.92 A A In N0 3 =-4.703+0.345 In DIS 0.489 0. 56 NS In S i 0 2 =-1.730+0.648 In DIS 0.528 0.77 A A ** ?» In NH4 =-4.946+0.300 In DIS 0.717 0.38 NS In P 0 4 =-4.182+0.236 In DIS 0.415 0.48 NS Monthly i o n i c loads are i n kg/ha DIS i s discharge i n mm Number of degrees of freedom i s 11 * S i g n i f i c a n t at P < 0.05 ** S i g n i f i c a n t at P < 0.01 NS Not s i g n i f i c a n t S.E. i s standard error of estimate f o r the dependent variable. 105. to p r e c i p i t a t i o n i s not s i g n i f i c a n t l y correlated with discharge Hem (1970) has noted that streams which have a consistent r e l a t i o n s h i p between solute loads and water discharg generally receive a large part of t h e i r mineral load from r e l a t i v e l y undisturbed sources. This observation appears to be v e r i f i e d by the Jamieson Creek watershed. VI-2.3 Ionic load balance The annual balances of ionic loads (Table 21) show that appreciable amounts of most ions were lo s t from the Jamieson Creek watershed- The exceptions to the above generalization were the small annual net gain of n i t r a t e (0.31, kg/ha-yr) and ammonium (0.03 kg/ha-yr) (Table 22). Fredriksen (197 2) has determined that a small watershed i n Oregon supporting mature Douglas-fir and western hemlock forest i s capable of accumulating 0.5 kg/ha-yr of nitrogen. This net gain, as c i t e d by the above authors, i s nearly equal to that reported by Cole et_ a l . (1967). Also, data published by Fisher et a l . (196 8) indicated that input i n tropospheric f a l l o u t of ammonium' and of n i t r a t e exceeded the discharge loads from the Hubbard Brook watershed. Fisher (op. c i t . ) suggested that ammonium and n i t r a t e from f a l l o u t are very l i k e l y u t i l i z e d by the forest f l o r a . The loss of 91.26 kg/ha-yr of s i l i c a from the Jamieson Creek watershed was comparable with loss of 99.3 kg/ha-yr from a watershed i n Oregon (Fredriksen, 1^72). Fisher ert a l ; (1968) reported TABLE 21 Jamieson Creek watershed Monthly Ionic Balances i n Bulk Fallout and Discharge Water, Water Year 197 0-71, Month PTN-DIS Na K Ca Mg HCO SO CI NO. SiO, NH PO, November 95. .76 -0. , 88 -0, .17 -2. ,91 -0. .47 -9. .47 -0, .10 0 , 09 -0. , 01 -4. .78 -0. .01 -0 . 01 December 4014. ,68 -0. . 24 -0. .09 -1. . 34 -0. .43 -0 , .67 0. .51 0 . , 54 -0. . 01 -8, .45 -0. .01 -0. .03 January 715. ,45 0. ,63 0. . 04 -1. , 52 -0 . 15 -0. . 31 0 . , 33 1. ,33. . -0 . , 01 -7 , . 84 -0. .01 -0 , .07 February 388. , 32 0 . , 50 -0. .07 -2 . 77 -0, . 54 -0, .16 0 . 03 0. , 23 -0 . 01 -12, .32 -0 , .01 -0. .02 March 376. ,73 0. , 21 i-0. .02 -1. , 20 -0, .05 -5. . 80 0 . , 52 0 . ,46 -0. , 01 -3. . 53 -0, . 01 -0 , .01 A p r i l -76. , 56 0. ,04 -0. .09 -2. .02 -0. ,43 -2 , .16 -0. .19 0 . ,39 0 . , 04 -6 , .47 0. . 01 -0 . 02 May -585. , 57 -3. ,47 -0. . 25 -5 . ,27 -1. .14 -0, . 55 -1. .19 -4. ,95 0 , 04 -3, . 53 0 , .01 -0. .06 June -387. , 33 -3. , 78 -0. .40 -5. .55 -1. .11 -2. .72 -1. .06 -3. ,73 0. , 04 -14, .18 0 , .01 -0 . 01 July -281. ,41 -3. ,69 -0. . 50 -8. ,17 -1. . 20 -7. .08 -0, .66 -5. ,19 0. ,05 -16 , . 01 0, .01 -0. .06 August 97. ,75 -0, ,04 -0. ,01 -0. ,09 -0. .06 -0, .16 -0. , 01 -0. ,01 0. , 08 -0. .92 0 , .02 -0 . 01 September 53. , 50 -0. , 27 -0. .06 -0 . , 20 -0. .26 -0. .65 -0 , .09 -0. ,95 0 , 07 -4, .17 0, .01 -0 . 01 October 71, .82 -0. ,45 -0 , .08 -3. , 37 -0. .77 -0 , .04 -0. .43 -3. ,16 0. , 04 -9 , .06 0 , . 01 -0 , .02 Monthly i o n i c balances are i n kg/ha. (PTN - DIS) i s a difference between p r e c i p i t a t i o n (mm) and discharge (mm). TABLE 2 2 Jamieson Creek Watershed S t a t i s t i c a l Characteristics of Monthly Ionic Balances i n Bulk Fallout and Discharge Water, Water Year 1973-71. Annual Total Mean S.D. M o n t h l y C.V. Max. Min. PTN-DIS 873.14 72.76 370.45 509.12 715.45 -585.57 Na -12.44 -1.04 1.67 -161.28 -0.63 -3.78 K -1.70 -0.14 0.16 -115.36 0.04 -0. 50 Ca -34.41 -2.87 2 .41 -84.00 -0.09 -8.17 Mg -6.61 -0.55 0.42 -75.49 -0.05 -1. 20 HCO 3 -29.77 -2.48 3.20 -129.18 -0.04 -9.47 SOu -2.34 -0.19 0.56 -285.04 0.52 -1.19 CI -14.95 -1.25 2.34 -187.62 1.33 -5.19 N0 3 0.31 0.03 0.03 131.49 0.08 -0.01 S i 0 2 -91.26 -7.60 4.65 -61.16 -0.92 -16.01 NH, 0.03 0.002 0 .01 45 5.27 0.02 -0.01 P0l -0.33 -0.03 0.02 -82.23 -0.01 -0.07 Monthly i o n i c balances are i n kg/ha. (PTN - DIS) i s a difference between p r e c i p i t a t i o n and discharge i n mm. s i l i c a losses of 20.7 and 32.8 kg/ha-yr (f o r two consecutive years) from the Hubbard Brook ecosystem. The anionic losses of bicarbonate and chloride are considerable (Table 21), while the annual net loss of sulfate appreciable. There was also a net loss of phosphate of 0.33 kg/ha-yr. Of the basic cations the loss of calcium 34.41 kg/ha-yr was the greatest. The value i s comparable to those of 32.49 and 23.38 kg/ha-yr during 1969 and 1970 r e s p e c t i v e l y , reported for a watershed i n Oregon (Fredriksen, 1972). The losses of sodium and magnesium (Table 22) are larger than those of Hubbard Brook (Bormann and Likens, 1971) but smaller than those reported by Fredriksen (1972). Losses of 1.7 kg/ha-yr of potassium are higher than those reported by Fredriksen (1972). Bormann et a l . (1971) report the same value f o r potassium loss from the Hubbard Brook ecosystem. However, the most c h a r a c t e r i s t i c feature of the watershed i s that the monthly budgets of certain ions show marked seasonal behaviour. As shown i n Table 21 some i o n i c loads, such as sodium, chloride, sulfate and to a less extent potassium show net gains i n one or several of the winter months which are characterized by extremely high amounts of p r e c i p i t a t i o n , p a r t i c u l a r l y as snow. Nitrogen compounds on the other hand show a net gain during the vegetative season which i s characterized by low p r e c i p i t a t i o n . 