@prefix vivo: . @prefix edm: . @prefix ns0: . @prefix dcterms: . @prefix skos: . vivo:departmentOrSchool "Science, Faculty of"@en, "Earth, Ocean and Atmospheric Sciences, Department of"@en ; edm:dataProvider "DSpace"@en ; ns0:degreeCampus "UBCV"@en ; ns0:identifierCitation "Larson, Leila. 2010. An Assessment of the Greywater and Composting Toilet Tea Leach Field Geochemistry at the C.K. Choi Building, University of British Columbia Vancouver Campus. Undergraduate Honours Thesis. Department of Earth and Ocean Sciences. University of British Columbia."@en ; ns0:rightsCopyright "Larson, Leila"@en ; dcterms:creator "Larson, Leila"@en ; dcterms:issued "2010-02-17T19:26:54Z"@en, "2010-02-17"@en ; dcterms:description """The geochemistry of a wetland system around the C.K. Choi Building on the University of British Columbia’s Vancouver Campus was assessed. The wetland system accepts compost tea from 5 composting toilets in the building as well as greywater from the building sinks. The system was estimated to receive approximately 400L/day and has an area of 30m2 and a depth of approximately 1m. Dilution and geochemical processes reduce the concentrations of trace metals and nutrients in the inflowing greywater and compost tea. Removal efficiencies of 99% for ammonia were observed in the system and are attributed to nitrification and dilution. Nitrate/nitrite sees removal efficiencies of 98%, due to denitrification and dilution. Manganese(IV) and Iron(III) reduction is observed to produce soluble Mn(II) and Fe(II) which are then easily adsorbed by phosphorus and precipitated as hydroxyapatite, MnHPO4, vivianite and strengite.Sulfate reduction also takes place and facilitates the precipitation of metal sulfides such as iron sulfide."""@en ; edm:aggregatedCHO "https://circle.library.ubc.ca/rest/handle/2429/20363?expand=metadata"@en ; skos:note " An Assessment of the Greywater and Composting Toilet Tea Leach Field Geochemistry at the C.K. Choi Building, University of British Columbia Vancouver Campus By Leila Larson A Thesis Submitted for the Partial Fulfillment of the Requirements for the Degree of Bachelor of Applied Science In The Faculty of Applied Science (Geological Engineering) This thesis conforms to the required standard ?????????????.. Roger Beckie, Supervisor The University of British Columbia (Vancouver) February 2010 Abstract The geochemistry of a wetland system around the C.K. Choi Building on the University of British Columbia?s Vancouver Campus was assessed. The wetland system accepts compost tea from 5 composting toilets in the building as well as greywater from the building sinks. The system was estimated to receive approximately 400L/day and has an area of 30m2 and a depth of approximately 1m. Dilution and geochemical processes reduce the concentrations of trace metals and nutrients in the inflowing greywater and compost tea. Removal efficiencies of 99% for ammonia were observed in the system and are attributed to nitrification and dilution. Nitrate/nitrite sees removal efficiencies of 98%, due to denitrification and dilution. Manganese(IV) and Iron (III) reduction is observed to produce soluble Mn(II) and Fe(II) which are then easily adsorbed by phosphorus and precipitated as hydroxyapatite, MnHPO4, vivianite and strengite. Sulfate reduction also takes place and facilitates the precipitation of metal sulfides such as iron sulfide. Table of Contents 1. Introduction ..................................................................................................................... 5 1.1 Wetlands ................................................................................................................... 6 1.2 Geological Surroundings .......................................................................................... 8 2. Fieldwork ...................................................................................................................... 10 2.1 Materials and Testing Methods ............................................................................... 11 2.1.1 pH Testing ........................................................................................................ 11 2.1.2 Nutrient Testing ............................................................................................... 11 2.1.3 Inductively Coupled Plasma Emission Spectrometry (ICP) Analysis ............. 12 2.1.4 Phreeqc Simulation .......................................................................................... 12 3. Background Literature Review ..................................................................................... 13 3.1 Nitrogen Removal ................................................................................................... 13 3.2 Organic Matter Oxidation ....................................................................................... 15 3.3 Plant Uptake ............................................................................................................ 17 4. Performance Indicators ................................................................................................. 18 4.1 Chemical Indicators ................................................................................................ 19 4.1.1 Total Nitrogen .................................................................................................. 20 4.1.2 Manganese (IV) Reduction .............................................................................. 20 4.1.3 Iron(III) Reduction ........................................................................................... 21 4.1.4 Sulphate Reduction .......................................................................................... 21 4.1.5 Phosphorus Removal ....................................................................................... 22 4.1.6 Alkalinity ......................................................................................................... 25 4.2 Physical Indicators .................................................................................................. 25 4.2.1 Loading Rate .................................................................................................... 25 5. Results ........................................................................................................................... 26 6. Analysis......................................................................................................................... 28 6.1 Dilution Effects ....................................................................................................... 28 6.2 Loading Rate ........................................................................................................... 29 6.3 Rate Constant and Mass Balance ............................................................................ 30 6.4 Removal Efficiencies .............................................................................................. 31 6.5 Phreeqc Simulation ................................................................................................. 32 6.5.1 Assumptions ..................................................................................................... 32 6.5.2 Results .............................................................................................................. 33 6.5.3 Discussion ........................................................................................................ 34 7. Discussion ..................................................................................................................... 35 7.1 pH ............................................................................................................................ 35 7.2 Ammonia................................................................................................................. 36 7.3 Nitrate/Nitrite .......................................................................................................... 36 7.4 Mn(IV)-Fe(III) Reduction, Sulphate Reduction and Phosphorus Removal ........... 36 8. Conclusion .................................................................................................................... 37 References ......................................................................................................................... 39 Appendix A: Lachat QuickChem FIA+ Analysis Methods .............................................. 41 Appendix B: ICP Data ...................................................................................................... 43 Appendix C: Phreeqc Simulation Data ............................................................................. 45 List of Figures Figure 1: C.K. Choi Wetland System (Oberlander 2008) Figure 2: Plan View of C.K. Choi Wetland System (Oberlander 2008) Figure 3: Cross-Sectional View of C.K. Choi Wetland System (Oberlander 2008) Figure 4: Map of the UBC Campus (Google Maps) Figure 5: Cross Section of Point Grey Cliff Large Scale Stratigraphy (Dakin 2002) Figure 6: Model Development for Nitrogen Removal (Sonavane 2009) Figure 7: Dilution Test List of Tables Table 1: Liquid Samples Table 2: Composition of Septic System Effluent from Ptacek?s Study (1998) Table 3: Organic Matter Oxidation (Ptacek, 1998) Table 4: Phosphorus Removal (Spiterri et al. 2007) Table 5: pH Results Table 6: Ortho-phosphate Results Table 7: Chloride Results Table 8: Ammonia Results Table 9: Nitrate/Nitrite Results Table 10: Concentrations (mg/L) of Trace Metals Retrieved in November 2008 Table 11: Concentrations (mg/L) of Trace Metals Retrieved in March 2009 Table 12: Removal Efficiencies Table 13: Phreeqc Output Saturation Indices 5 1. Introduction The C. K. Choi Building which contains the Institute of Asian Research on the University of British Columbia campus was selected to be a demonstration green building in 1992 as part of a half-billion dollar expansion program of the UBC campus. The building has a 3,000m2 floor space and $4.5million budget. As part of the initiative, a greywater recycling system and composting toilets were implemented. The building contains 3,000 square meters of office space, workstations and seminar rooms. The building has 5 composting toilets. At the moment, there are approximately 200 people who consistently occupy the building and are regular toilet users. A component of the building design is a 15 meter long rubble wetland system with an open end that processes the tea from the composting toilets as well as the greywater from the sinks. The compost tea and greywater mixture is discharged by beign pumped up to the wetland where it flows a few feet under the ground surface, in a perforated pipe. Vegetation, mainly reeds, throughout the wetland uses the effluent for moisture and nutrients, in the process removing pathogens and harmful compounds. The filtered end product finally leaves the wetland and acts as irrigation in the natural ground. The purpose of this thesis is to assess the physical and chemical factors that influence the performance of the rubble wetlands of the C. K. Choi Building. The nutrients and trace metals concentrations of the influent and effluent of the wetland is characterized. The wetland geochemistry and physical characteristics will also be compared to other similar wetland systems in environments comparable to Vancouver?s. 6 1.1 Wetlands Wetlands have characteristics of both aquatic and terrestrial systems. They are a transition from one system to the next, characterized by a water table at or near the surface or by a land covered