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An Assessment of the Greywater and Composting Toilet Tea Leach Field Geochemistry at the C.K. Choi Building,.. Larson, Leila 2010

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   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. -----------  

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