109 . VI-2.4 Output to input r a t i o s The sequence of heavily accumulative snowfall during winter months and the subsequent high discharge i n spring months strongly influences the seasonal pattern of i o n i c fluxes into and out of the watershed. The pattern i n the differences between outputs and inputs of ions and of the water i t s e l f can be shown by p l o t t i n g the monthly r a t i o s of outputs to inputs as presented in Fig. 27. With respect to the outputs and inputs of ions a r a t i o of one represents equality or perfect balance. Ratios less than one indicate storage within the watershed, r a t i o s greater than one represent discharge from temporarily stored and t e r r e s t r i a l l y derived ions. Monthly r a t i o s of water discharges to p r e c i p i t a t i o n inputs are included i n Fig. 27 because of t h e i r value for interpreting the patterns of i o n i c balances. However, because precipitated water leaves the watershed through evapo-transpiration losses, as well as by streamflow, the magnitudes of the r a t i o s of water discharge to p r e c i p i t a t i o n are not e n t i r e l y comparable to the i o n i c r a t i o s . On the other hand, the d i s t o r t i o n of the curves caused by ignoring evapotrans-p i r a t i o n i s rendered small since the annual evaporation i s probably less than 2 0 percent of annual p r e c i p i t a t i o n . As shown i n F i g . 2 7 the r a t i o curves f o r most of the major cations p a r a l l e l the reference curve of discharge/ O P Cr 1 ? d C P J r—1 r+ O Hi CO PJ H O H Hi O c ex r+ H-CO Hi O 0 tf 4 P J HOP 3J (D CD r+ C-i O P J p. HJ CD CD 01 O O H" H-O rt H fU CD r+ CD h" >T O 3 c PJ PJ r+ 3 CD f i Cfl O tf Hi CD a H -o O H-4 O H- I—' 3 O P J P J d- CL CD CO cn H -O 3 OJ H a CD H -cn H- O cn 3" pj r—1 H O Oq Ot) CD fu 4 s; H- P J r+ r+ 3 J CD H-O r+ ^ O Ratio (output/input) Ratio (output/input) p r e c i p i t a t i o n quite cl o s e l y . Sodium and magnesium do so somewhat; better than potassium and calcium. The chloride r a t i o follows the reference r a t i o i n a l l months although deviating appreciably i n magnitude during l a t e r summer and early f a l l . Several investigators (Eriksson, 1955; Juang and Johnson, 1967; Likens et a l . , 1967) proposed that i n summer most of the chloride i s deposited i n the dry state, probably by s a l t capture on vegetation, and i s subsequently washed into the stream. The r a i n i n the l a t t e r part of August and the beginning of September may cause the washout of the s a l t accumulated on the tree foliages during summer and increase the net loss of this constituent observed i n September and October. The s i l i c a output/input r a t i o i s noteworthy f o r i t s consistently high value. It increased gradually during the autumn and winter, and showed a pronounced peak i n July, after the peaks of water discharge r e s u l t i n g from snowmelt. The minimum was observed i n August p r i o r to the sta r t of the autumn r i s e . Sulfate output/input r a t i o p a r a l l e l s the discharge/ p r e c i p i t a t i o n r a t i o closely during the water year. On the other hand, bicarbonate, phosphate and n i t r a t e output/input rat i o s show considerable deviation from the reference r a t i o . As shown i n Fig. 27 the trends of the output/input ratios f o r n i t r a t e and ammonium are very s i m i l a r during the 113 . year. I t suggests that related factors control t h e i r retention or loss from the forest ecosystem. The data i n Table 21 indicates that the absolute amount of n i t r a t e loss i s consis-te n t l y higher than the ammonium loss . This probably r e f l e c t s the greater tendency of ca t i o n i c ammonium to be absorbed i n the s o i l than the anionic n i t r a t e (Buckman and Brady, 1960). VI-2.5 Sources of calculated i o n i c loads Probable sources of ions to discharge water from the Jamieson Creek have been partly discussed i n the fore-going sections (VI-2.3 and VI-2 . - 4 ) . It i s now possible to estimate the separate contribution of tropospheric f a l l o u t and t e r r e s t r i a l sources respectively to calculated loads and to discuss more s p e c i f i c a l l y the probable sources. The separate contributions may be estimated by the following formula: 0 = I b + I t (13) where 0 = measured annual io n i c output load i n discharge (kg/ha) 1^ = measured annual i o n i c input load i n bulk f a l l o u t (troposperic sources) i n kg/ha I t = calculated annual i o n i c load from t e r r e s t r i a l sources (kg/ha). The r e s u l t s of equation (13) tabulated i n Table 23 indicate that t e r r e s t r i a l sources are the major suppliers of s i l i c a , calcium, bicarbonate, magnesium and potassium. Nitrate and ammonium sulfate and chloride are mainly from tropospheric sources. 