by shallow water. A wetland can function as a chemical sink, retaining more nutrients or sediments than it is releasing. This is due to a variety of properties: wetlands accumulate organics and retain nutrients and sediments; they are autotrophic systems, converting inorganic nutrients to organic biomass; they are calm, low velocity systems and so are good sedimentation basins; and they provide an excellent soil-water contact zone for biochemical processes (Mitsch & Fennesy 1991). Wetlands are subject to seasonal changes. During the summer, the uptake of chemicals by plants and immobilization of nutrients by flora creates retention of nutrients in the system. When the flora dies, nutrients are left to decompose and leach back into the water stream. In fall and spring, there is a net release of nutrients (Mitsch & Fennesy 1991). The following image of the C.K. Choi Building?s wetland system was taken during the summer months. As can be seen, there are numerous reeds and tall grasses growing on a gravel bed. 7 Figure 1: C.K. Choi Wetland System (Oberlander 2008) The next two images are, respectively, a plan and a cross-sectional view of the wetland system around the C.K. Choi Building. The wetland is approximately 15m long, 2m wide and 1m deep. The cross-sectional schematic shows that the wetland receives water from the sinks, the composting toilets and some from the building drains. Figure 2: Plan View of C.K. Choi Wetland System (Oberlander 2008) 8 Figure 3: Cross-Sectional View of C.K. Choi Wetland System (Oberlander 2008) 1.2 Geological Surroundings The following image shows the location of the C.K. Choi Building on the UBC campus. The C.K. Choi Building is located on the North-West side of the campus, close to the cliffs leading down to the Strait of Georgia. 9 Figure 4: Map of the UBC Campus (Google Maps) In the West Point Grey/UBC area, the stratigraphy allows for two water tables. There are two aquifers, one at sea level and another approximately 30m above that. The stratigraphy can be determined from observation of the UBC cliffs approximately 100m from the C.K. Choi building. On average, the stratigraphy of the slope consists of a 3m thick layer of glacial till, underlain by about 30m of sand and interbedded silt and clay until the upper aquifer. Under this, there is about 30m of dense silt overlying the second, lower aquifer at beach level. See Figure 5 below for reference: 10 Figure 5: Cross Section of Point Grey Cliff Large Scale Stratigraphy (Dakin 2002) 2. Fieldwork Two distinct rounds of samples were collected and analyzed. Water samples were collected from two different wells along the wetland (see Figure 2), one at the end of the wetland and one in the middle of the wetland closer to where the untreated compost tea and greywater first enter. A third and fourth sample were also taken from the tanks where the tea and greywater are stored inside the building. These liquids are stored in separate tanks where they sit until their level reach a certain height and are then pumped up to the wetland. The following table lists the location of the samples collected, their volumes, methods of preservation and their use: 11 Table 1: Liquid Samples Location Date Volume (mL) Method of Preservation Parameters Measured Compost Tea Tank Nov-08 120mL Air tight seal and refrigerate. Acidified with HCl before using Inductively Coupled Plasma Emission Spectrometer pH, P, Cl, N-NH4, NOx,trace metals Greywater Tank pH, P, Cl, N-NH4, Nox Borehole Closest to Source pH, P, Cl, N-NH4, NOx,trace metals Borehole Furthest From Source pH, P, Cl, N-NH4, NOx,trace metals Borehole Closest to Source Mar-09 pH, P, Cl, N-NH4, NOx,trace metals Borehole Furthest From Source pH, P, Cl, N-NH4, NOx,trace metals 2.1 Materials and Testing Methods Four different analyses were conducted to assess the wetland water: pH probe analysis, nutrient analysis, Inductively Coupled Plasma Emission Spectrometry (ICP) analysis, and phreeqc simulation. 2.1.1 pH Testing To test the pH of the samples, I used a pH probe directly on-site. Firstly, I calibrated the pH probe with standard buffers: pH 4 solution, pH 7 solution and pH 10 solution. Once the system was calibrated, I was able to measure the pH for the samples. I rinsed the pH probe with distilled water after each use to ensure that it was not contaminated. 2.1.2 Nutrient Testing Nutrients, consisting of ammonia, chloride, nitrate/nitrite and orthophosphate were measured in the Soil Water Environment Laboratory at UBC. Samples were run 12 with blanks so as to detect any potential errors or contamination from sample preparation. The instrument used is called the Lachat QuickChem FIA+ (8000 series) and analyzed the concentrations automatically. A summary of the methods used by this instrument can be found in Appendix A. 2.1.3 Inductively Coupled Plasma Emission Spectrometry (ICP) Analysis The ICP is used to determine cation and trace metal concentrations on samples acidified to pH< 1.5 with HCl. It works by injecting a nebulized mist from a liquid into the center of an argon plasma. A plasma is created by a flow of gas in a high energy field which ionizes the gas and causes intense heating, up to 10,000 K. As the mist of the sample enters the plasma, the heat dissociates most chemical compounds. The energy that the atoms absorb causes them to undergo excitation and ionization energy transitions. These transitions produce spectral emissions that are characteristic of the elements being excited. The spectrum produced by the plasma is separated into individual spectral lines by the ICP?s spectrometer, which the computer can then analyze as concentrations of specified elements (Ammann, 2007). Element concentrations are given in parts per million (ppm) on a sample volume basis, taking into account dilutions prior to testing. 2.1.4 Phreeqc Simulation Phreeqc is a software tool for the simulation of one-dimensional unsaturated flow and solute transport. Inverse modeling was used with Phreeqc to follow the chemical changes that occur as the input water evolves along the flow path. Inverse modeling 13 calculates the moles of minerals and gases that enter or leave the system to account for the changes in composition along the flow path. 3. Background Literature Review To date, researchers from around North America have conducted analyses on wetlands that process greywater, stormwater and sewage. Experiments have been conducted on sites of different scales, from industrial and commercial size wetlands to domestic wetland systems. Different experiments have emphasized their analysis on different characteristics of wetlands or different processes that occur in them, ranging from nitrogen removal to organic matter oxidation to plant uptake of nutrients. Their findings are summarized below. 3.1 Nitrogen Removal Tuncsiper (2009) conducted a study to determine appropriate conditions for nitrogen removal. He looked at hydraulic loading rates, nitrogen loading rates, effluent recirculation, plant uptake and seasonal change on nitrogen removal efficiency. Tuncsiper states that the most important processes that remove nitrogen from domestic sewage in small constructed wetlands are nitrification and denitrification (see Equation 2 and Table 3 respectively for equations). He quotes a study by Platzer (1997) that showed that for a constructed wetland with 250 to 630 g N/m2/yr loading rates, the removal efficiency of total nitrogen ranges from 40% to 55%. This study also showed that horizontal constructed wetlands have a high denitrification capacity and vertical constructed wetlands have a high nitrification capacity. So by combining these two flows, higher total nitrogen removal efficiencies are optimized. 14 Tunciper?s study found that the raw wastewater had a pH of 7, total nitrogen of 52.9mg/L, ammonium (NH4+(aq)) of 36.8mg/L and nitrate (NO3-) of 2.32mg/L. Nitrite (NO2-) concentrations were below 0.3mg/L. His study showed that the aerobic conditions in the vertical constructed wetland led to high nitrification rates and the anaerobic conditions in the horizontal constructed wetland led to high denitrification rates. Also, during colder months, the removal efficiencies decreased because the temperature dropped from 23 to 9 degrees Celcius. The temperature dependent rate constant (KT) for ammonium and nitrate were calculated by Tuncsiper using the following equation: tKCCCCTie ??=??????????**ln (Equation 1) Where Ce is the final concentration, Ci is the initial concentration, C* is the irreducible background concentration and t is the hydraulic residence time. Tuncsiper quotes studies by Bavor et al (1988), Reed & Brown (1995) that calculate nitrification rate constants of 0.107L/d, 0.4107L/d respectively. He also quotes a study by Reddy & Patrick that calculates denitrification rate constants of 0.004 to 2.57L/d. These study conditions are similar to those of the C.K. Choi wetlands in its pH conditions. However, they are dissimilar in that the nitrate/nitrite and ammonium concentrations are approximately ten times the ones found in C.K. Choi wetlands, which is expected since the C.K. Choi building does not produce as much sewage as was observed in Tuncsiper?s study and its loading rate is smaller. Also, the summer and winter temperatures around UBC usually range between 11 and -5 degrees Celcius, lower than those measured for this study. 15 3.2 Organic Matter Oxidation Ptacek (1998) studied the major ion and trace metal geochemistry of a septic plume in a shallow sand aquifer, much like the one around the C.K. Choi building. She studied the geochemical processes linked with the movement and exchange of nutrients with their host environment along their flow path. Septic system effluent shows high levels of dissolved organic carbon, ammonia, phosphorus, and pathogens. The study by Ptacek looks at an area contaminated with blackwater (wastewater from toilets and showers). The water use in the area reaches 2500L/day and is gravity-fed from a holding tank to a tile bed. This loading rate and consequently the nutrient concentrations in the effluent are considerably higher than those observed in the wetland around the C.K. Choi building. Concentrations in the holding tank were as follows: Table 2: Composition of Septic System Effluent from Ptacek?s Study (1998) Parameter Concentration (mg/L) DOC 31.8 NH4 97.9 Total P 11.8 Ca 83.6 Mg 12.9 Na 42.8 K 20.6 Cl 57.0 SO4 34.1 SiO2 9.65 Fe 0.599 Mn 0.480 Cu 0.029 Zn 0.069 Al 0.10 16 In her study Ptacek observed the highest concentrations of dissolved organic carbon (DOC) near to the septic plume source, decreasing with distance from the bed. Removal efficiencies ranged from 60 to 80%. The main oxidant of ammonia is oxygen. O2 has low solubility and as a result, most oxidation takes place in the unsaturated zone. Oxidation is not, however, excluded from the saturated zone; it only occurs at much slower rates and occurs when oxidation is incomplete in the unsaturated zone. NH4+(aq) was found in the saturated zone, which means that oxidation in the unsaturated zone is incomplete. This could have several causes: short residence times in the unsaturated zone due to high permeability of the sands, high loading rates, and a shallow water table; or insufficient active microbes due to the sporadic discharge of wastewater. PO4 removal efficiencies were approximately 80%, which agrees with other sites? removal efficiencies of 50 to 80%. The main removal mechanism is through precipitation as hydroxyapatite and ferrihydrite. Decreases in pH were observed and agree with the expected changes due to the release of CO2 from organic matter oxidation and of H+ from NH4+(aq) oxidation (see following equation): OHHNOONH 2324 22 ++?