114. TABLE 23 Jamieson Creek Watershed Percentage Contribution of Ions i n Discharge Water Water Year 1970-71 From T e r r e s t r i a l Sources Na 51.4 48 .6 K 33 .6 66.4 Ca 17 .4 82.6 Mg 25.1 74.9 HC03 20.3 79 .7 s o 4 74 .1 25.9 CI 60 . 7 39.3 NO 3 13.7 . 8 - 37.8 S i 0 2 0.8 99 .2 NH 4 105 .5 - 5.5 P O 4 54.8 45 .2 _ From o n Tropospheric Fallo u t 115 . Phosphate and sodium are supplied equally by the two sources. From Table 23 i t may be concluded that the t e r r e s -t r i a l sources are generally the major suppliers of i o n i c loads to the discharge of the Jamieson Creek watershed. The t e r r e s -t r i a l sources can be divided into three main components as follows: (a) weathering of s o i l s and rocks, (b) the net change of i o n i c constituents within the l i v i n g biomass of the watershed, and (c) net change within the organic debris. Because the ecosystem of the Jamieson Creek water-shed i s i n or very near to the climatic climax stage, components (b) and (c) may be assumed to be very small. Weathering of the mineral materials of the s o i l s , underlying unconsolidated materials and rocks i s therefore the major source of the t o t a l i o n i c loads. According to Loughnan (19 69) weathering of quartz d i o r i t e releases considerable quantities of s i l i c a as well as calcium, sodium, magnesium and potassium, leaving a residue enriched i n aluminum and i r o n . Lewis (19 73) believed that the weathering process i s primarily responsible for the formation of the podsol s o i l s of the coastal area of B r i t i s h Columbia and therefore large releases of s i l i c a and bases are to be expected. Thus, the large loss of s i l i c a and basic cations from the Jamieson Creek watershed can very l i k e l y be accounted for by the process of weathering and podsol s o i l formation. 116 . For sulfate loads, tropospheric f a l l o u t accounts for 74.7 percent of the t o t a l . The estimated y i e l d of 2 5.3 percent from a t e r r e s t r i a l source indicates that weathering within the watershed also contributes to the su l f u r content in discharge water. According to Roddick (1965) the occurrence of s u l f u r bearing minerals such as pyrite i s not uncommon within the general area of the watershed. In the foregoing i t has been shown that the contribution of bulk f a l l o u t to the chemical composition of discharge water i n the Jamieson Creek watershed i s of great importance. This implies that i t i s appropriate to undertake a detailed study of p r e c i p i t a t i o n chemistry i n any sit u a t i o n i n which the chemical quality of water, and man's impact thereon are considered important. SUMMARY AND CONCLUSIONS The study of the chemical composition of tropo-spheric f a l l o u t and discharge from the Jamieson Creek water-shed, located i n Greater Vancouver Water D i s t r i c t , was conducted for a period of one water year. The analyses of i o n i c concentrations i n bulk f a l l o u t were compared with those of stream discharge using a mathematical model for i o n i c input and output loads. Chemical analyses were carried out f o r sodium, potassium, calcium, magnesium, bicarbonate, chloride, n i t r a t e , s i l i c a , ammonium, phosphate and pH. In bulk f a l l o u t , the proportion of sodium, potassium, calcium, magnesium, chloride, and sulfate were appreciably higher than the values of sea water. S o i l dust and pa r t i c u l a t e and gaseous matter from anthropogenic sources are believed to have an influence on the excess loads of sodium, potassium, calcium, magnesium and s u l f a t e . The loads of sodium, chloride, sulfate and to a lesser extent potassium deposited i n bulk f a l l o u t exceeded the loads i n the discharge water i n winter because of extremely high p r e c i p i t a t i o n and high accumulation of snow. Nitrate and ammonium loads i n the tropospheric input exceeded the loads in discharge water during the greater part of the vegetative season. Stream analyses showed considerable influence of 1 1 8 . high p r e c i p i t a t i o n and p a r t i c u l a r l y high accumulation of snow on the v a r i a t i o n of i o n i c loads i n discharge water during the water year. The r i s e of chloride and sodium loads i n discharge water i n September and also the increased i o n i c concentration of these constituents i n discharge water r e l a t i v e to t h e i r concentrations i n bulk f a l l o u t suggest that there was an influence of sea s a l t deposition i n a dry state on the vegetation. The accumulated sea s a l t washed by r a i n i n late summer and i n f a l l , very l i k e l y caused these increases. Estimates have been made of the r e l a t i v e contribu-tions of the tropospheric and t e r r e s t r i a l sources to t o t a l chemical loads ca r r i e d by stream water from the watershed. T e r r e s t r i a l sources, including weathering and b i o l o g i c a l a c t i v i t i e s are the major suppliers of s i l i c a , calcium, b i c a r -bonate, magnesium and potassium, as well as half the load of sodium and phosphate. On the other hand n i t r a t e , ammonium, sulfate and chloride are mainly of tropospheric o r i g i n . While the annual loads deposited i n bulk f a l l o u t are characterized by the high proportion of ions of marine o r i g i n , the annual loads i n discharge water are characterized by great loads of s i l i c a , calcium, bicarbonate and magnesium. A c h a r a c t e r i s t i c feature of i o n i c loads deposited by bulk f a l l o u t and those carried by stream discharge includes pronounced seasonal v a r i a t i o n . 119 . VII PRECIPITATION CHEMISTRY - POINT GREY In order to obtain further information on the nature and extent of v a r i a b i l i t y of p r e c i p i t a t i o n chemistry, a Point Grey sampling s i t e was selected f o r i t s a c c e s s i b i l i t y and supporting f a c i l i t i e s . Sampling of snowfall and r a i n f a l l was carried out at d a i l y i n t e r v a l s . The objectives of t h i s research can be summarized as follows: to test the differences i n i o n i c concentrations i n bulk f a l l o u t and wet f a l l o u t , to examine the respective influence of snow and r a i n on i o n i c composition of bulk f a l l o u t , to provide further information on the s p a t i a l v a r i a t i o n of bulk f a l l o u t within the general v i c i n i t y of Vancouver, to examine temporal d i s t r i b u t i o n of wet f a l l o u t during r a i n storms. For the purpose of t h i s study an automatic c o l l e c t o r was designed as i l l u s t r a t e d i n F i g . 14, and Figs. 18 and 23. This s p e c i a l instrument enables one to c o l l e c t samples of the bulk f a l l o u t , wet f a l l o u t , and samples during i n d i v i d u a l storms. VII-1 Comparison of Tonic Concentrations i n Bulk  and Wet Fallout To test whether differences e x i s t i n the i o n i c con-centrations of bulk and wet f a l l o u t (section I I - l . 6.1 and I I - l . 6 . 2 ) , samples of p r e c i p i t a t i o n were co l l e c t e d using two 120 . types of c o l l e c t o r s . Bulk f a l l o u t was co l l e c t e d through the continuously open funnel, while wet f a l l o u t was coll e c t e d through the sensor-controlled funnel. The sampling instrument was v i s i t e d d a i l y at 8 a.m. and samples were coll e c t e d i f any p r e c i p i t a t i o n had occurred. During the sampling period from December 19 71 to A p r i l 19 72 there were 92 days of p r e c i p i t a t i o n with 21 occasions of snowfall. Fig . 28 shows that the i o n i c concentrations i n bulk f a l l o u t as plotted against concentrations i n wet f a l l o u t f a l l very clo s e l y to the diagonal l i n e of unit slope. However, the concentrations i n the wet f a l l o u t exhibited consistently s l i g h t l y lower values than that of bulk f a l l o u t . The differences i n i o n i c concentrations between these two phases of tropospheric f a l l o u t were calculated i n percent according to the formula: B I W X 100 (14) where B = i o n i c concentrations i n bulk f a l l o u t W = i o n i c concentrations i n wet f a l l o u t . A summary of results i s shown i n Table 24. The concentrations of s i l i c a and sulfate gave the highest mean percentage difference, followed i n order by calcium, potassium, n i t r a t e , magnesium and others as i l l u s t r a t e d i n Table 24. CONCENTRATION IN BULK FALL OUT (MG/L) i LU"L, i i 1 L i " l . . i 1 i tV "I... i l l CONCENTRHTION IN BULK FALL OUT 1MB/L) CONCENTRATION IN BULK FALL OUT IMG/L) Fig.28. Comparison of i o n i c concentrations i n bulk f a l l o u t and wet f a l l o u t on Po i n t Grey, winter 1971-72 (a x i s scales are l o g a r i t h m i c ) . H 123 . TABLE 24 Point Grey S t a t i s t i c a l Characteristics of Daily Differences Between Ionic Concentrations i n Bulk and Wet Fallo u t Expressed as Percentage of Bulk F a l l o u t , Winter 1971-72 Mean S .D. C .V. Max. Min. Na 4.70 0.95 20.28 8.30 0.0 K 8.44 6 .76 80 .14 62.80 0.0 Ca 8.91 2 .60 29 .24 16 . 70 0.0 Mg 7.27 5 . 04 69 .29 16 .70 0 .0 HC03 5.92 8 .15 137.70 18.20 0.0 s o 4 10.76 0 .17 1.57 11.10 10 .30 CI 3 .00 0.60 20.30 5 .30 0.0 NO 3 7.96 2.50 31.43 14 .30 0.0 s i o 2 13 .78 8.23 59 .72 25 .00 0.0 NH4 5 .96 7.17 120 .44 20.00 0.0 P 0 4 0.07 0.65 959.17 6.20 0.0 124 . Generally, the s l i g h t l y higher i o n i c concentrations i n bulk f a l l o u t can be ascribed to addition of these ions from l o c a l sources such as s o i l dust and anthropogenic sources. Presumably, s o i l dust w i l l be the main cause of higher content of such constituents as s i l i c a , calcium, potassium, magnesium bicarbonate and, to a certain extent, the nitrogen species. The higher concentration of sulfate can be attributed to anthropogenic sources (Junge, 1963). The t - t e s t was used to determine whether the i o n i c concentrations i n bulk and wet f a l l o u t are s i g n i f i c a n t l y d i f f e r e n t . The raw concentration data were transformed logarithmically (as i n sections VI-1 and VI-2) i n order to obtain frequency d i s t r i b u t i o n s more clos e l y resembling the normal d i s t r i b u t i o n than those of untransformed data. This procedure i s s i m i l a r to that carried out by Gorham (19 5 8b). The results of the t - t e s t , as shown i n Table 25, indicate no s i g n i f i c a n t difference between the mean i o n i c concentrations i n bulk and wet f a l l o u t on Point Grey i n winter 1971-72. The e a r l i e r data on comparison of bulk and wet f a l l o u t reported by Whitehead and Feth (1964) from Menlo Park, C a l i f o r n i a showed s i g n i f i c a n t differences between these two phases