++?+ (Equation 2) The study site contained excess carbonate minerals. The decrease in pH due to CO2 release from organic matter oxidation and H+ release is expected to lead to carbonate mineral dissolution, which results in an increase in alkalinity, Ca2+ concentrations, and other cations from the carbonate minerals. Alkalinity values ranged from 200mg/L at the effluent plume margins and 350-500mg/L in the plume core. 17 In Ptacek?s study site, high concentrations of Mn and Fe were observed near the leachate plume, likely due to reductive dissolution of Mn(IV) oxides coupled with DOC oxidation and due to reductive dissolution of Fe(III) oxyhydroxide solids coupled with DOC oxidation respectively. Furthermore, the upper meters of sand are stained with an orange colour, indicating the presence of Fe(III) oxyhydroxide solids. N/Cl ratios are assumed to remain relatively constant over time in the raw effluent. In Ptacek?s study, given that the N/Cl ratio decreased over time, it was assumed that there was loss of N during transport from the source area. The loss of total N could be due to nitrate reduction, dilution, oxidation of NH4+(aq), or cation exchange reactions with NH4+(aq). 3.3 Plant Uptake The performance of wetlands depends on numerous factors: influent characteristics, loading rate, storage capacity, the design of the wetland system, and environmental factors such as light and temperature. To better understand the components and mechanisms that determine the level of performance of a wetland system, Breen (1990) conducted a study using a mass balance approach to investigate individual aspects of the system. The approach intended to ?describe system performance, indicate the relative size and importance of various components, suggest which removal processes are operating, and allow quantification of the removal rates? (Breen 1990). The study wetland system consisted of washed gravel as substratum and rhizomes of Typha Orientalis planted in the gravel. The system had an upflow format, with influent entering at the bottom and effluent collected at the top of the system, much like the one 18 around the C.K. Choi building. Results showed that the planted system removed over 80% of the chemical oxygen demand(COD), a measure of the organic compounds in the water, and 95% of the N and P. In the unplanted system, however, there as little as 7% N storage, demonstrating the plant uptake has a large effect on N absorption. Using the mass balance approach, Breen concluded that there are only two mechanisms that remove P from the system: adsorption onto the substratum and absorption by plants. Gravel has a low adsorption capacity and so adsorption did not prove useful for nutrient removal in this experiment. Plants were the major nutrient sink for N and P, absorbing 50% of the influent N and 67% of the influent P. In addition to this, denitrification was also determined to be a significant process for N removal, in both the planted and unplanted systems (Breen 1990). 4. Performance Indicators In this analysis, I am observing a passive treatment system. Passive treatment is identified as ?the deliberate improvement of water quality using only naturally-available energy sources (eg. gravity, microbial metabolic energy, photosynthesis) in systems which require only infrequent (albeit regular) maintenance in order to operate effectively over the entire system design life? (Younger et al. 2002). Therefore, I will not be looking at inputs of artificial energy or chemical reagents. With an understanding of the literature, chemistry and related experiments, the chemical and physical processes that are expected to occur in the C.K. Choi wetlands can be identified. 19 4.1 Chemical Indicators With the migration of the compost tea and greywater, N and P are released from organic compounds and oxidation of DOC leads to higher concentrations of NO3-, PO4, CO2 and H+. The principal oxidant of DOC and ammonia is oxygen. Most oxidation of the effluent takes place in the unsaturated zone. However, oxidation can occur in the saturated zone, only at much slower rates; this occurs when oxidation is incomplete in the unsaturated zone. Therefore, if products of organic matter oxidation reactions are found in the saturated zone, it is an indicator that oxidation is incomplete in the unsaturated zone. The following table lists the main oxidation reactions that take place in the effluent and their free energy. A more negative free energy means that the reaction is more likely to occur. Table 3: Organic Matter Oxidation (Ptacek, 1998) In the saturated zone, oxygen is not present in high enough concentrations to completely oxidize DOC and NH4+(aq); their oxidation depends on another electron acceptor. The expected sequence of reactions goes from denitrification, to reductive dissolution of Mn-oxides, followed by reductive dissolution of Fe-oxides (see Table 3 above). These processes are indicated by a decrease in NO3- concentrations and an increase in dissolved Mn2+ and Fe2+ concentrations. Other reactions, only under strongly 20 reducing conditions, include sulfate reduction and methanogenesis (see Table 3 above) (Ptacek 1998). 4.1.1 Total Nitrogen The following processes were used in the model development for nitrogen removal: Figure 6: Model Development for Nitrogen Removal (Sonavane 2009) Ammonification, which occurs in the composting tanks, transforms the organic nitrogen into NNH 4 and nitrification transforms NNH 4 into nitrates (NO3-). Overall the nitrogen concentration increases with nitrification and decreases with denitrification. NH4+(aq) is released by aerobic degradation. It is then removed from solution by nitrification and adsorption. The process of nitrification produces nitrate (NO3-) (see Equation 2 on page 15), also increasing the H+ concentration, thus decreasing the pH of the solution. So, drops in dissolved NH4+ concentrations are due to either dilution or due to oxidation or cation exchange reactions (Ptacek 1998).Denitrification can then occur (see Table 3 on page 18). This process uses NO3- to produce gaseous nitrogen (N2(g)). 4.1.2 Manganese (IV) Reduction Reducing conditions, as are present in the wetland system around the C.K. Choi Building, reduce manganese to its reduced state of Mn2+. The reductive dissolution of 21 Mn-oxyhydroxides is marked by an increase in pH and DOC. Mn(IV) is more readily reduced with organic compounds than Fe(III) and so reduction of Mn(IV) occurs before that of Fe(III). In some instances, Mn(IV) and Fe(III) reduction can occur simultanesouly. This is the case with unstable Fe minerals and organically complexed Fe3+. In most cases however, such as under near neutral pH conditions, organic compounds such as oxalate, pyruvate and syringic acid reduce Mn(IV) before Fe(III) is reduced (Grybos et al. 2009). 4.1.3 Iron(III) Reduction Redox indicators include the redox couples NH4+ - NO3- and Mn4+ - Mn2+, as mentioned above, and Fe2+ - Fe3+. Reducing conditions cause iron to be in the ferrous oxidation state (Fe2+). Between a pH of 5 to 9, Fe3+ concentrations are low due to the solubility of ferric oxyhydroxide minerals such as ferrihydrite (Fe(OH)3), producing Fe2+ (see equation is Table 3). The presence of more than 0.1 mg/L Fe is a good indicator of reducing conditions. 4.1.4 Sulphate Reduction Reduction of sulphate improves water quality in several ways. Firstly, sulphate reduction increases alkalinity and pH. Secondly, the reduction of sulfate to sulfide induces the precipitation of metal-sulfide minerals that have low solubility. Thirdly, sulfate reduction promotes the formation of gaseous sulfur species that diffuse into the atmosphere. In Table 3, we can see how sulfate is reduced to produce sulfide (H2S) in a reducing environment such as the wetland observed. At pH values higher than 4.5, sulfate 22 reduction also produces bicarbonate. If Fe or other metals are present, they can combine with sulfide as is demonstrated in equation 3. ++ +?+ HFeSSHFe 222 (Equation 3) If the sulfide gas does not react with a metal, it can diffuse upwards and escape into the atmosphere. According to a study by Wilderman et al. (1990), sulfate reduction and precipitation of metal sulfides removes 95% of dissolved Fe, Zn, Mn, Ni and Cd. 4.1.5 Phosphorus Removal Phosphorus concentrations (~5 ? 20 mg/L) normally found in sewage effluent are much higher than the concentrations (~0.30 mg/L) observed in other aquatic environments. Phosphate is absorbed strongly by most sediments and combines with various metal cations such as iron, aluminum, manganese and calcium to form various minerals. The main processes affecting phosphorus transport are adsorption/desorption and precipitation/dissolution. Phosphate ( ?34PO ) can be adsorbed by various minerals. It is a proteolytic acid with a negative 3 charge that can protonate to form ?24HPO , ?42 POH and 43POH . Under near neutral groundwater pH conditions,?24HPO and ?42 POH are the two dominant forms present. Therefore, if positively charged minerals are present such as Al, Mn(IV) and Fe(III) containing oxides and oxyhydroxides, these anions will be adsorbed (See Table 4 below). As for precipitation and dissolution of PO4 containing solids, the most common solids containing PO4 are Al, Fe and Ca solids (Nriagu and Dell, 1974). At low 23 temperatures, the solids that control the dissolution of PO4 include hydroxyapatite ( OHPOCa 345 )( ), variscite ( OHAlPO 24 2? ), strengite ( OHFePO 24 2? ), and vivianite ( OHPOFe 22423 8)( ?+ ) (Strumm and Morgan 1981). Groundwater that contains phosphate and carbonate minerals is usually saturated with respect to hydroxyapatite, but its formation is kinetically limited. Also, when both phosphate and CaCO3 are present, precipitation of Ca PO4 is likely to occur. Siderite (FeCO3) can also be a controlling factor for the concentration of dissolved PO4, by keeping ferrous iron concentrations low (Ptacek 1998, Akratos 2009). The portion not sorbed to sediments is available for phytoplanctons to uptake or it just flows out through the water stream. 24 Table 4: Phosphorus Removal (Spiterri et al. 2007) 25 4.1.6 Alkalinity Passive treatment systems, or reducing conditions, add alkalinity to wastewater. The wetland contains alkalinity producing materials such as dead plant matter (Walton-Day 2003). A study by Lorah et al (2008) observed alkalinity values of 0.5 to 1meq/L for a naturally attenuating landfill leachate. The study also showed that this value doubled during the wet season when plant growth was higher. Similar results for alkalinity (0.9 to 1.2meq/L) were observed in a natural pond setting in a study by Espinar and Serrano (2008). 4.2 Physical Indicators 4.2.1 Loading Rate Estimated loading rates at the entrance of the wetland system and retention times were calculated. The total amount of water flowing into the wetland (Q), divided by the area of the study wetland (A), gives an estimate of the loading rate of a wetland (L). L = Q/A (Equation 3) The turnover rate (t-1) is calculated by dividing the loading rate by the average depth of the wetland (d). t-1 = L/d (Equation 4) The retention time (t) is the reciprocal of the turnover rate. The longer the retention time of the wetland, the longer the water is in contact with the biologically active soil and the greater the rate of physical processes and sedimentation. 