of f a l l o u t . The above authors a t t r i b u t e d the higher i o n i c concentrations i n bulk f a l l o u t on Menlo Park to the influence of the nearby i n d u s t r i a l area. 125 . TABLE 25 Point Grey Test of Differences Between Bulk and Wet Fallout Concentrations Winter 1971-72 Bulk Fallout Wet Fallout t-value D.F. t-prob. In Na vs. In Na 0.27 6 182 0.774 In K vs. In K 0.681 182 0.504 In Ca vs. In Ca 0.623 182 0.542 In Mg . . vs. In Mg 0.527 182 0.606 In HC03 vs. In HCO 3 0,378 182 0.706 In s o 4 vs. In SOu 0.979 182 0.331 In c i vs. In CI 0 .179 182 0.836 In NO 3 vs. In NO 3 0.758 182 0.456 In S i 0 2 vs. In S i 0 2 182 0.257 In NH4 vs. In NHU 0 .615 182 ' 0.547 In PO 4 vs. In P0 U 0.029 182 0 .927 126. I t can also be expected that the influence of t e r r e s t r i a l sources on the composition of bulk f a l l o u t varies to some extent with the c l i m a t o l o g i c a l area and the season (Junge, 1963). Gorham (1961) also postulated that the addition of s o i l materials to the troposphere i s more i n f l u e n t i a l i n a r i d regions than i n humid regions. In the Vancouver area the frequent occurrence of large rainstorms during the winter period i s an important factor causing small variations between concentrations i n bulk and wet f a l l o u t during the winter months. VII-2 Ionic Concentrations i n Bulk F a l l o u t The d a i l y amount of p r e c i p i t a t i o n and i o n i c concen-trations (mg/1) i n bulk f a l l o u t on Point Grey are i l l u s t r a t e d i n F i g . 29. S t a t i s t i c a l c h a r a c t e r i s t i c s of the concentrations and loads f o r each constituent during the 92-day p r e c i p i t a t i o n period are given i n Table 26. As i l l u s t r a t e d i n F i g . 29 the winter season 19 71-72 was characterized by both high p r e c i p i t a t i o n and frequent storm events. This figure shows the considerable v a r i a t i o n in d a i l y i o n i c concentrations of bulk f a l l o u t throughout the entire sampling period. The observed mean concentration of 3.25 mg/1 of sulfate was the highest followed by chloride (2.99 mg/1) and by the concentrations of other ions as shown i n Table 26. Concentrations of bicarbonate, chloride, sulfate and sodium CONCENTRATION IHG/U I I I l l l l l l I I I I I I HI I I I I I HII I I DRILY PRECIPITATION (MB) 10.0 liJt 20.0 39.0 30.0 39.0 CONCENTRATION IHG/L) CONCENTRATION IHG/L) 'LIT 129 . TABLE 26 Point Grey S t a t i s t i c a l Characteristics of Daily Ionic Concentrations i n Bulk F a l l o u t , Winter 19 71-7 2 92-day Mean S.p. C.V. . Max. Min. Max/Min, Na K Ca Mg . HC03 S OLL CI N0 3 S i 0 9 NHj, P°u pH 1. 91 2. 13 111. 45 10. 07 0.04 251. 75 0. 44 0. 47 106. 90 ?• 18 0, 01 318. 00 0 . 62 0 . 63 101. 16 . 2. 9 0 0.03 . 96 . 67 0. ?1 0. 23 110. 59 • + • 11 0.01 111. 0 0 1. 91 4. 01 210 . 24 24. 08 0,0 3. 25 2. 73 84. 09 13. 05 0.48 27 . 19 2. 99 3. 32 111. 11 15. 75 0.06 262 . 50 0. 32 . 0. 25 77 . 64 1. 75 0 t 03 58. 33 0. 09 0 . 09 100. 82 0. 54 0.01 54. 00 .0. 07 0. 08 114. 47 0. 36 0.01 36. 00 0 . 02 0 . 02 153 . 20 . 0. 16 0,. 0 4. 34 0. 35 8 . 14 • 5. 18 3 . 50 1. 48 Ionic concentratipns are i n mg/1 S t a t i s t i c a l Characteristics of Daily Ionic Loads i n Bulk Fallout Winter Period 1971-72 92-iday Total 92-Day Me an S.D. c.v. Max. Min. PTN 694.10 7.. 54 . 7.06 93 . 54 34.70 0 . 2000 Na 7 . 84 0.09 0.09 106.48 0.45 0.0006 K 2. 27 0.02 0.03 124.04 0.13 0.0002 Ca '•; 2.91 0.03 0.03 99 .96 0.14 0.0002 Mg 0 .88 0.01 0.01 106.63 0.05 0.0001 HC0„ 11. 59 0.13 0.35 280.70 2.30 0.0000 s<v 16.04 0.17 0.16 • 90.71 0.79' 0.0016 CI 12.36 0.13 0 .14 10 6.7 6 0,6 9 0.0010 N0 3 1.69 0.02 0.02 102.61 0.12 0.0002 S i 0 2 0.44 0.005 0.01 112.45 0 . 02 0.0001 NH4 : 0.3 8 0.0 04 0 .007 162.48 0.05 0.0000 PO 4 0.09 0.001 0.002 219.73 0.02 0.0000 Daily i o n i c loads are i n kg/ha PTN i s p r e c i p i t a t i o n i n mm 130. showed large and pronounced maximums which can be explained by the influence of additional sources from mineral dust and by man's a c t i v i t i e s . In terms of i o n i c loads i n kg/ha per 9 2-day sampling period, the loads of sulfate (16.10), chloride (12.31), and bicarbonate (11.58) were outstanding i n magnitude. The loads of other ions as shown i n Table 2 6 were also appreciable. To the author's knowledge, there are no comparative data available on the d a i l y mean io n i c concentrations i n bulk f a l l o u t . However, an approximate comparison i s made with the annual average i o n i c concentrations i n wet f a l l o u t as interpolated from the U.S. p r e c i p i t a t i o n maps (Junge and Werby, 1958). This comparison i s done although the Point Grey data show io n i c concentrations i n bulk f a l l o u t only during the winter. The comparison may be j u s t i f i e d since differences between i o n i c concentration i n bulk and wet f a l l o u t on Point Grey are not s i g n i f i c a n t since the majority of p r e c i p i t a t i o n occurs i n the winter. Volume of io n i c concentrations as interpolated from the U.S. p r e c i p i t a t i o n maps (Fig. 5, section II-l.6.2) for sodium, potassium, calcium and sulfate compare very closely with mean concentrations of these ions observed on Point Grey (Table 26). The mean concentration of 2.9 9 mg/1 of chloride was s l i g h t l y higher on Point Grey whereas concentrations of n i t r a t e (0.32 mg/1) and ammonium (0.07 131. mg/1) observed on Point Grey compare reasonably well with those of Junge and Werby (19 58) for the area of the P a c i f i c Northwest Coast.of U.S. VII-3 Influence of Snow and Rain on Ionic Concentrations  i n Bulk Fallout In order to examine the respective influence of snow and r a i n on the i o n i c concentrations i n bulk f a l l o u t a covariance method was used (Snedecor and Cochran, 1967). The purpose of t h i s method i s to examine whether the l i n e a r regressions of i o n i c concentrations on p r e c i p i t a t i o n amount are the same for snowfall as for r a i n f a l l . The computation approach i s to compare re s i d u a l variances f i r s t , then the slopes and elevations of the two simple l i n e a r regressions. The raw data of i o n i c concentrations used for the regression analysis were normalized by use of the natural logarithmic transformation. To enable t h i s transformation a l l measurements of constituents having some zero values (Table 26) were increased by a common fac t o r . Thus, a l l bicarbonate observations were increased by 0.1 and phosphate observations were increased by 0.005. These factors were chosen since they approximate the detection l i m i t s of the analysis under consideration. The r e s u l t s of the homogeneity of variance of ion i c concentration, and the test of equality of regression slopes and lev e l s are given i n Table 27. The regression equations are shown i n Table 28 and t h e i r graphical TABLE 27 Point Grey Results of Covariance Comparison of Ionic Concentration Variation with P r e c i p i t a t i o n f o r R a i n f a l l and Snowfall Homogeneity Consti- of Slopes Levels tuent Residual Variances D.F. F Sig. D.F. F Sig. D.F. F. Sig Na 69/19 1. 26 NS 1/88 4.78 ft 1/89 0 . 07 NS K 69/19 2.11 ft 1/88 3.03 NS 1/89 1.09 NS Ca 69/19 1.60 NS 1/88 5.57 ft 1/89 1. 31 NS Mg 69/19 1.25 NS 1/88 4.64 ft 1/89 0 .12 NS HC0 3 69/19 1.01 NS 1/88 0 .45 ft 1/89 0.15 NS so 4 69/19 0.88 NS 1/88 5.03 ft 1/89 0 . 36 NS CI 69/19 1. 27 NS 1/88 4.67 ft 1/89 0.18 NS N0 3 69/19 0.78 NS 1/88 1.37 NS 1/89 0 .30 NS S i 0 2 69/19 1.48 NS 1/88 2.11 NS 1/89 0.23 NS NHu 69/19 0.75 NS 1/88 1.02 NS 1/89 0 .15 NS PO 4 69/19 1.00 NS 1/88 1.05 NS 1/89 1.60 NS * S i g n i f i c a n t at P < 0.0 5 NS Not s i g n i f i c a n t 133. TABLE 28 Point Grey Regression Equations Relating Ionic Concentrations i n R a i n f a l l and Snowfall to P r e c i p i t a t i o n Amount. •Consti- S.E. ' Corr. tuent Regression Equation (In units? D.F . Coef. Sign. Rain In Na = 0.829 _ 0. 514 In PTN 1.063 70 -0. 51 ft ft Snow In Na = 0.079 0.056 In PTN 0.945 20 -0.02 NS Rain In' K = 0.141 0.335 i n PTN 1.321 70 -0. 37 ft ft Snow In K =-1.227 0.013 In PTN 0.909 20 0.15 NS Rain In Ca 1 = 0.306 — 0.236 In 1 PTN 1.022 70 -0.41 Snow In Ca =-1,494 0.062 In PTN 0.807 20 . 0.15 NS Rain In Mg =-0.528 mm 0.312 In PTN 1.045 70 -0.50 ft ft Snow In Mg =-2.057 — 0.027 In PTN 0.932 20 -0.06 NS Rain In HC0 3 =-0.824 _ 0.038 In PTN 1.829 70 -0.04 NS Snow In HC0 3 =-0.191 — 0.198 In PTN 1.819 20 -0.21 NS Rain In SOu = 1.906 0.196 In PTN 0.687 70 -0.49 Snow In S0 U = 0.775 + 0.005 In PTN 0.732 20 0.12 NS Rain In CI = 2.173 0.322 In PTN 1.044 1 " 70 -0.51 ft ft Snow In CI = 0.621 0.038 In PTN 0.925 20 -0.08 NS Rain In NO 3 =-0.728 0.142 In PTN 0.746 70 -0. 34 ft ft Snow In NO, =-1.212 - 0.025 In PTN 0.841 20 -0.06 NS Pooled In N O 3 =-0.837 - 0.115 In PTN 0 .766 9 1 -0. 28 Rain In S i 0 2 =-1.853 0.200 In PTN 0.972 7 0 -0.38 ft ft Snow In S i 0 2 =-2.857 0.024 In PTN 0.799 20 -0.06 NS Pooled In S i 0 2 =-2.079 — 0.164 In PTN 0.939, 91 -0.32 ft ft Rain In NHU =-2.431 _ 0.154 In PTN 1.042 7 0 -0.28 ft Snow In NHu =-3.043 -I • 6.013 In PTN 1.201 20 0.02 NS Pooled In NHa =-2.568 - 0.122 In PTN 1.073 91 -0. 22 ft Rain In P0 U =-4.211 0.062 In PTN 0.824 70 -0.15 •NS Snow In P0 U =-4.506 + 0.046 In PTN 0.823 20 0.11 NS Pooled i n P0 U =-4.277 0.038 In PTN 0.827 91 -0.08 NS * S i g n i f i c a n t at P < 0.05, *>'•' S i g n i f i c a n t at"P<0.01, NS Not S i g n i f . i -cant, S.E. i s standard e r r o r of estimate f o r the dependent v a r i a b l e . 134. i l l u s t r a t i o n s appear i n F i g . 30. I t should be noted that regressions for a l l i o n i c constituents are i l l u s t r a t e d here even though some are not s i g n i f i c a n t or do not have homogenous variances. The test for comparison of regression of i n d i v i d u a l i o n i c concentrations versus amount of snowfall or r a i n f a l l shows the following: 1) The concentrations of potassium have heterogeneous variances i n the two types of p r e c i p i t a t i o n (Table 27). Thus no conclusion can be drawn as to whether the relationships of concentrations to p r e c i p i t a t i o n f o r t h i s constituent are. d i f f e r e n t for snowfall and r a i n f a l l . 2) Based on the i n s i g n i f i c a n t differences i n regression slopes (Table 27), combined regressions of i o n i c concentrations versus snowfall or r a i n f a l l can be used for n i t r a t e , s i l i c a and ammonium. However, the test shows that concentrations of these constituents are s i g n i f i c a n t l y related to r a i n f a l l but not to snowfall (Table 28). Bicarbonate and phosphate do not show any s i g n i f i c a n t r e l a t i o n s h i p with either r a i n or snow. 3) Since the regression slopes d i f f e r e d (P < 0.05) for the concentrations of sodium, calcium, magnesium sulfate and chloride versus snowfall and r a i n f a l l , combined regressions for the above constituents LH (CONCENTRATION. MG/L) -3.6 -3^ -2.8 -2.4 -2.0 LN (CONCEN -5.2 -a.e -4.4 -4ll NCENTRATION. MG/L) 2.8 -2.4 -2.0 LN ICONCENTRRTION. MG/L) -2.5 -2M • 9ei 137. i s not j u s t i f i e d . The test also shows the r e l a t i o n -ship of the concentrations of the above constituents to snowfall i s not s i g n i f i c a n t at P < 0.05 (Table 28) . It can be concluded that there were no s i g n i f i c a n t correlations between the concentration of i o n i c constituents and the amount of snowfall. The r e s u l t s therefore suggest that snowfall was less e f f i c i e n t i n removing chemical sub-stances from the a i r than was r a i n f a l l . From a previous study Herman and Gorham (1957) also reported that s u l f u r and nitrogen concentrations were much lower i n snow than i n winter r a i n , at K e n t v i l l e , Nova Scotia. VII-4 Ionic Ratios i n Bulk Fallout The concentration r a t i o s of major ions to sodium and chloride were calculated from data obtained on bulk f a l l o u t on Point Grey. These r a t i o s were compared to i o n i c r a t i o s i n sea water. Comparisons are also made with corres-ponding i o n i c r a t i o s i n bulk f a l l o u t on the Jamieson Creek watershed to obtain information v a l i d for the whole Vancouver area. Several of the i o n i c r a t i o s for Point Grey bulk f a l l -out are almost one order of magnitude higher than those i n sea water, thus i n d i c a t i n g the influence of additional sources of ions. The r a t i o of magnesium i n bulk f a l l o u t was close to that i n sea water. By comparison with sea water 138 . the higher r a t i o s of sulfate to both sodium and chloride (Table 29), show evidence that anthropogenic sources, known commonly to contribute sul f u r to the troposphere are i n f l u e n t i a l i n t h i s area. The higher r a t i o s of calcium and potassium indicate the influence of mineral s o i l dust on the composition of b u l k ' f a l l o u t . Exposed c l i f f s , composed of i n t e r g l a c i a l sands and clays occur above the shore westward from the Point Grey s i t e . S o i l p a r t i c l e s from these eroding c l i f f s are possibly released and transported by winds blowing from the ocean. Further, as mentioned i n section II-1.4.3, bulk shipments of grain, coal, potash, sulfu r and phosphate i n Vancouver harbour, located northerly from Point Grey are p o t e n t i a l sources of mineral p a r t i c l e s when wind i s blowing from the core of the c i t y . City streets are also p o t e n t i a l sources of mineral materials. In addition, the global c i r c u l a t i o n of aerosolic dust with tropospheric winds and deposits on land surfaces i n r a i n f a l l was demonstrated by Junge (1963), and Jackson et a l . , (1971). The bulk f a l l o u t on the Jamieson Creek watershed i s characterized by a considerably greater deviation of the calcium to sodium r a t i o from the sea water values (Table 29). The r a t i o s of magnesium and chloride to sodium are also higher than i n bulk f a l l o u t on Point Grey. Sulfate r a t i o s to sodium and chloride, on the other hand, show lower deviations from the sea water values i n bulk f a l l o u t on the TABLE 29 Comparison Between Ionic Ratios i n Bulk Fallout on Point Grey, and Jamieson Creek with Ionic Ratios i n Sea Water Ratio Point Grey Jamieson Creek Sea Water K/Na 0 , . 230 0 .062 0 .036 Ca/Na 0 . 320 0 .656 0 .038 Mg/Na 0, .110 0 .187 0 .121 S0 4/Na 1, .700 0, . 625 0 . 250 Cl/Na 1 . 560 1. .970 1 .800 Na/Cl •. 0 . 640 0. 507 0. 555 K/Cl 0 . 147 0 . 031 0. ,020 Ca/Cl 0. 207 0 . 333 0. 021 Mg/Cl 0. 070 0 . ,095 0 . 061 s o 4 / c i 1. 086 0. 317 0. 140 (Values of the r a t i o s for sea water are from Junge 1963* and Holden, 1966) . ' 140 . Jamieson Creek watershed than on Point Grey. This suggests that anthropogenic sources are less i n f l u e n t i a l on the chemical composition of bulk f a l l o u t on the Jamieson Creek watershed than on Point Grey. However, the higher r a t i o s of calcium, magnesium and chloride to sodium suggest that dry f a l l o u t derived from mineral s o i l dust contributes substantially to the chemical makeup of bulk f a l l o u t on the Jamieson Creek watershed. In general, the influence of t e r r e s t r i a l sources on the composition of bulk f a l l o u t on Point Grey i s r e f l e c t e d i n those concentration r a t i o s which have potassium, sodium and sulfate i n t h e i r numerators. In contrast, the contribu-t i o n of t e r r e s t r i a l sources to composition of bulk f a l l o u t on the Jamieson Creek watershed i s characterized by those r a t i o s which have calcium, magnesium and chloride i n t h e i r numerators. VII-5 Temporal D i s t r i b u t i o n of Wet Fallout During Rainstorms Changes i n i o n i c concentrations i n wet f a l l o u t during three i n d i v i d u a l rainstorms were examined. The storms were characterized by d i f f e r e n t wind d i r e c t i o n s : southeast north and southwest. The r e s u l t s i n Table 30 show that most of the chemical constituents exhibited decreasing concentrations as the t o t a l amount of r a i n increased during the course of the storms. However, the decreasing trend i n concentrations was not consistent. While chloride, sodium, magnesium and T A B L E 30 Point Grey Ionic Concentrations i n Wet F a l l o u t During I n d i v i d u a l Rainstorms Sampling Cumulative Time PTN Na K Ca Mg HCOg S0 U CI N0 3 S i 0 2 NH U P0 a pH Rainstorm 1 South-east Wind 0411-16: •2-0 2 .50 1. 