26 5. Results The following tables summarize the lab results obtained for pH and for the concentrations of ortho-phosphate, chloride, nitrate/nitrite, and ammonia in the wetland around the C.K. Choi building. These results were given from the Lachat QuickChem FIA+ (8000 series) instrument. Table 5: pH Results Sample ID pH (Nov 2008) pH (Mar 2009) Compost Tea 7.71 Greywater 4.72 Effluent closest to source 6.15 7.03 Effluent furthest from source 6.04 6.92 Table 6: Ortho-phosphate Results Sample ID Ortho-phosphate (mg P/L) (Nov 2008) Compost Tea 145.43 Greywater 0.58 Effluent closest to source 6.42 Effluent furthest from source 5.88 Table 7: Chloride Results Sample ID Chloride (mg Cl/L) (Nov 2008) Compost Tea 3017 Greywater 36 Effluent closest to source 66 Effluent furthest from source 79 Table 8: Ammonia Results Sample ID Ammonia (mg N-NH4/L) (Nov 2008) Compost Tea 692.9 Greywater 7.8 Effluent closest to source 2.6 Effluent furthest from source 5.4 Table 9: Nitrate/Nitrite Results Sample ID Nitrate/Nitrite (mg NOx/L) (Nov 2008) Compost Tea 307.74 Greywater 0.12 Effluent closest to source 3.45 Effluent furthest from source 3.3 27 The following tables summarize the ICP results for the compost tea and liquid flowing through the C.K. Choi wetlands. The same trace metal was sometimes identified with different wavelengths, so if two different concentrations were identified, the most reasonable concentration was taken. Detection limits were set as follow: 0.1 to 100ppm for P, 10 to 500ppm for S, and 0.1 to 100ppm for all other trace metals. Therefore, if metals were present at lower concentrations than these, they should not be detected by the ICP machine. However, some of the metals were detected at lower concentrations than the standards. I chose to accept this data if concentrations for a particular metal were similar at different wavelengths. The greywater liquid was too thick to run through the ICP machine, so was not analyzed using this instrument. Table 10: Concentrations (mg/L) of Trace Metals Retrieved in November 2008 Element Compost Tea Effluent Closest to Source Effluent Further From Source K 6067 27.9 33.81 Na 5910 38.85 38.57 S 1133 5.922 3.546 P 762.7 4.968 5.707 Ca 156.3 6.026 7.592 Fe 9.961 0.325 0.166 Mn 2.014 0.424 0.452 Zn 0.7415 0.3817 1.224 Mo 0.5117 0.02195 0.0155 Cu 0.4639 0.04734 0.1721 Ni 0.06526 0.1603 0.4537 28 Table 11: Concentrations (mg/L) of Trace Metals Retrieved in March 2009 Element Effluent Closest to Source Effluent Further From Source Na 81.74 94.58 K 42.67 50.56 Ca 16.42 23.04 S 5.37 4.94 P 4.008 5.771 Mg 1.858 3.588 Mn 0.441 0.468 Zn 0.2287 0.218 Fe 0.211 1.025 Ni 0.1141 0.1246 Cu 0.06712 0.01969 Mo 0.01582 0.02117 6. Analysis 6.1 Dilution Effects A graph of nutrient concentrations divided by chloride concentration was made to observe how much of the loss of nutrients was due to dilution and how much was due to the geochemical processes occurring in the wetland. 29 0.00150.05150.10150.15150.20150.25150.30150.35153017 79Chloride (mg/L)Nutrients/ClFe/ClNOx/ClN-NH4/ClS/Cl Figure 7: Dilution Test As is observed from Figure 7 above, the lines for nutrient/Cl over Cl have a negative slope. This means that in addition to dilution, many processes are happening to reduce the concentrations of the nutrients present in the wastewater as it flows through the wetland. These processes will be discussed in Section 7: Discussion. 6.2 Loading Rate A loading rate can be estimated for the wetland system, using equations 3 and 4 (on page 24). In order to remain conservative, I assumed 200 people use the toilets and sinks in the C.K. Choi building. Not everyone will use these washrooms all day, so I assume each person produces 2L of greywater and compost tea per day. This totals as 400L of wastewater per day going into the wetlands. The area of the wetland was assumed to be 20m2, giving the wetland a loading rate of 0.02m/day. This loading rate is 30 smaller than the studies observed in literature (Platzer 1997, Ptacek 1998); however it is a reasonable estimate since not many people occupy this building at this time and so the wetland does not need to support as much wastewater. Assuming a conservative depth of 0.5m for the wetland, by taking the loading rate divided by the depth of the wetland, a hydraulic residence time can be calculated as 25 days. From the geochemistry changes observed as the wastewater flows through the system, we can confirm that 25 days residence time is sufficient to clean the effluent. From the lab results, we see that significant removal occurs early in the flow system, at the sampling well closest to the source (see Figure 2). 6.3 Rate Constant and Mass Balance As was earlier discussed in Tuncsiper?s literature review, the rate constant can be calculated using equation 1. Because of dilution, the calculated rate constants are approximate. Assuming a hydraulic residence time of 25 days and an estimated irreducible background concentration of 3mg/L for nitrate/nitrite, the rate constant for nitrification is calculated as 0.28L/d. This value is comparable to those calculated by Bavor et al (1988) and by Reed & Brown (1995) whose studies showed nitrification rate constants of 0.107L/d, 0.4107L/d respectively. A mass balance can also be calculated. It was assumed that the compost tea flow is an eighth of the total flow, or 50L/day, and the greywater flow is seven eighths of the total flow, or 350L/day. These flows are estimates. A mass balance for nitrogen can be calculated using equation 5: [ ] [ ] [ ]greywatercompostxgreywaterxcompostx QQNOQNOQNO++= (Equation 5) 31 The brackets indicate concentrations. This equation gives a nitrate/nitrite concentration of 38.57mg/L, which is much higher than the 3.45mg/L of nitrate/nitrite observed at the sampling well closest to the source. This is an indication of both dilution and denitrification. 6.4 Removal Efficiencies Removal efficiencies can be calculated using the load. I assumed that the flow through the system did not remain at 400L/day throughout the entire wetland system. I estimated that there was approximately 20L/d of flow lost to infiltration into the gravel. By using the following equation, removal efficiencies for various metals were calculated: %10011122 ??QCQC (Equation 6) Where C2 is the concentration of the trace metal at the furthest sampling point in the wetland and Q2 is the flow at the same place, C1 is the concentration of the trace metal in the compost tea and Q1 is the flow at the inlet to the wetland. As mentioned earlier, the flow at the inlet to the wetland is estimated as 400L/day and the flow at the furthest point in the wetland is 380L/day. The following table lists the removal efficiencies for various trace metals. Table 12: Removal Efficiencies These removal efficiencies are high compared to the 80% and 70% removal efficiencies observed for P and N in Tuncsiper (2009) and Ptacek?s (1998) studies, but P Nitrate/Nitrite Ammonia C2 (mg/L) 5.707 3.3 5.4 Q2 (L/day) 400 400 400 C1 (mg/L) 762.7 307.74 692.9 Q1 (L/day) 380 380 380 Removal Efficiency (%) 99.1 98.8 99.1 32 are closer to the 95% P and N removal efficiencies observed by Breen (1990). The high removal efficiencies observed in the wetland system around the C.K. Choi building are likely due to the concentrations of trace metals and nutrients being low when they enter the system and so are easily removed. Also, as observed by Breen (1990) and Walton-Day (2003), plant uptake is a significant contribution to metal removal. Plants immobilize metals and accumulate them in their structures, a process that takes place in the C.K.Choi wetland system. 6.5 Phreeqc Simulation The Phreeqc simulation was only run with the compost tea because trace metal data was available not available for the greywater since the ICP machine could not handle the amount of sediment in the greywater. A solution simulating the trace metal concentrations in the compost tea was run through an environment simulating the wetland system. Precipitates were then observed. 6.5.1 Assumptions Assumptions were necessary while performing the Phreeqc simulation. Firstly, a total sulfur concentration was obtained from the ICP machine. Because an input of either sulfate or sulfide is necessary in Phreeqc, it was assumed that all the sulfur in the compost tea was in its oxidized form as sulfate. This is an appropriate assumption since the wetlands are a reducing environment and sulfate is also observed in wetland studies such as Ptacek?s (1998). High sulfide, instead of sulfate, is extremely toxic and is only present in highly alkaline solutions, which is not likely the case for this wetland. Additionally, the nitrate/nitrite concentration obtained from the Lachat QuickChem 33 analysis was input in the Phreeqc model as nitrate because this is the most likely species present. The model was initially run without a charge balance. The output then gave a positive imbalance to the solution. Cl was then used as a charge balance to give an electrically neutral solution. The electrically balance system allows Phreeqc to run as many processes as it can with the input given. The input and output Phreeqc files can be found in Appendix C. 6.5.2 Results The Phreeqc model was used to observe what reactions occurred to produce precipitate from the wastewater running through the wetland system. Looking at the output file, the minerals with positive saturation indices will precipitate out of solution. Table 13 below summarizes the minerals with positive saturation indices. 34 Table 13: Phreeqc Output Saturation Indices Mineral Saturation Index Chalcopyrite CuFeS2 14.5 Pyrite FeS2 11.8 Chalcocite Cu2S 9.01 Anilite Cu0.25Cu1.5S 6.43 Djurleite Cu0.066Cu1.868S 8.88 BlaubleiII Cu0.6Cu0.8S 6.85 BlaubleiI Cu0.9Cu0.2S 6.33 Covellite CuS 5.3 MnHPO4 4.78 Greigite Fe3S4 4.72 Millerite NiS 3.37 Sphalerite ZnS 1.91 N2(g) 1.79 Mackinawite FeS 0.85 FeS(ppt) 0.12 Hydroxyapatite Ca5(PO4)3OH 0 Vivianite Fe3(PO4)2:8H2O 0 It should be noted that the measured 66mg/L Cl is larger than the 13mg/L Cl computed using charge balance by Phreeqc. This charge balance discrepancy indicates either an error in the measurement of the dissolved constituents or that a significant analyte was not measured. 6.5.3 Discussion From Table 13, as was also suggested by Strumm and Morgan (1981), we expect to see phosphate precipitate as hydroxyapatite, vivianite and MnHPO4. Sulfide metals such as chalcopyrite, pyrite, chalcocite, anilite, djurleite, blaubleill, blaubeil, covellite, greigite, millerite, sphalerite, mackinawite and FeS (ppt) are expected to precipitate out of the wastewater solution flowing through the wetland. In addition to this, nitrogen gas will be produced in the system. The expected alkalinity from the phreeqc simulation for the wastewater flowing through the wetland is 4.41meq/L. This value is the same order of magnitude as the 35 alkalinity values observed in ponds, marshes and sewage leachate plumes in studies by Espinar & Serrano (2009) and by Lorah (2009). This could be explained by the fact that testing was performed in November, a month during which vegetation is dying and organics are collecting on the ground. In the case of the wetland around the C.K. Choi building, most of the wetland is covered with reeds during the summer months and starting around October, these plants begin to die and decompose on the gravel of the wetland system. 