85 0 . 51 0. 30 0 .06 0 .41 2 .40 2 .55 0 . 25 0. 10 0. 16 0. 04 5.10 0411-20: ;21 5 .05 1. 72 0 . 30 0. 26 0 .06 0 .41 2 .32 2 .42 0 . 20 0. 10 0. 02 0. 01 4. 99 0411-21: :06 7 .70 1. 14 0. 23 0. 30 0 .05 0 .41 2 .32 2 .30 0. 20 0. 09 0. 01 0. 01 5.20 0412-05: :09 9 . 35 1. 28 0. 25 0 . 11 0 .05 0 .CO 2 .29 2 .00 0. 25 0. 11 0. 02 0. 12 4.98 0412-09; :10 10 .90 0. 94 0 . 25 0. 12 0 .04 0 .00 2 .30 1 .73 0. 25 0. 11 0. 03 0. 10 4. 57 0412-10: :11 12 .40 0. 74 0. 36 0 . 11 0 .03 0 .00 2 . 29 1 .45 0. 25 0. 11 0. 02 0. 10 4.-45 Weighted mean 1.35 0.31 0.22 0.05 0.25 2.33 2.16 0.23 0.10 0.03 0.05 4.99 Rainstorm 2 North Wind 0414-04.: 08 0414-08:10 0414-10:12 Weighted mean 0. 60 4. 60 0 . 75 1. 20 0 .52 0 .10 .6 .50 7 .05 0 .41 0 .12 0 .01 0. 01 4. 70 1. 18 4. 38 0. 65 1. 18 0 .48 0 .00 6 .18 6 .87 0 .39 0 .12 0 .01 0. 01 4. 00 1. 70 4. 26 0. 70 1. 15 0 .46 0 .00 6 .10 6 .82 0 .40 0 .12 0 .01 0. 01 3. 90 4. 42 0. 70 1. 18 0 .49 0 .04 6 .27 6 .92 0 .40 0 .12 0 .01 0. 01 4. 22 Rainstorm 3 Southwest Wind 0416-21:22 2 .14 1. 75 0416-22:23 4 .21 1. 69 0416-23:05 6 . 21 1. 65 0416-23 45 8 .21 1. 65 Weighted mean 1. 69 0.55 1.05 0.22 0.10 3.16 0.51 0.99 0.20 0.00 3.12 0.50 0.95 0.20 0.00 3.10 0.50 0.99 0.16 0.00 3.09 0.52 1.00 0.20 0.03 3.10 2 .85 0 .42 0 .13 0. 01 0. 01 5 .09 2 .70 0 .40 0 .13 0. 01 0. 01 4 .69 2 .65 0 .41 0 .13 0. 01 0. 01 4 .66 2 . 55 0 .39 0 .13 0. 01 0. 01 4 .66 2 .69 0 .41 0 .13 0. 01 0. 01 4 .78 Ionic concentrations are i n mg/1. PTN i s p r e c i p i t a t i o n i n mm. 14 2, sulfate showed a marked response to the changes i n t o t a l r a i n f a l l , the concentrations of calcium, potassium and ni t r a t e did not decrease consistently during the storms. For bicarbonate, s i l i c a , ammonium and phosphate, t o t a l r a i n f a l l did not seem to be the c o n t r o l l i n g factor since t h e i r con-centrations did not drop markedly i n proportion to the increasing amount of r a i n f a l l as the storms progressed. In order to compare the i o n i c concentrations among the three i n d i v i d u a l storms, weighted mean concentrations were computed since each storm was characterized by d i f f e r e n t t o t a l amounts of p r e c i p i t a t i o n (Table, 30). Ionic concentra-tions i n rainstorms associated with winds from southwest and southeast do not appear to be appreciably d i f f e r e n t . However, the rainstorms associated with a northerly wind i s charac-t e r i z e d by higher i o n i c concentrations than the other storms. This arises because Point Grey l i e s i n the southwestern part of Vancouver. Therefore, the sampling s i t e i s on the down-wind side of the influence of anthropogenic sources when wind i s coming from the north. 143. SUMMARY AND CONCLUSIONS Sampling of d a i l y snowfall and r a i n f a l l was conducted on Point Grey from December 1971 to A p r i l 1972. Bulk f a l l o u t associated with snow and r a i n was colle c t e d continuously by an open funnel and the wet f a l l o u t by a sensor-controlled funnel. Samples of both types of tropospheric f a l l o u t were analyzed for sodium, potassium, calcium, magnesium, bi c a r -bonate, s u l f a t e , chloride, n i t r a t e , s i l i c a , ammonium and phosphate by a Technicon Analyser AAII. Although the difference i n i o n i c concentrations i n bulk and wet f a l l o u t was not s i g n i f i c a n t l y d i f f e r e n t , the concentrations of bulk f a l l o u t were consistently somewhat higher than those of wet f a l l o u t . Local sources of mineral s o i l dust contributed to a higher content of s i l i c a , calcium, potassium, magnesium and bicarbonate i n bulk f a l l o u t on Point Grey. Anthropogenic sources were i n f l u e n t i a l i n the higher concentration of sulfate and presumably of n i t r a t e i n bulk f a l l o u t . S i g n i f i c a n t relationships between concentrations of most i o n i c constituents and r a i n f a l l and the lack of significance f o r snowfall indicate that snowfall was less e f f i c i e n t than r a i n f a l l i n removing chemical constituents from the a i r . By comparison with sea water values, the i o n i c r a t i o s to sodium and chloride i n bulk f a l l o u t on the Jamieson Creek watershed show large excesses, mainly with respect to calcium, magnesium and chloride. The concentration r a t i o s i n bulk f a l l o u t on Point Grey were characterized by the excesses of potassium, sodium and su l f a t e . Generally, the samples of snow and r a i n on Point Grey show higher i o n i c concentrations than those from the Jamieson Creek area. This f a c t may be par t l y caused by the di f f e r e n t c o l l e c t i o n method. The Point Grey r e s u l t s are derived from d a i l y samples whereas samples from the watershed are derived from weekly composites. In addition, the data for the two areas are for d i f f e r e n t years and length of time and are therefore not comparable i n d e t a i l s . 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