7. Discussion 7.1 pH As is expected, the greywater is acidic because of the soap and the compost tea slightly basic to begin with. Standard freshwater has a pH of approximately 5.5 to 6 (Laurenzi 2010). The water flowing through the system should resemble that of standard freshwater since it is being cleaned by the wetland, so the pH of the wastewater was slightly acidic in March 2009, but was close to that of standard freshwater in November 2008. As the compost tea and greywater are mixed and begin to flow through the wetland system, the pH decreases from 7.71 in the compost tea to 6.04 at the furthest point from the building. This is as expected and is due to the oxidation of DOC increasing the concentration of H+ in the system. The drop in pH is also due to nitrification, consuming NH4+(aq) to produce H+. The pH observed during sample collection (pH 6.04) is also close to the one output by the Phreeqc model (pH 6.054), which means that pH sampling was accurate. 36 7.2 Ammonia Ammonia concentrations go from 692.9mg/L in the compost tea and 7.8mg/L in the greywater to 2.6mg/L at the sample tube closest to the building outlet to 5.4mg/L at the sample tube furthest from the building. This decrease is due to nitrification, converting NH4+(aq) to nitrates. 7.3 Nitrate/Nitrite NOx concentrations go from 307.7mg/L in the compost tea and 0.12mg/L in the greywater to 3.45mg/L at the sample tube closest to the building outlet to 3.30mg/L at the sample tube furthest from the building. This decrease is due to both dilution and denitrification. Denitrification uses NO3- and converts it to N2 gas. The nitrogen gas can then escape upwards through the soil and be released into the atmosphere. Formation of nitrogen gas is also also agrees with the Phreeqc analysis performed. 7.4 Mn(IV)-Fe(III) Reduction, Sulphate Reduction and Phosphorus Removal Looking at the ICP results, we see a decrease in Mn, Fe and S concentrations. This is due to the oxidation of DOC and the reduction of metals and S listed in Table 3 and due to precipitation of Mn, Fe and S solids. Manganese (IV) reduction uses some of the H+ produced from the denitrification process and converts the solid manganese dioxide, from the ground, into soluble Mn(II). Iron (III) reduction uses the solid phase iron hydroxide and H+ to produce aqueous Fe (II). Finally, sulfate reduction uses sulfate and converts it to hydrogen sulfide. This then facilitates the precipitation of metal-sulfides such as iron sulfide and also induces the 37 formation of sulfur gases that migrate up through the soil and diffuse in the atmosphere. Phreeqc also shows that many other sulfide metals will precipitate with metals such as copper, nickel and zinc (see Table 13 on page 32). Soluble Mn and Fe, in addition to Ca, are easily adsorbed by phosphorus (Strumm and Morgan 1981). Phosphorus concentrations in the compost tea are high. As the liquid flows through the system, phosphorus is removed through bacterial removal, plant uptake, adsorption by the gravel and sand, and by precipitation. ?24HPO and ?42 POH are the dominant forms of phosphate present at the pH conditions observed. Because of this, minerals such as hydroxyapatite, MnHPO4, vivianite and strengite precipitate out of the solution. 8. Conclusion Based upon the sampled analyzed, the wetlands processing the compost tea and greywater from the C.K. Choi building seem to be performing well. The concentrations of trace metals and minerals observed from the lab analyses agree well with the literature on wetland performance. It is expected that some trace metal concentrations will be lower than seen in other environments since the C.K. Choi building does not have many occupants, so wastewater concentrations are low to begin with. When the data from the compost tea was input in Phreeqc and simulated to run through an environment similar to that of the wetland, precipitate outputs also agreed with previous studies. Alkalinity, pH and metal concentrations are at levels that are normal and not harmful to the environment. 38 In further experiments, I would analyse the soil to observe what precipitates are present, so as to compare with the Phreeqc model. In this way, we could see whether some solids are present that are not available through the Phreeqc database and whether the precipitates identified with by Phreeqc are correct. 39 References Akratos, C. et al. ?Artificial Neural Networkd Use in Ortho-phosphate and Total Phosphorus Removal Prediction in Horizontal Subsurface Flow Constructed Wetlands?. Biosystems Engineering I02.pp.190-201. 2009. Ammann, Adrian. ?Inductively Coupled Plasma Mass Spectrometry (ICP MS): A Versatile Tool?. Journal of Mass Spectrometry. Vol 42, Issue 4. pp 419-427. March 2007. Bavor, H.J., Roser, D.J., McKersie, S.A. and Breen, P. ?Treatment of Secondary Effluent. Report to Sydney Water Board?. Sydney, Australia, 1988. Breen, P. ?A Mass Balance Method for Assessing the Potential of Artificial Wetlands for Wasterwater Treatment?. Wat. Res. Vol.24, No.6, pp. 689-697. 1990. Dakin R.A. ?Hydrogeological and Geotechnical Assessment of Northwest Area UBC Campus?. Vancouver. Piteau Associates. 2002. Espinar, J. & Serrano, L. ?A Quantitative Hydrogeomorphic Approach to the Classification of Temporary Wetlands in the Donana National Park (SW Spain)?. Aquat Ecol. Vol43. pp.323-334. 2009. Google. ?Google Maps?. Retrieved from http://maps.google.com/ on February 13 2010. Grybos, M. et al. ?Increasing pH Drives Organic Matter Solubilization From Wetland Soils Under Reducing Conditions?. Geoderma. Vol154, Issues1-2. pp13-19. 2009. Laurenzi, Laura. Geochemist at Golder Associates. Interview on February 4th 2010. Lorah, M. et al. ?Biogeochemistry of a Wetland Sediment-Alluvial Aquifer Interface in a Landfill Leachate Plume?. Journal of Contaminant Hydrology. Vol105. Issues3-4. pp.99-117. 2009. Nriagu, J.O., Dell, C.I. Diagenetic Formation of Iron Phosphates in Recent Lake Sediments. Am. Mineral. 59, pp.934-946. 1974. Oberlander, C.H. ?C.K. Choi Building at UBC?. Cornelia Hahn Oberlander. 2008. Platzer, C. and Mauch, K. ?Soil Clogging in Vertical Flow Reed Beds?Mechanisms, Parameters, Consequences and Solutions?. Water Science Technology, 35 (5). pp175?181. 1997. Ptacek, C.J. ?Geochemistry of a Septic-system Plume in a Coastal Barrier bar, Point Pelee, Ontario, Canada?. Journal of Contaminant Hydrology 33 (1998) 293-312. 40 Reddy, K.R. and Patrick,W.H. ?Nitrogen Transformations and Loss in Flooded Soils and Sediments\". CRC Critical Reviews. Environ. Control. 13. pp273?309.1984. Reed, S.C. and Brown, D., ?Subsurface Flow Wetlands: A Performance Evaluation?. Water Environ. Res., 67 (2) 244?248.1995. Sonavane, P.G. and Munavalli, G.R. ?Modeling Nitrogen Removal in a Constructed Wetland Treatment System?. Water Science & Technology 60.2 pp. 301-309. 2009. Spiterri, C. et al. ?Modelling the Geochemical Fate and Transport of Wastewater-Derived Phosphorus in Contrasting Groundwater Systems?. Journal of Contaminant Hydrology 92, 87-108. 2007. Stumm, W., Morgan, J.J., 1981. ?Aquatic Chemistry?. Wiley-Interscience, New York. Tuncsiper, B. ?Nitrogen Removal in a Combined Vertical and Horizontal Subsurface-Flow Constructed Wetland System?. Elsevier Science Publishers B.V. Turkey. 2009. pp. 466-475. Walton-Day, K. ?Passive and Active Treatment of Mine Drainage?. Environmental Aspects of Mine Wastes. Editors J.L. Jambor, D.W. Blowes & A.I.M. Ritchie. Vancouver, BC. Vol3. pp.335-359. 2003. William J. Mitsch & M. Siobhan Fennesy. ?Modelling Nutrient Cycling in Wetlands?. Chapter 8 of Modelling in Environmental Chemistry, edited by S.E. Jorgensen. Elsevier Science Publishers B.V. New York. 1991. pp. 249-275. Younger et al. ?Mine Water Hydrology, Pollution, Remediation?. Kluwer Academic, Dordrecht, The Netherlands. 2002. 41 Appendix A: Lachat QuickChem FIA+ Analysis Methods Instrument: Lachat QuickChem FIA+ (8000 series) Methods: Chloride, nitrate/nitrite, low ammonia, low orthophosphate Applications: Drinking, ground and surface waters, and domestic and industrial wastes QuickChem Methods Overview Analyte QuickChem Method # Range (mg/L) Detection Limits* (mg/L) Ammonia (N as NH3+) 10-107-06-2-A 0.1 ? 5.00 0.005 Chloride (Cl-) 10-117-07-1-A 6 ? 300 0.5 Nitrate / Nitrite (N as NO3- / NO2-) 12-107-04-1-B ? 0.02 ? 20.0 0.02 Orthophosphate (P as PO43-) 10-115-01-1-A 0.01 ? 2.00 0.01 * blanks should always be run with a sample set to determine any potential error or contamination from sample preparation (including filtration steps). ? Method for 2M KCl soil extracts, but used with a straight water matrix/carrier. Quality Control: - Standard curves are re-run each day. - During the run, a check standard is run every 10-15 samples to check for drift or other problems. Method descriptions: (taken directly from QuickChem Methods) Ammonia: When ammonia is heated with salicylate and hypochlorite in an alkaline phosphate buffer, an emerald green colour is produced which is proportional to the ammonia concentration. The colour is intensified by the addition of sodium nitroprusside. Chloride: Chloride reacts with mercuric thiocyanate to form a strong, covalent complex which displaces thiocyanate. The free thiocyanate reacts with aqueous iron(III) to produce ferric thiocyanate (red colour), which absorbs stongly at 480 nm. Nitrate: Nitrate is quantitatively reduced to nitrite by passage of the sample through a copperized cadmium column. The nitrite (reduced nitrate + original nitrite) is then determined by diazotizing with sulfanilamide followed by coupling with N-(1-42 naphthyl)ethylenediamine dihydrochloride. The resulting water soluble dye has a magenta colour which is read at 520 nm. Orthophosphate: The orthophosphate ion (PO43-) reacts with ammonium molybdate and antimony potassium tartrate under acidic conditions to form a complex. This complex is reduced with ascorbid acid to form a blue complex which absorbs light at 880 nm. The absorbance is proportional to the concentration of orthophosphate in the sample. Potential interferences Ammonia 1. In alkaline solution, Ca and Mg form a precipitate that scatters light (EDTA in buffer to prevent this). 2. Non-volatile amines such as cysteine, ethanolamine, and ethylenediamene cause decreased sensitivey. 3. Lauryl sulfate and some detergents can cause low recoveries. Chloride 1. Substances that reduce iron(III) to iron(II) and mercury(III) to mercury(II) (e.g. sulfite, thiosulfate). 2. Other halides that form a strong complex with mercuric ion (e.g. Br-, I-). Nitrate/Nitrite 1. Build up of suspended matter in column (pre-filter samples) 2. High concentrations of Fe, Cu, or other metals (EDTA in buffer to reduce this interference). 3. Large concentrations of oil and grease (must pre-extract sample with an organic solvent). Orthophosphate 1. Silica forms a complex that also absorbs at 880 nm (generally an insignificant interference). 2. Concentrations of ferric iron (Fe3-) > 50 mg/L cause negative error due to precipitation of orthophosphate. 3. Sample turbidity. 4. Glassware contamination. Soil Water Environment Laboratory (SWEL) University of British Columbia 112 ? 2357 Main Mall, MacMillan Building Vancouver, BC Canada V6T 1Z4 Summary information compiled by T Naugler. January 13, 2009. 43 Appendix B: ICP Data Sampling Date Location Tube Sample Labels Mo 204.598 Cu 327.395 Cu 324.754 Mo 202.032 Zn 213.857 Zn 202.548 Zn 202.548 Cu 324.754 Nov-08 furthest from building 1 : 1 1a 0.015502 0.172134 0.219616 0.004884 1.2245 1.28063 1.28063 0.219616 Nov-08 closest to building 1 : 2 2a 0.02195 0.047343 0.096855 0.009299 0.381696 0.445887 0.445887 0.096855 Nov-08 compost tea 1 : 3 3a 0.511685 0.463857 0.72447 0.532739 0.741511 1.06938 1.06938 0.72447 Mar-09 furthest from building 1 : 4 1b 0.021174 0.019693 0.069954 0.009077 0.218021 0.277426 0.277426 0.069954 Mar-09 closest to building 1 : 5 2b 0.015817 0.067127 0.11485 0.009137 0.228709 0.286614 0.286614 0.11485 Sampling Date Location Tube Sample Labels Cr 267.716 As 193.696 As 188.980 Cr 276.653 Cr 205.560 Ni 230.299 Nov-08 furthest from building 1 : 1 1a -0.031774 -0.005275 -0.064523 -0.012689 -0.017747 0.453686 Nov-08 closest to building 1 : 2 2a -0.032141 0.008806 -0.074675 -0.013508 -0.019497 0.160351 Nov-08 compost tea 1 : 3 3a -0.121301 0.17158 -0.032018 -0.047006 -0.064639 0.065269 Mar-09 furthest from building 1 : 4 1b -0.032544 -0.002639 -0.074707 -0.013028 -0.017643 0.124578 Mar-09 closest to building 1 : 5 2b -0.031231 0.006542 -0.062359 -0.012020 -0.018946 0.114064 44 Sampling Date Location Tube Sample Labels Ni 231.604 Ca 317.933 Ca 396.847 Ca 422.673 Fe 234.350 Fe 238.204 Fe 259.940 K 766.491 Nov-08 furthest from building 1 : 1 1a 0.43298 7.592 7.815 6.576 0.166 0.153 0.156 33.81 Nov-08 closest to building 1 : 2 2a 0.148449 6.026 6.225 5.115 0.325 0.318 0.319 27.9 Nov-08 compost tea 1 : 3 3a -0.034293 156.3 145.2 145.9 9.961 10.16 10.11 6067 x Mar-09 furthest from building 1 : 4 1b 0.114231 23.04 22.22 21.95 1.025 1.03 1.034 50.56 Mar-09 closest to building 1 : 5 2b 0.111669 16.42 16.12 15.11 0.211 0.201 0.206 42.67 Sampling Date Location Tube Sample Labels Mg 279.553 Mg 280.270 Mn 257.610 Mn 293.931 Na 588.995 Na 589.592 Si 212.412 Si 250.690 Nov-08 furthest from building 1 : 1 1a -2.523 -0.161 0.452 0.452 38.57 36.17 -7.615 -7.935 Nov-08 closest to building 1 : 2 2a -2.866 -0.438 0.424 0.424 38.85 36.42 -8.271 -8.611 Nov-08 compost tea 1 : 3 3a -1.605 7.965 2.014 2.013 5910 x 5369 x -29.81 -30.62 Mar-09 furthest from building 1 : 4 1b 2.202 3.588 0.468 0.467 94.58 91.87 -8.451 -8.782 Mar-09 closest to building 1 : 5 2b 0.001 1.858 0.441 0.439 81.74 79.77 -8.915 -9.267 Sampling Date Location Tube Sample Labels Se 203.985 Se 185.457 S 181.972 S 182.562 P 178.222 P 213.618 P 214.914 Nov-08 furthest from building 1 : 1 1a 0.033511 2.04771 3.54607 4.1466 5.707 5.331 5.353 Nov-08 closest to building 1 : 2 2a 0.044579 -3.08811 5.92219 6.75888 4.968 5.049 5.059 Nov-08 compost tea 1 : 3 3a 0.363731 9.93926 1133.11 1194.17 762.7 762.7 758.3 Mar-09 furthest from building 1 : 4 1b 0.057906 -1.40246 4.94004 5.7107 5.771 5.719 5.779 Mar-09 closest to building 1 : 5 2b 0.026885 1.34879 5.36984 5.49449 4.008 4.165 4.217 45 Appendix C: Phreeqc Simulation Data Input File: SELECTED_OUTPUT -file thesis_trial1.xls -water -charge balance -pH -pe -alkalinity -percent_error -totals Cl S S(-2) S(6) N N(5) N(-3) N(3) N Ca Mg Na K Al Cu Fe Mn P Zn -saturation_indices hydroxyapatite strengite vivianite hematite magnetite cupricFerrite Fe(OH)3(a) goethite maghemite MnHPO4 -equilibrium_phases strengite vivianite PHASES Fix_H+ H+ = H+ log_k 0.0 46 # Water Type SOLUTION 1 pH 7.71 Temp 25 pe 4 redox pe units mg/L density 1 Cl 3017 charge S(6) 1133 as SO4 N(-3) 693 as N #NH4 N(5) 308 as N #NO3- Ca 156 K 6067 Na 5910 Cu 0.4638 Fe 9.961 Mn 2.014 Ni 0.0653 P 762.7 as P Zn 0.7415 -water 1 #kg END USE Solution 1 EQUILIBRIUM_PHASES 1 CO2(g) -3.5 10 siderite 0 0 hydroxyapatite 0 0 strengite 0 0 vivianite 0 0 ZnS(a) 0 0 Ni(OH)2 0 0 Calcite 0 0 SAVE EQUILIBRIUM_PHASES 2 SAVE SOLUTION 2 END 47 Output File: Input file: E:\\thesis\\data\\phreeqc trials\\trial 2\\Phrqc1_t1.pqi Output file: E:\\thesis\\data\\phreeqc trials\\trial 2\\Phrqc1_t1.pqo Database file: C:\\Program Files\\USGS\\Phreeqc Interactive 2.15.0\\wateq4f.dat ------------------ Reading data base. ------------------ SOLUTION_MASTER_SPECIES SOLUTION_SPECIES PHASES EXCHANGE_MASTER_SPECIES EXCHANGE_SPECIES SURFACE_MASTER_SPECIES SURFACE_SPECIES RATES END ------------------------------------ Reading input data for simulation 1. ------------------------------------ DATABASE C:\\Program Files\\USGS\\Phreeqc Interactive 2.15.0\\wateq4f.dat SELECTED_OUTPUT file thesis_trial1.xls water charge_balance balance ph pe alkalinity percent_error totals Cl S S(-2) S(6) N N(5) N(-3) N(3) N Ca Mg Na K Al Cu Fe Mn P Zn saturation_indices hydroxyapatite 48 strengite vivianite hematite magnetite cupricFerrite Fe(OH)3(a) goethite maghemite MnHPO4 equilibrium_phases strengite vivianite PHASES Fix_H+ H+ = H+ log_k 0.0 SOLUTION 1 pH 7.71 Temp 25 pe 4 redox pe units mg/L density 1 Cl 3017 charge S(6) 1133 as SO4 N(-3) 693 as N #NH4 N(5) 308 as N #NO3- Ca 156 K 6067 Na 5910 Cu 0.4638 Fe 9.961 Mn 2.014 Ni 0.0653 P 762.7 as P Zn 0.7415 water 1 #kg END 49 ------------------------------------------- Beginning of initial solution calculations. ------------------------------------------- Initial solution 1. -----------------------------Solution composition------------------------------ Elements Molality Moles Ca 3.964e-003 3.964e-003 Cl 3.828e-001 3.828e-001 Charge balance Cu 7.433e-006 7.433e-006 Fe 1.816e-004 1.816e-004 K 1.580e-001 1.580e-001 Mn 3.733e-005 3.733e-005 N(-3) 5.039e-002 5.039e-002 N(5) 2.239e-002 2.239e-002 Na 2.618e-001 2.618e-001 Ni 1.133e-006 1.133e-006 P 2.508e-002 2.508e-002 S(6) 1.201e-002 1.201e-002 Zn 1.155e-005 1.155e-005 ----------------------------Description of solution---------------------------- pH = 7.710 pe = 4.000 Activity of water = 0.985 Ionic strength = 4.926e-001 Mass of water (kg) = 1.000e+000 Total alkalinity (eq/kg) = 2.417e-002 Total carbon (mol/kg) = 0.000e+000 Total CO2 (mol/kg) = 0.000e+000 Temperature (deg C) = 25.000 Electrical balance (eq) = -1.818e-015 Percent error, 100*(Cat-|An|)/(Cat+|An|) = -0.00 Iterations = 16 50 Total H = 1.112404e+002 Total O = 5.572208e+001 ---------------------------------Redox couples--------------------------------- Redox couple pe Eh (volts) N(-3)/N(5) 5.2077 0.3081 ----------------------------Distribution of species---------------------------- Log Log Log Species Molality Activity Molality Activity Gamma OH- 6.894e-007 5.055e-007 -6.162 -6.296 -0.135 H+ 2.549e-008 1.950e-008 -7.594 -7.710 -0.116 H2O 5.551e+001 9.846e-001 1.744 -0.007 0.000 Ca 3.964e-003 Ca+2 2.144e-003 5.599e-004 -2.669 -3.252 -0.583 CaHPO4 1.379e-003 1.545e-003 -2.860 -2.811 0.049 CaPO4- 2.557e-004 1.875e-004 -3.592 -3.727 -0.135 CaSO4 1.542e-004 1.728e-004 -3.812 -3.763 0.049 CaH2PO4+ 3.088e-005 2.264e-005 -4.510 -4.645 -0.135 CaOH+ 6.399e-009 4.692e-009 -8.194 -8.329 -0.135 CaHSO4+ 2.692e-011 1.974e-011 -10.570 -10.705 -0.135 Cl 3.828e-001 Cl- 3.828e-001 2.469e-001 -0.417 -0.608 -0.190 MnCl+ 9.873e-006 7.239e-006 -5.006 -5.140 -0.135 CuCl2- 3.660e-006 2.683e-006 -5.437 -5.571 -0.135 CuCl3-2 3.633e-006 1.050e-006 -5.440 -5.979 -0.539 ZnCl+ 1.932e-006 1.417e-006 -5.714 -5.849 -0.135 FeCl+ 1.348e-006 9.884e-007 -5.870 -6.005 -0.135 ZnOHCl 7.858e-007 8.802e-007 -6.105 -6.055 0.049 MnCl2 6.964e-007 7.800e-007 -6.157 -6.108 0.049 ZnCl2 3.270e-007 3.663e-007 -6.485 -6.436 0.049 NiCl+ 1.885e-007 1.382e-007 -6.725 -6.859 -0.135 ZnCl3- 1.384e-007 1.015e-007 -6.859 -6.994 -0.135 NiCl2 1.106e-007 1.239e-007 -6.956 -6.907 0.049 51 MnCl3- 7.233e-008 5.304e-008 -7.141 -7.275 -0.135 ZnCl4-2 4.343e-008 1.255e-008 -7.362 -7.901 -0.539 CuCl+ 2.404e-009 1.763e-009 -8.619 -8.754 -0.135 CuCl2 2.086e-010 2.337e-010 -9.681 -9.631 0.049 CuCl3- 2.792e-013 2.047e-013 -12.554 -12.689 -0.135 FeCl+2 7.146e-014 2.065e-014 -13.146 -13.685 -0.539 FeCl2+ 3.106e-014 2.277e-014 -13.508 -13.643 -0.135 CuCl4-2 8.763e-016 2.533e-016 -15.057 -15.596 -0.539 FeCl3 5.019e-016 5.622e-016 -15.299 -15.250 0.049 Cu(1) 7.292e-006 CuCl2- 3.660e-006 2.683e-006 -5.437 -5.571 -0.135 CuCl3-2 3.633e-006 1.050e-006 -5.440 -5.979 -0.539 Cu+ 1.899e-010 1.392e-010 -9.721 -9.856 -0.135 Cu(2) 1.406e-007 Cu(OH)2 1.262e-007 1.413e-007 -6.899 -6.850 0.049 Cu+2 9.180e-009 2.653e-009 -8.037 -8.576 -0.539 CuCl+ 2.404e-009 1.763e-009 -8.619 -8.754 -0.135 CuOH+ 1.827e-009 1.340e-009 -8.738 -8.873 -0.135 CuSO4 7.480e-010 8.378e-010 -9.126 -9.077 0.049 CuCl2 2.086e-010 2.337e-010 -9.681 -9.631 0.049 Cu2(OH)2+2 2.717e-012 7.853e-013 -11.566 -12.105 -0.539 Cu(OH)3- 5.865e-013 4.300e-013 -12.232 -12.366 -0.135 CuCl3- 2.792e-013 2.047e-013 -12.554 -12.689 -0.135 CuCl4-2 8.763e-016 2.533e-016 -15.057 -15.596 -0.539 Cu(OH)4-2 1.499e-017 4.333e-018 -16.824 -17.363 -0.539 Fe(2) 6.718e-005 FeHPO4 5.188e-005 5.812e-005 -4.285 -4.236 0.049 Fe+2 1.004e-005 2.901e-006 -4.998 -5.538 -0.539 FeH2PO4+ 3.134e-006 2.298e-006 -5.504 -5.639 -0.135 FeCl+ 1.348e-006 9.884e-007 -5.870 -6.005 -0.135 FeSO4 7.122e-007 7.978e-007 -6.147 -6.098 0.049 FeOH+ 6.317e-008 4.632e-008 -7.199 -7.334 -0.135 Fe(OH)2 1.777e-011 1.991e-011 -10.750 -10.701 0.049 FeHSO4+ 1.395e-013 1.022e-013 -12.856 -12.990 -0.135 Fe(OH)3- 5.094e-014 3.735e-014 -13.293 -13.428 -0.135 Fe(3) 1.145e-004 Fe(OH)3 8.770e-005 9.823e-005 -4.057 -4.008 0.049 Fe(OH)2+ 2.060e-005 1.510e-005 -4.686 -4.821 -0.135 52 Fe(OH)4- 6.170e-006 4.524e-006 -5.210 -5.345 -0.135 FeOH+2 3.125e-009 9.031e-010 -8.505 -9.044 -0.539 FeHPO4+ 5.118e-012 3.752e-012 -11.291 -11.426 -0.135 FeH2PO4+2 4.078e-012 1.178e-012 -11.390 -11.929 -0.539 FeCl+2 7.146e-014 2.065e-014 -13.146 -13.685 -0.539 FeSO4+ 6.407e-014 4.698e-014 -13.193 -13.328 -0.135 Fe+3 4.523e-014 2.770e-015 -13.345 -14.558 -1.213 FeCl2+ 3.106e-014 2.277e-014 -13.508 -13.643 -0.135 Fe2(OH)2+4 3.147e-015 2.195e-017 -14.502 -16.659 -2.156 Fe(SO4)2- 2.168e-015 1.590e-015 -14.664 -14.799 -0.135 FeCl3 5.019e-016 5.622e-016 -15.299 -15.250 0.049 Fe3(OH)4+5 1.621e-016 6.926e-020 -15.790 -19.160 -3.369 FeHSO4+2 8.487e-021 2.453e-021 -20.071 -20.610 -0.539 H(0) 4.806e-027 H2 2.403e-027 2.692e-027 -26.619 -26.570 0.049 K 1.580e-001 K+ 1.552e-001 1.001e-001 -0.809 -1.000 -0.190 KSO4- 1.483e-003 1.088e-003 -2.829 -2.963 -0.135 KHPO4- 1.340e-003 9.822e-004 -2.873 -3.008 -0.135 Mn(2) 3.733e-005 Mn+2 2.491e-005 7.198e-006 -4.604 -5.143 -0.539 MnCl+ 9.873e-006 7.239e-006 -5.006 -5.140 -0.135 MnSO4 1.767e-006 1.980e-006 -5.753 -5.703 0.049 MnCl2 6.964e-007 7.800e-007 -6.157 -6.108 0.049 MnCl3- 7.233e-008 5.304e-008 -7.141 -7.275 -0.135 MnOH+ 1.274e-008 9.342e-009 -7.895 -8.030 -0.135 Mn(NO3)2 6.897e-009 7.725e-009 -8.161 -8.112 0.049 Mn(OH)3- 2.003e-017 1.469e-017 -16.698 -16.833 -0.135 Mn(3) 3.632e-026 Mn+3 3.632e-026 2.224e-027 -25.440 -26.653 -1.213 Mn(6) 0.000e+000 MnO4-2 0.000e+000 0.000e+000 -45.391 -45.930 -0.539 Mn(7) 0.000e+000 MnO4- 0.000e+000 0.000e+000 -51.179 -51.314 -0.135 N(-3) 5.039e-002 NH4+ 4.849e-002 3.555e-002 -1.314 -1.449 -0.135 NH4SO4- 9.662e-004 7.084e-004 -3.015 -3.150 -0.135 NH3 9.277e-004 1.039e-003 -3.033 -2.983 0.049 53 N(5) 2.239e-002 NO3- 2.239e-002 1.642e-002 -1.650 -1.785 -0.135 Mn(NO3)2 6.897e-009 7.725e-009 -8.161 -8.112 0.049 Na 2.618e-001 Na+ 2.574e-001 1.826e-001 -0.589 -0.738 -0.149 NaHPO4- 2.444e-003 1.792e-003 -2.612 -2.747 -0.135 NaSO4- 1.931e-003 1.416e-003 -2.714 -2.849 -0.135 Ni 1.133e-006 Ni+2 7.713e-007 2.229e-007 -6.113 -6.652 -0.539 NiCl+ 1.885e-007 1.382e-007 -6.725 -6.859 -0.135 NiCl2 1.106e-007 1.239e-007 -6.956 -6.907 0.049 NiSO4 6.002e-008 6.723e-008 -7.222 -7.172 0.049 NiOH+ 2.119e-009 1.554e-009 -8.674 -8.809 -0.135 Ni(OH)2 5.075e-011 5.684e-011 -10.295 -10.245 0.049 Ni(SO4)2-2 1.932e-011 5.584e-012 -10.714 -11.253 -0.539 Ni(OH)3- 3.915e-014 2.870e-014 -13.407 -13.542 -0.135 O(0) 9.960e-040 O2 4.980e-040 5.578e-040 -39.303 -39.253 0.049 P 2.508e-002 HPO4-2 1.741e-002 5.033e-003 -1.759 -2.298 -0.539 NaHPO4- 2.444e-003 1.792e-003 -2.612 -2.747 -0.135 H2PO4- 2.156e-003 1.581e-003 -2.666 -2.801 -0.135 CaHPO4 1.379e-003 1.545e-003 -2.860 -2.811 0.049 KHPO4- 1.340e-003 9.822e-004 -2.873 -3.008 -0.135 CaPO4- 2.557e-004 1.875e-004 -3.592 -3.727 -0.135 FeHPO4 5.188e-005 5.812e-005 -4.285 -4.236 0.049 CaH2PO4+ 3.088e-005 2.264e-005 -4.510 -4.645 -0.135 FeH2PO4+ 3.134e-006 2.298e-006 -5.504 -5.639 -0.135 PO4-3 1.900e-006 1.164e-007 -5.721 -6.934 -1.213 FeHPO4+ 5.118e-012 3.752e-012 -11.291 -11.426 -0.135 FeH2PO4+2 4.078e-012 1.178e-012 -11.390 -11.929 -0.539 S(6) 1.201e-002 SO4-2 7.473e-003 1.547e-003 -2.127 -2.811 -0.684 NaSO4- 1.931e-003 1.416e-003 -2.714 -2.849 -0.135 KSO4- 1.483e-003 1.088e-003 -2.829 -2.963 -0.135 NH4SO4- 9.662e-004 7.084e-004 -3.015 -3.150 -0.135 CaSO4 1.542e-004 1.728e-004 -3.812 -3.763 0.049 MnSO4 1.767e-006 1.980e-006 -5.753 -5.703 0.049 54 FeSO4 7.122e-007 7.978e-007 -6.147 -6.098 0.049 ZnSO4 6.903e-007 7.732e-007 -6.161 -6.112 0.049 NiSO4 6.002e-008 6.723e-008 -7.222 -7.172 0.049 Zn(SO4)2-2 3.363e-008 9.720e-009 -7.473 -8.012 -0.539 HSO4- 3.999e-009 2.932e-009 -8.398 -8.533 -0.135 CuSO4 7.480e-010 8.378e-010 -9.126 -9.077 0.049 CaHSO4+ 2.692e-011 1.974e-011 -10.570 -10.705 -0.135 Ni(SO4)2-2 1.932e-011 5.584e-012 -10.714 -11.253 -0.539 FeHSO4+ 1.395e-013 1.022e-013 -12.856 -12.990 -0.135 FeSO4+ 6.407e-014 4.698e-014 -13.193 -13.328 -0.135 Fe(SO4)2- 2.168e-015 1.590e-015 -14.664 -14.799 -0.135 FeHSO4+2 8.487e-021 2.453e-021 -20.071 -20.610 -0.539 Zn 1.155e-005 Zn+2 7.379e-006 2.132e-006 -5.132 -5.671 -0.539 ZnCl+ 1.932e-006 1.417e-006 -5.714 -5.849 -0.135 ZnOHCl 7.858e-007 8.802e-007 -6.105 -6.055 0.049 ZnSO4 6.903e-007 7.732e-007 -6.161 -6.112 0.049 ZnCl2 3.270e-007 3.663e-007 -6.485 -6.436 0.049 ZnOH+ 1.610e-007 1.181e-007 -6.793 -6.928 -0.135 ZnCl3- 1.384e-007 1.015e-007 -6.859 -6.994 -0.135 Zn(OH)2 6.111e-008 6.845e-008 -7.214 -7.165 0.049 ZnCl4-2 4.343e-008 1.255e-008 -7.362 -7.901 -0.539 Zn(SO4)2-2 3.363e-008 9.720e-009 -7.473 -8.012 -0.539 Zn(OH)3- 1.491e-011 1.093e-011 -10.827 -10.961 -0.135 Zn(OH)4-2 3.027e-016 8.748e-017 -15.519 -16.058 -0.539 ------------------------------Saturation indices------------------------------- Phase SI log IAP log KT Anhydrite -1.70 -6.06 -4.36 CaSO4 Antlerite -6.02 2.27 8.29 Cu3(OH)4SO4 Atacamite -1.99 5.35 7.34 Cu2(OH)3Cl Bianchite -6.76 -8.52 -1.76 ZnSO4:6H2O Birnessite -9.92 33.68 43.60 MnO2 Bixbyite -6.45 -7.07 -0.61 Mn2O3 Brochantite -6.24 9.10 15.34 Cu4(OH)6SO4 Bunsenite -3.69 8.76 12.45 NiO 55 Chalcanthite -8.78 -11.42 -2.64 CuSO4:5H2O Cu(OH)2 -1.81 6.83 8.64 Cu(OH)2 Cu2(OH)3NO3 -5.07 4.17 9.24 Cu2(OH)3NO3 Cu2SO4 -20.57 -22.52 -1.95 Cu2SO4 Cu3(PO4)2 -2.75 -39.60 -36.85 Cu3(PO4)2 Cu3(PO4)2:3H2O -4.50 -39.62 -35.12 Cu3(PO4)2:3H2O CuMetal -5.10 -13.86 -8.76 Cu CuOCuSO4 -16.08 -4.55 11.53 CuO:CuSO4 CupricFerrite 18.08 23.96 5.88 CuFe2O4 Cuprite -2.75 -4.30 -1.55 Cu2O CuprousFerrite 15.33 6.41 -8.92 CuFeO2 CuSO4 -14.40 -11.39 3.01 CuSO4 Fe(OH)2.7Cl.3 9.10 6.06 -3.04 Fe(OH)2.7Cl0.3 Fe(OH)3(a) 3.66 8.55 4.89 Fe(OH)3 Fe3(OH)8 6.75 26.97 20.22 Fe3(OH)8 Fix_H+ -7.71 -7.71 0.00 H+ Goethite 9.56 8.56 -1.00 FeOOH Goslarite -6.57 -8.53 -1.96 ZnSO4:7H2O Gypsum -1.50 -6.08 -4.58 CaSO4:2H2O H2(g) -23.42 -26.57 -3.15 H2 H2O(g) -1.52 -0.01 1.51 H2O Halite -2.93 -1.35 1.58 NaCl Hausmannite -6.81 54.22 61.03 Mn3O4 Hematite 21.13 17.12 -4.01 Fe2O3 Hydroxyapatite 11.10 7.68 -3.42 Ca5(PO4)3OH Jarosite(ss) 4.42 -5.41 -9.83 (K0.77Na0.03H0.2)Fe3(SO4)2(OH)6 Jarosite-K 5.14 -4.07 -9.21 KFe3(SO4)2(OH)6 Jarosite-Na 1.47 -3.81 -5.28 NaFe3(SO4)2(OH)6 JarositeH -5.40 -10.79 -5.39 (H3O)Fe3(SO4)2(OH)6 Langite -7.69 9.10 16.79 Cu4(OH)6SO4:H2O Maghemite 10.74 17.12 6.39 Fe2O3 Magnetite 23.26 27.00 3.74 Fe3O4 Manganite -3.37 21.97 25.34 MnOOH Melanothallite -13.52 -9.79 3.73 CuCl2 Melanterite -6.19 -8.40 -2.21 FeSO4:7H2O Mirabilite -3.24 -4.35 -1.11 Na2SO4:10H2O Mn2(SO4)3 -56.03 -61.74 -5.71 Mn2(SO4)3 Mn3(PO4)2 -5.47 -29.30 -23.83 Mn3(PO4)2 56 MnCl2:4H2O -9.09 -6.38 2.71 MnCl2:4H2O MnHPO4 5.51 -7.44 -12.95 MnHPO4 MnSO4 -10.62 -7.95 2.67 MnSO4 Morenosite -7.15 -9.51 -2.36 NiSO4:7H2O Nantokite -3.70 -10.46 -6.76 CuCl NH3(g) -4.75 -2.98 1.77 NH3 Ni(OH)2 -2.05 8.75 10.80 Ni(OH)2 Ni3(PO4)2 -2.52 -33.82 -31.30 Ni3(PO4)2 Ni4(OH)6SO4 -15.20 16.80 32.00 Ni4(OH)6SO4 Nsutite -8.88 33.68 42.56 MnO2 O2(g) -36.36 -39.25 -2.89 O2 Portlandite -10.65 12.15 22.80 Ca(OH)2 Pyrochroite -4.94 10.26 15.20 Mn(OH)2 Pyrolusite -7.70 33.68 41.38 MnO2 Retgersite -7.46 -9.50 -2.04 NiSO4:6H2O Strengite 4.89 -21.51 -26.40 FePO4:2H2O Tenorite -0.78 6.84 7.62 CuO Thenardite -4.11 -4.29 -0.18 Na2SO4 Vivianite 5.47 -30.53 -36.00 Fe3(PO4)2:8H2O Zincite(c) -1.40 9.74 11.14 ZnO Zincosite -11.49 -8.48 3.01 ZnSO4 Zn(NO3)2:6H2O -12.72 -9.28 3.44 Zn(NO3)2:6H2O Zn(OH)2-a -2.71 9.74 12.45 Zn(OH)2 Zn(OH)2-b -2.01 9.74 11.75 Zn(OH)2 Zn(OH)2-c -2.46 9.74 12.20 Zn(OH)2 Zn(OH)2-e -1.76 9.74 11.50 Zn(OH)2 Zn(OH)2-g -1.97 9.74 11.71 Zn(OH)2 Zn2(OH)2SO4 -6.25 1.25 7.50 Zn2(OH)2SO4 Zn2(OH)3Cl -4.04 11.16 15.20 Zn2(OH)3Cl Zn3(PO4)2:4w 1.13 -30.91 -32.04 Zn3(PO4)2:4H2O Zn3O(SO4)2 -26.24 -7.22 19.02 ZnO:2ZnSO4 Zn4(OH)6SO4 -7.68 20.72 28.40 Zn4(OH)6SO4 Zn5(OH)8Cl2 -6.44 32.06 38.50 Zn5(OH)8Cl2 ZnCl2 -13.92 -6.89 7.03 ZnCl2 ZnMetal -39.43 -13.67 25.76 Zn ZnO(a) -1.57 9.74 11.31 ZnO ZnSO4:H2O -7.92 -8.49 -0.57 ZnSO4:H2O 57 ------------------ End of simulation. ------------------ ------------------------------------ Reading input data for simulation 2. ------------------------------------ USE Solution 1 EQUILIBRIUM_PHASES 1 CO2(g) -3.5 10 siderite 0 0 hydroxyapatite 0 0 strengite 0 0 vivianite 0 0 ZnS(a) 0 0 Ni(OH)2 0 0 Calcite 0 0 SAVE EQUILIBRIUM_PHASES 2 SAVE SOLUTION 2 END ----------------------------------------- Beginning of batch-reaction calculations. ----------------------------------------- Reaction step 1. Using solution 1. Using pure phase assemblage 1. -------------------------------Phase assemblage-------------------------------- Moles in assemblage Phase SI log IAP log KT Initial Final Delta Calcite -4.78 -13.26 -8.48 0.000e+000 0 0.000e+000 CO2(g) -3.50 -4.97 -1.47 1.000e+001 1.000e+001 -1.791e-005 Hydroxyapatite -0.00 -3.42 -3.42 0.000e+000 6.008e-004 6.008e-004 58 Ni(OH)2 -5.36 5.44 10.80 0.000e+000 0 0.000e+000 Siderite -4.44 -15.33 -10.89 0.000e+000 0 0.000e+000 Strengite -4.15 -30.55 -26.40 0.000e+000 0 0.000e+000 Vivianite 0.00 -36.00 -36.00 0.000e+000 4.774e-005 4.774e-005 ZnS(a) -0.66 -9.71 -9.05 0.000e+000 0 0.000e+000 -----------------------------Solution composition------------------------------ Elements Molality Moles C 1.789e-005 1.791e-005 Ca 9.588e-004 9.600e-004 Cl 3.823e-001 3.828e-001 Cu 7.424e-006 7.433e-006 Fe 3.838e-005 3.843e-005 K 1.578e-001 1.580e-001 Mn 3.729e-005 3.733e-005 N 7.269e-002 7.278e-002 Na 2.615e-001 2.618e-001 Ni 1.131e-006 1.133e-006 P 2.315e-002 2.318e-002 S 1.200e-002 1.201e-002 Zn 1.154e-005 1.155e-005 ----------------------------Description of solution---------------------------- pH = 6.054 Charge balance pe = -2.435 Adjusted to redox equilibrium Activity of water = 0.985 Ionic strength = 4.388e-001 Mass of water (kg) = 1.001e+000 Total alkalinity (eq/kg) = 4.412e-003 Total CO2 (mol/kg) = 1.789e-005 Temperature (deg C) = 25.000 Electrical balance (eq) = -1.536e-015 Percent error, 100*(Cat-|An|)/(Cat+|An|) = -0.00 Iterations = 25 Total H = 1.112390e+002 59 Total O = 5.571354e+001 ----------------------------Distribution of species---------------------------- Log Log Log Species Molality Activity Molality Activity Gamma H+ 1.149e-006 8.834e-007 -5.940 -6.054 -0.114 OH- 1.527e-008 1.116e-008 -7.816 -7.952 -0.136 H2O 5.551e+001 9.851e-001 1.744 -0.007 0.000 C(-4) 2.775e-010 CH4 2.775e-010 3.070e-010 -9.557 -9.513 0.044 C(4) 1.789e-005 CO2 9.732e-006 1.077e-005 -5.012 -4.968 0.044 HCO3- 7.633e-006 5.340e-006 -5.117 -5.272 -0.155 NaHCO3 5.005e-007 5.537e-007 -6.301 -6.257 0.044 CaHCO3+ 1.785e-008 1.306e-008 -7.748 -7.884 -0.136 MnHCO3+ 4.618e-009 3.377e-009 -8.336 -8.471 -0.136 NaCO3- 1.331e-009 9.734e-010 -8.876 -9.012 -0.136 FeHCO3+ 1.217e-009 8.897e-010 -8.915 -9.051 -0.136 CO3-2 1.184e-009 2.835e-010 -8.927 -9.547 -0.621 NiCO3 4.171e-010 4.614e-010 -9.380 -9.336 0.044 NiHCO3+ 2.213e-010 1.618e-010 -9.655 -9.791 -0.136 MnCO3 1.444e-010 1.598e-010 -9.840 -9.796 0.044 CaCO3 8.230e-011 9.105e-011 -10.085 -10.041 0.044 FeCO3 1.024e-011 1.133e-011 -10.990 -10.946 0.044 ZnHCO3+ 1.862e-015 1.362e-015 -14.730 -14.866 -0.136 Ni(CO3)2-2 7.948e-016 2.273e-016 -15.100 -15.643 -0.544 ZnCO3 1.036e-016 1.146e-016 -15.985 -15.941 0.044 Zn(CO3)2-2 2.428e-021 6.946e-022 -20.615 -21.158 -0.544 CuHCO3+ 4.077e-022 2.981e-022 -21.390 -21.526 -0.136 CuCO3 1.533e-022 1.696e-022 -21.814 -21.771 0.044 Cu(CO3)2-2 2.116e-028 6.053e-029 -27.674 -28.218 -0.544 Ca 9.588e-004 Ca+2 7.190e-004 1.917e-004 -3.143 -3.717 -0.574 CaH2PO4+ 9.232e-005 6.752e-005 -4.035 -4.171 -0.136 CaHPO4 9.192e-005 1.017e-004 -4.037 -3.993 0.044 CaSO4 5.518e-005 6.105e-005 -4.258 -4.214 0.044 60 CaPO4- 3.724e-007 2.724e-007 -6.429 -6.565 -0.136 CaHCO3+ 1.785e-008 1.306e-008 -7.748 -7.884 -0.136 CaHSO4+ 4.320e-010 3.159e-010 -9.365 -9.500 -0.136 CaCO3 8.230e-011 9.105e-011 -10.085 -10.041 0.044 CaOH+ 4.851e-011 3.548e-011 -10.314 -10.450 -0.136 Cl 3.823e-001 Cl- 3.823e-001 2.497e-001 -0.418 -0.603 -0.185 MnCl+ 9.870e-006 7.218e-006 -5.006 -5.142 -0.136 FeCl+ 7.853e-007 5.743e-007 -6.105 -6.241 -0.136 MnCl2 7.112e-007 7.868e-007 -6.148 -6.104 0.044 NiCl+ 1.883e-007 1.377e-007 -6.725 -6.861 -0.136 NiCl2 1.129e-007 1.249e-007 -6.947 -6.904 0.044 MnCl3- 7.400e-008 5.412e-008 -7.131 -7.267 -0.136 CuCl3-2 4.346e-010 1.243e-010 -9.362 -9.905 -0.544 CuCl2- 4.295e-010 3.141e-010 -9.367 -9.503 -0.136 ZnCl+ 1.862e-012 1.362e-012 -11.730 -11.866 -0.136 ZnCl2 3.218e-013 3.561e-013 -12.492 -12.448 0.044 ZnCl3- 1.364e-013 9.976e-014 -12.865 -13.001 -0.136 ZnCl4-2 4.365e-014 1.249e-014 -13.360 -13.904 -0.544 ZnOHCl 1.689e-014 1.868e-014 -13.772 -13.729 0.044 CuCl+ 1.024e-019 7.487e-020 -18.990 -19.126 -0.136 FeCl+2 1.540e-020 4.404e-021 -19.813 -20.356 -0.544 CuCl2 9.075e-021 1.004e-020 -20.042 -19.998 0.044 FeCl2+ 6.717e-021 4.912e-021 -20.173 -20.309 -0.136 FeCl3 1.109e-022 1.227e-022 -21.955 -21.911 0.044 CuCl3- 1.216e-023 8.896e-024 -22.915 -23.051 -0.136 CuCl4-2 3.892e-026 1.113e-026 -25.410 -25.953 -0.544 Cu(1) 8.641e-010 CuCl3-2 4.346e-010 1.243e-010 -9.362 -9.905 -0.544 CuCl2- 4.295e-010 3.141e-010 -9.367 -9.503 -0.136 Cu+ 2.178e-014 1.593e-014 -13.662 -13.798 -0.136 Cu(2) 7.423e-006 Cu(HS)3- 7.423e-006 5.428e-006 -5.129 -5.265 -0.136 Cu+2 3.894e-019 1.114e-019 -18.410 -18.953 -0.544 CuCl+ 1.024e-019 7.487e-020 -18.990 -19.126 -0.136 CuSO4 3.281e-020 3.630e-020 -19.484 -19.440 0.044 CuCl2 9.075e-021 1.004e-020 -20.042 -19.998 0.044 Cu(OH)2 2.616e-021 2.894e-021 -20.582 -20.538 0.044 61 CuOH+ 1.699e-021 1.242e-021 -20.770 -20.906 -0.136 CuHCO3+ 4.077e-022 2.981e-022 -21.390 -21.526 -0.136 CuCO3 1.533e-022 1.696e-022 -21.814 -21.771 0.044 CuCl3- 1.216e-023 8.896e-024 -22.915 -23.051 -0.136 CuCl4-2 3.892e-026 1.113e-026 -25.410 -25.953 -0.544 Cu(OH)3- 2.659e-028 1.945e-028 -27.575 -27.711 -0.136 Cu(CO3)2-2 2.116e-028 6.053e-029 -27.674 -28.218 -0.544 Cu(OH)4-2 1.513e-034 4.328e-035 -33.820 -34.364 -0.544 Cu2(OH)2+2 2.361e-036 6.752e-037 -35.627 -36.171 -0.544 Fe(2) 3.838e-005 FeH2PO4+ 1.572e-005 1.149e-005 -4.804 -4.940 -0.136 Fe(HS)2 9.690e-006 1.072e-005 -5.014 -4.970 0.044 Fe+2 5.825e-006 1.666e-006 -5.235 -5.778 -0.544 FeHPO4 5.800e-006 6.417e-006 -5.237 -5.193 0.044 FeCl+ 7.853e-007 5.743e-007 -6.105 -6.241 -0.136 FeSO4 4.274e-007 4.728e-007 -6.369 -6.325 0.044 Fe(HS)3- 1.356e-007 9.920e-008 -6.868 -7.004 -0.136 FeHCO3+ 1.217e-009 8.897e-010 -8.915 -9.051 -0.136 FeOH+ 8.034e-010 5.875e-010 -9.095 -9.231 -0.136 FeCO3 1.024e-011 1.133e-011 -10.990 -10.946 0.044 FeHSO4+ 3.754e-012 2.746e-012 -11.425 -11.561 -0.136 Fe(OH)2 5.041e-015 5.577e-015 -14.298 -14.254 0.044 Fe(OH)3- 3.160e-019 2.311e-019 -18.500 -18.636 -0.136 Fe(3) 2.347e-015 Fe(OH)2+ 2.123e-015 1.553e-015 -14.673 -14.809 -0.136 Fe(OH)3 2.016e-016 2.231e-016 -15.695 -15.652 0.044 FeOH+2 1.470e-017 4.204e-018 -16.833 -17.376 -0.544 FeH2PO4+2 7.564e-018 2.163e-018 -17.121 -17.665 -0.544 Fe(OH)4- 3.102e-019 2.269e-019 -18.508 -18.644 -0.136 FeHPO4+ 2.079e-019 1.521e-019 -18.682 -18.818 -0.136 FeCl+2 1.540e-020 4.404e-021 -19.813 -20.356 -0.544 FeSO4+ 1.397e-020 1.022e-020 -19.855 -19.991 -0.136 Fe+3 9.759e-021 5.839e-022 -20.011 -21.234 -1.223 FeCl2+ 6.717e-021 4.912e-021 -20.173 -20.309 -0.136 Fe(SO4)2- 4.879e-022 3.568e-022 -21.312 -21.448 -0.136 FeCl3 1.109e-022 1.227e-022 -21.955 -21.911 0.044 FeHSO4+2 8.451e-026 2.417e-026 -25.073 -25.617 -0.544 Fe2(OH)2+4 7.108e-032 4.758e-034 -31.148 -33.323 -2.174 62 Fe3(OH)4+5 0.000e+000 0.000e+000 -42.414 -45.812 -3.397 H(0) 7.415e-011 H2 3.707e-011 4.101e-011 -10.431 -10.387 0.044 K 1.578e-001 K+ 1.560e-001 1.019e-001 -0.807 -0.992 -0.185 KSO4- 1.562e-003 1.143e-003 -2.806 -2.942 -0.136 KHPO4- 2.628e-004 1.922e-004 -3.580 -3.716 -0.136 Mn(2) 3.729e-005 Mn+2 2.481e-005 7.095e-006 -4.605 -5.149 -0.544 MnCl+ 9.870e-006 7.218e-006 -5.006 -5.142 -0.136 MnSO4 1.820e-006 2.014e-006 -5.740 -5.696 0.044 MnCl2 7.112e-007 7.868e-007 -6.148 -6.104 0.044 MnCl3- 7.400e-008 5.412e-008 -7.131 -7.267 -0.136 MnHCO3+ 4.618e-009 3.377e-009 -8.336 -8.471 -0.136 MnOH+ 2.781e-010 2.034e-010 -9.556 -9.692 -0.136 MnCO3 1.444e-010 1.598e-010 -9.840 -9.796 0.044 Mn(OH)3- 2.133e-022 1.560e-022 -21.671 -21.807 -0.136 Mn(NO3)2 0.000e+000 0.000e+000 -164.885 -164.842 0.044 Mn(3) 1.345e-032 Mn+3 1.345e-032 8.047e-034 -31.871 -33.094 -1.223 Mn(6) 0.000e+000 MnO4-2 0.000e+000 0.000e+000 -84.382 -84.925 -0.544 Mn(7) 0.000e+000 MnO4- 0.000e+000 0.000e+000 -96.609 -96.745 -0.136 N(-3) 1.094e-002 NH4+ 1.072e-002 7.839e-003 -1.970 -2.106 -0.136 NH4SO4- 2.204e-004 1.612e-004 -3.657 -3.793 -0.136 NH3 4.571e-006 5.057e-006 -5.340 -5.296 0.044 N(0) 6.174e-002 N2 3.087e-002 3.415e-002 -1.510 -1.467 0.044 N(3) 0.000e+000 NO2- 0.000e+000 0.000e+000 -58.671 -58.807 -0.136 N(5) 0.000e+000 NO3- 0.000e+000 0.000e+000 -80.010 -80.146 -0.136 Mn(NO3)2 0.000e+000 0.000e+000 -164.885 -164.842 0.044 Na 2.615e-001 Na+ 2.590e-001 1.844e-001 -0.587 -0.734 -0.148 NaSO4- 2.017e-003 1.475e-003 -2.695 -2.831 -0.136 63 NaHPO4- 4.757e-004 3.479e-004 -3.323 -3.459 -0.136 NaHCO3 5.005e-007 5.537e-007 -6.301 -6.257 0.044 NaCO3- 1.331e-009 9.734e-010 -8.876 -9.012 -0.136 Ni 1.131e-006 Ni+2 7.676e-007 2.196e-007 -6.115 -6.658 -0.544 NiCl+ 1.883e-007 1.377e-007 -6.725 -6.861 -0.136 NiCl2 1.129e-007 1.249e-007 -6.947 -6.904 0.044 NiSO4 6.176e-008 6.833e-008 -7.209 -7.165 0.044 NiCO3 4.171e-010 4.614e-010 -9.380 -9.336 0.044 NiHCO3+ 2.213e-010 1.618e-010 -9.655 -9.791 -0.136 NiOH+ 4.622e-011 3.380e-011 -10.335 -10.471 -0.136 Ni(SO4)2-2 2.048e-011 5.857e-012 -10.689 -11.232 -0.544 Ni(OH)2 2.468e-014 2.731e-014 -13.608 -13.564 0.044 Ni(CO3)2-2 7.948e-016 2.273e-016 -15.100 -15.643 -0.544 Ni(OH)3- 4.164e-019 3.045e-019 -18.380 -18.516 -0.136 O(0) 0.000e+000 O2 0.000e+000 0.000e+000 -71.663 -71.619 0.044 P 2.315e-002 H2PO4- 1.882e-002 1.377e-002 -1.725 -1.861 -0.136 HPO4-2 3.382e-003 9.675e-004 -2.471 -3.014 -0.544 NaHPO4- 4.757e-004 3.479e-004 -3.323 -3.459 -0.136 KHPO4- 2.628e-004 1.922e-004 -3.580 -3.716 -0.136 CaH2PO4+ 9.232e-005 6.752e-005 -4.035 -4.171 -0.136 CaHPO4 9.192e-005 1.017e-004 -4.037 -3.993 0.044 FeH2PO4+ 1.572e-005 1.149e-005 -4.804 -4.940 -0.136 FeHPO4 5.800e-006 6.417e-006 -5.237 -5.193 0.044 CaPO4- 3.724e-007 2.724e-007 -6.429 -6.565 -0.136 PO4-3 8.252e-009 4.938e-010 -8.083 -9.306 -1.223 FeH2PO4+2 7.564e-018 2.163e-018 -17.121 -17.665 -0.544 FeHPO4+ 2.079e-019 1.521e-019 -18.682 -18.818 -0.136 S(-2) 7.752e-004 H2S 5.932e-004 6.563e-004 -3.227 -3.183 0.044 HS- 1.162e-004 8.497e-005 -3.935 -4.071 -0.136 Zn(HS)2 1.152e-005 1.274e-005 -4.939 -4.895 0.044 Fe(HS)2 9.690e-006 1.072e-005 -5.014 -4.970 0.044 Cu(HS)3- 7.423e-006 5.428e-006 -5.129 -5.265 -0.136 Fe(HS)3- 1.356e-007 9.920e-008 -6.868 -7.004 -0.136 S5-2 5.781e-008 2.444e-008 -7.238 -7.612 -0.374 64 S4-2 3.795e-008 1.426e-008 -7.421 -7.846 -0.425 S6-2 2.728e-008 1.265e-008 -7.564 -7.898 -0.334 Zn(HS)3- 2.140e-008 1.565e-008 -7.670 -7.806 -0.136 S-2 4.062e-011 1.162e-011 -10.391 -10.935 -0.544 S3-2 1.562e-011 5.025e-012 -10.806 -11.299 -0.493 S2-2 1.033e-012 2.852e-013 -11.986 -12.545 -0.559 S(6) 1.122e-002 SO4-2 7.364e-003 1.596e-003 -2.133 -2.797 -0.664 NaSO4- 2.017e-003 1.475e-003 -2.695 -2.831 -0.136 KSO4- 1.562e-003 1.143e-003 -2.806 -2.942 -0.136 NH4SO4- 2.204e-004 1.612e-004 -3.657 -3.793 -0.136 CaSO4 5.518e-005 6.105e-005 -4.258 -4.214 0.044 MnSO4 1.820e-006 2.014e-006 -5.740 -5.696 0.044 FeSO4 4.274e-007 4.728e-007 -6.369 -6.325 0.044 HSO4- 1.874e-007 1.371e-007 -6.727 -6.863 -0.136 NiSO4 6.176e-008 6.833e-008 -7.209 -7.165 0.044 CaHSO4+ 4.320e-010 3.159e-010 -9.365 -9.500 -0.136 Ni(SO4)2-2 2.048e-011 5.857e-012 -10.689 -11.232 -0.544 FeHSO4+ 3.754e-012 2.746e-012 -11.425 -11.561 -0.136 ZnSO4 6.852e-013 7.580e-013 -12.164 -12.120 0.044 Zn(SO4)2-2 3.438e-014 9.834e-015 -13.464 -14.007 -0.544 CuSO4 3.281e-020 3.630e-020 -19.484 -19.440 0.044 FeSO4+ 1.397e-020 1.022e-020 -19.855 -19.991 -0.136 Fe(SO4)2- 4.879e-022 3.568e-022 -21.312 -21.448 -0.136 FeHSO4+2 8.451e-026 2.417e-026 -25.073 -25.617 -0.544 Zn 1.154e-005 Zn(HS)2 1.152e-005 1.274e-005 -4.939 -4.895 0.044 Zn(HS)3- 2.140e-008 1.565e-008 -7.670 -7.806 -0.136 Zn+2 7.083e-012 2.026e-012 -11.150 -11.693 -0.544 ZnCl+ 1.862e-012 1.362e-012 -11.730 -11.866 -0.136 ZnSO4 6.852e-013 7.580e-013 -12.164 -12.120 0.044 ZnCl2 3.218e-013 3.561e-013 -12.492 -12.448 0.044 ZnCl3- 1.364e-013 9.976e-014 -12.865 -13.001 -0.136 ZnCl4-2 4.365e-014 1.249e-014 -13.360 -13.904 -0.544 Zn(SO4)2-2 3.438e-014 9.834e-015 -13.464 -14.007 -0.544 ZnOHCl 1.689e-014 1.868e-014 -13.772 -13.729 0.044 ZnOH+ 3.387e-015 2.477e-015 -14.470 -14.606 -0.136 ZnHCO3+ 1.862e-015 1.362e-015 -14.730 -14.866 -0.136 65 ZnCO3 1.036e-016 1.146e-016 -15.985 -15.941 0.044 Zn(OH)2 2.867e-017 3.172e-017 -16.543 -16.499 0.044 Zn(CO3)2-2 2.428e-021 6.946e-022 -20.615 -21.158 -0.544 Zn(OH)3- 1.530e-022 1.119e-022 -21.815 -21.951 -0.136 Zn(OH)4-2 6.912e-029 1.977e-029 -28.160 -28.704 -0.544 ------------------------------Saturation indices------------------------------- Phase SI log IAP log KT Anhydrite -2.15 -6.51 -4.36 CaSO4 Anilite 8.43 -23.45 -31.88 Cu0.25Cu1.5S Antlerite -43.76 -35.47 8.29 Cu3(OH)4SO4 Aragonite -4.93 -13.26 -8.34 CaCO3 Atacamite -27.71 -20.37 7.34 Cu2(OH)3Cl Azurite -46.95 -43.20 3.75 Cu3(OH)2(CO3)2 Bianchite -12.76 -14.53 -1.76 ZnSO4:6H2O Birnessite -29.42 14.18 43.60 MnO2 Bixbyite -29.27 -29.89 -0.61 Mn2O3 BlaubleiI 6.33 -17.83 -24.16 Cu0.9Cu0.2S BlaubleiII 6.85 -20.43 -27.28 Cu0.6Cu0.8S Brochantite -57.67 -42.33 15.34 Cu4(OH)6SO4 Bunsenite -7.01 5.44 12.45 NiO Calcite -4.78 -13.26 -8.48 CaCO3 CH4(g) -6.65 -9.51 -2.86 CH4 Chalcanthite -19.14 -21.78 -2.64 CuSO4:5H2O Chalcocite 9.01 -25.61 -34.62 Cu2S Chalcopyrite 14.50 -20.77 -35.27 CuFeS2 CO2(g) -3.50 -4.97 -1.47 CO2 Covellite 5.30 -16.97 -22.27 CuS Cu(OH)2 -15.50 -6.86 8.64 Cu(OH)2 Cu2(OH)3NO3 -109.15 -99.91 9.24 Cu2(OH)3NO3 Cu2SO4 -28.44 -30.39 -1.95 Cu2SO4 Cu3(PO4)2 -38.62 -75.47 -36.85 Cu3(PO4)2 Cu3(PO4)2:3H2O -40.37 -75.49 -35.12 Cu3(PO4)2:3H2O CuCO3 -18.87 -28.50 -9.63 CuCO3 CuMetal -2.60 -11.36 -8.76 Cu CuOCuSO4 -40.13 -28.60 11.53 CuO:CuSO4 66 CupricFerrite -18.90 -13.02 5.88 CuFe2O4 Cuprite -13.94 -15.49 -1.55 Cu2O CuprousFerrite -1.91 -10.83 -8.92 CuFeO2 CuSO4 -24.76 -21.75 3.01 CuSO4 Djurleite 8.88 -25.04 -33.92 Cu0.066Cu1.868S Fe(OH)2.7Cl.3 -2.05 -5.09 -3.04 Fe(OH)2.7Cl0.3 Fe(OH)3(a) -7.98 -3.09 4.89 Fe(OH)3 Fe3(OH)8 -20.09 0.13 20.22 Fe3(OH)8 FeS(ppt) 0.12 -3.80 -3.92 FeS Fix_H+ -6.05 -6.05 0.00 H+ Goethite -2.09 -3.09 -1.00 FeOOH Goslarite -12.58 -14.54 -1.96 ZnSO4:7H2O Greigite 4.72 -40.31 -45.03 Fe3S4 Gypsum -1.95 -6.53 -4.58 CaSO4:2H2O H2(g) -7.24 -10.39 -3.15 H2 H2O(g) -1.52 -0.01 1.51 H2O H2S(g) -2.19 -3.18 -1.00 H2S Halite -2.92 -1.34 1.58 NaCl Hausmannite -32.94 28.09 61.03 Mn3O4 Hematite -2.16 -6.16 -4.01 Fe2O3 Hydroxyapatite -0.00 -3.42 -3.42 Ca5(PO4)3OH Jarosite(ss) -25.18 -35.01 -9.83 (K0.77Na0.03H0.2)Fe3(SO4)2(OH)6 Jarosite-K -24.79 -34.00 -9.21 KFe3(SO4)2(OH)6 Jarosite-Na -28.47 -33.75 -5.28 NaFe3(SO4)2(OH)6 JarositeH -33.68 -39.07 -5.39 (H3O)Fe3(SO4)2(OH)6 Langite -59.12 -42.33 16.79 Cu4(OH)6SO4:H2O Mackinawite 0.85 -3.80 -4.65 FeS Maghemite -12.55 -6.16 6.39 Fe2O3 Magnetite -3.58 0.16 3.74 Fe3O4 Malachite -30.18 -25.03 5.15 Cu2(OH)2CO3 Manganite -14.78 10.56 25.34 MnOOH Melanothallite -23.89 -20.16 3.73 CuCl2 Melanterite -6.41 -8.62 -2.21 FeSO4:7H2O Millerite 3.37 -4.68 -8.04 NiS Mirabilite -3.22 -4.33 -1.11 Na2SO4:10H2O Mn2(SO4)3 -68.87 -74.58 -5.71 Mn2(SO4)3 Mn3(PO4)2 -10.23 -34.06 -23.83 Mn3(PO4)2 MnCl2:4H2O -9.09 -6.38 2.71 MnCl2:4H2O 67 MnHPO4 4.78 -8.16 -12.95 MnHPO4 MnS(Green) -6.97 -3.17 3.80 MnS MnSO4 -10.61 -7.95 2.67 MnSO4 Morenosite -7.14 -9.50 -2.36 NiSO4:7H2O N2(g) 1.79 -1.47 -3.26 N2 Nahcolite -5.46 -6.01 -0.55 NaHCO3 Nantokite -7.64 -14.40 -6.76 CuCl Natron -9.77 -11.08 -1.31 Na2CO3:10H2O NH3(g) -7.07 -5.30 1.77 NH3 Ni(OH)2 -5.36 5.44 10.80 Ni(OH)2 Ni3(PO4)2 -7.29 -38.59 -31.30 Ni3(PO4)2 Ni4(OH)6SO4 -25.15 6.85 32.00 Ni4(OH)6SO4 NiCO3 -9.37 -16.21 -6.84 NiCO3 Nsutite -28.38 14.18 42.56 MnO2 O2(g) -68.73 -71.62 -2.89 O2 Portlandite -14.42 8.38 22.80 Ca(OH)2 Pyrite 11.80 -6.68 -18.48 FeS2 Pyrochroite -8.25 6.95 15.20 Mn(OH)2 Pyrolusite -27.20 14.18 41.38 MnO2 Retgersite -7.45 -9.49 -2.04 NiSO4:6H2O Rhodochrosite -3.57 -14.70 -11.13 MnCO3 Rhodochrosite(d) -4.31 -14.70 -10.39 MnCO3 Siderite -4.44 -15.33 -10.89 FeCO3 Siderite(d)(3) -4.88 -15.33 -10.45 FeCO3 Smithsonite -11.24 -21.24 -10.00 ZnCO3 Sphalerite 1.91 -9.71 -11.62 ZnS Strengite -4.15 -30.55 -26.40 FePO4:2H2O Sulfur -0.78 -15.81 -15.03 S Tenorite -14.47 -6.85 7.62 CuO Thenardite -4.09 -4.27 -0.18 Na2SO4 Thermonatrite -11.15 -11.02 0.13 Na2CO3:H2O Trona -16.24 -17.04 -0.80 NaHCO3:Na2CO3:2H2O Vivianite 0.00 -36.00 -36.00 Fe3(PO4)2:8H2O Wurtzite -0.03 -9.71 -9.68 ZnS Zincite(c) -10.73 0.41 11.14 ZnO Zincosite -17.50 -14.49 3.01 ZnSO4 Zn(NO3)2:6H2O -175.46 -172.02 3.44 Zn(NO3)2:6H2O Zn(OH)2-a -12.05 0.40 12.45 Zn(OH)2 68 Zn(OH)2-b -11.35 0.40 11.75 Zn(OH)2 Zn(OH)2-c -11.80 0.40 12.20 Zn(OH)2 Zn(OH)2-e -11.10 0.40 11.50 Zn(OH)2 Zn(OH)2-g -11.31 0.40 11.71 Zn(OH)2 Zn2(OH)2SO4 -21.59 -14.09 7.50 Zn2(OH)2SO4 Zn2(OH)3Cl -21.05 -5.85 15.20 Zn2(OH)3Cl Zn3(PO4)2:4w -21.68 -53.72 -32.04 Zn3(PO4)2:4H2O Zn3O(SO4)2 -47.59 -28.57 19.02 ZnO:2ZnSO4 Zn4(OH)6SO4 -41.69 -13.29 28.40 Zn4(OH)6SO4 Zn5(OH)8Cl2 -49.79 -11.29 38.50 Zn5(OH)8Cl2 ZnCl2 -19.93 -12.90 7.03 ZnCl2 ZnCO3:H2O -10.99 -21.25 -10.26 ZnCO3:H2O ZnMetal -32.58 -6.82 25.76 Zn ZnO(a) -10.90 0.41 11.31 ZnO ZnS(a) -0.66 -9.71 -9.05 ZnS ZnSO4:H2O -13.93 -14.50 -0.57 ZnSO4:H2O ------------------ End of simulation. ------------------ ------------------------------------ Reading input data for simulation 3. ------------------------------------ ----------- End of run. ----------- "@en ; edm:hasType "Graduating Project"@en ; edm:isShownAt "10.14288/1.0053587"@en ; dcterms:language "eng"@en ; ns0:peerReviewStatus "Unreviewed"@en ; edm:provider "Vancouver : University of British Columbia Library"@en ; dcterms:rights "Attribution-NonCommercial-NoDerivatives 4.0 International"@en ; ns0:rightsURI "http://creativecommons.org/licenses/by-nc-nd/4.0/"@en ; ns0:scholarLevel "Undergraduate"@en ; dcterms:isPartOf "University of British Columbia. EOSC 449"@en ; dcterms:title "An Assessment of the Greywater and Composting Toilet Tea Leach Field Geochemistry at the C.K. Choi Building, University of British Columbia Vancouver Campus"@en ; dcterms:type "Text"@en ; ns0:identifierURI "http://hdl.handle.net/2429/20363"@en .