THE ROLE OF SOIL ORGANIC MATTER IN THE ...

THE ROLE OF SOIL ORGANIC MATTER IN THE DEGRADATION OF ORGANIC CONTAMINANTS IN RETORT WATER

Department of Chemical Engineering The University of Queensland May, 2002 Author: Susie Taaffe Supervisor: Dr Bill Clarke

Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe

DECLARATION I declare that the work presented in this individual inquiry report is, to the best of my knowledge, my own work, except as acknowledged in the report and has not been submitted either in full or in part, for a degree at this or any other university.

Susie Taaffe 17th May, 2002

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Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe

ACKNOWLEDGMENTS The work I have completed this semester towards this Inquiry would not have been possible without the invaluable assistance of various people. Firstly I would especially like to thank my supervisor Dr Bill Clarke for his continual assistance and feedback on my work. Furthermore I would like to express my gratitude for the extensive laboratory assistance provided by Angel Ho and Hyohak Song. Without their help I would have been lost. Finally I wish to thank Adam Copping and Anna Geddes for their unwavering support throughout this experience as well as my family for putting up with me.

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Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe

ABSTRACT Southern Pacific Petroleum N.L. (SPP/CPM) is an Australian company that specialises in the discovery and commercial development of oil shale deposits. In 1997, SPP/CPM commenced development of one of their ten oil shale deposits, the Stuart deposit. The production of oil shale creates immense quantities of solid (oil shale ash and overburden) and liquid waste (retort water). The efficient and cost effective management of the produced wastewater is vital. The proposed treatment method for retort water from the Stuart oil shale development near Gladstone is the use of a trickle biological filter, using overburden and oil shale ash in a 1:1 ratio as the trickle flow media. Recent studies have shown this method to be very effective in the degradation of the organic contaminants in the retort water to produce CO2. However both the oil shale ash and the overburden contain organic carbon. Therefore the question arises as to whether or not the carbon contained in the solids also contributes to the production of CO2. Another question is whether any of the carbon in the retort water is adsorbed by the oil shale ash and/or overburden. The experiments that will be performed in this investigation are designed to answer these questions. Rather than running trickle flow tests, this study will examine batch tests using a minimum amount of overburden and shale ash as a biological seed. The overall objectives of this inquiry were:

1. To detect if more CO2 is being produced than is degraded from the retort water by taking weekly measurements of the CO2 production then comparing this with the decrease in TOC expressed on a CO2 basis.

2. To detect if shale ash and/or overburden are adsorbing retort water carbon by taking weekly measurements of the CO2 production and then comparing this with the decrease in TOC expressed on a CO2 basis and simple mass balances. The major finding from this investigation was: ¾ The overburden degraded the organics in the retort water to a greater extent earlier than the oil shale ash. It is recommended that these experiments be repeated with a longer experiment time frame and improved experimental equipment to ensure the capture and recording of all CO2 production

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Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe

TABLE OF CONTENTS

DECLARATION.......................................................................................................................I ACKNOWLEDGMENTS ...................................................................................................... II ABSTRACT ........................................................................................................................... III TABLE OF CONTENTS.......................................................................................................IV 1.0 INTRODUCTION............................................................................................................ 1 2.0 LITERATURE REVIEW/SURVEY .............................................................................. 4 2.1 RETORT WATER CHARACTERISTICS AND TREATMENT METHODS ................................... 4 2.1.1 Introduction............................................................................................................ 4 2.1.2 Characteristics of Retort Water ............................................................................. 5 2.1.3 Characterisation of Oil Shale Ash and Overburden .............................................. 6 2.1.4 Review of Retort Water Treatment Methods .......................................................... 7 2.1.5 Biodegradation....................................................................................................... 7 2.1.6 Adsorption .............................................................................................................. 9 3.0 PLAN OF STUDY.......................................................................................................... 11 3.1 ORIGINAL PLAN ............................................................................................................. 11 3.2 REVISED PLAN .............................................................................................................. 11 4.0 EQUIPMENT AND METHODOLOGY ..................................................................... 12 4.1 PROCEDURE................................................................................................................... 12 4.1.1 Sterilisation .......................................................................................................... 12 4.1.2 Experimental Set-Up and Equipment................................................................... 12 4.2 SAMPLE ANALYSIS AND EQUIPMENT ............................................................................. 13 4.2.1 Carbon Dioxide Equipment and Sample Analysis ............................................... 13 4.2.2 Total Organic Carbon Equipment and Sample Analysis ..................................... 14 4.3 ERROR ANALYSIS .......................................................................................................... 16 4.3.3 CO2 Measurements............................................................................................... 16 4.3.4 TOC Measurements.............................................................................................. 16 5.0 RESULTS........................................................................................................................ 17 6.0 DISCUSSION ................................................................................................................. 21 6.1 OVERBURDEN VERSUS SHALE ASH................................................................................ 21 6.2 ACTUAL RESULTS VS. CALCULATED RESULTS .............................................................. 22 7.0 SUGGESTIONS FOR FURTHER WORK ................................................................. 23 8.0 REFERENCES ............................................................................................................... 24 APPENDIX A ......................................................................................................................... 25

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Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe

APPENDIX B.......................................................................................................................... 33 APPENDIX C ......................................................................................................................... 42

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Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe

LIST OF TABLES Table 2.1 Compositions of the Extractable Fraction of Stuart Oil Shale Retort Water (Bell and Coombs, 2001) ................................................................................................................... 5 Table 4.1 Summary of Experimental Conditions.................................................................... 13 Table 5.1 Overall TOC Degradation of the Retort Water ........................................................ 20

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Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe

LIST OF FIGURES Figure 2.1 Shale Ash and Overburden ....................................................................................... 6 Figure 4.1 Experimental Bottles............................................................................................... 12 Figure 4.2 Gas Chromatograph (GC)....................................................................................... 14 Figure 4.3 Dohrmann DC-190 TOC Analyser ......................................................................... 15 Figure 5.1 Degraded TOC Expressed as CO2 of Overburden Experiments............................. 17 Figure 5.2 Degraded TOC Expressed as CO2 of Shale Ash Experiments ............................... 17 Figure 5.3 Degraded TOC Expressed as CO2 of Control Experiments ................................... 18 Figure 5.4 Measured CO2 Concentration for Control Experiments ......................................... 18 Figure 5.5 Measured CO2 Concentration for Overburden Experiments .................................. 19 Figure 5.6 Measured CO2 Concentration for Shale Ash Experiments..................................... 19

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Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe

1.0 Introduction Retort water is a major waste from the production of oil from oil shale. The proposed treatment method for retort water from the Stuart oil shale development near Gladstone is the use of a trickle biological filter, using overburden and oil shale ash in a 1:1 ratio as the trickle flow media. Recent studies have shown this method to be very effective in the degradation of organic contaminants in the retort water. Mass balances by Clarke (2002) have shown that the rate carbon, in the form of retort water contaminants, is supplied to the filter equals the rate that carbon leaves the biological reactor in the form of CO2. The mass balances are also supported by Clarke’s observations using the respirometry method, that the carbon levels in treated water exiting from the filter are less than 1% of the input carbon levels. These calculations and observations seem to lead to the simple conclusion that the biological components of the solids alone enable treatment of the retort water. However both the oil shale ash and the overburden contain organic carbon. Therefore the question arises as to whether or not the carbon contained in the solids also contributes to the production of CO2. This question leads to the consideration of whether any of the carbon in the retort water is adsorbed by the oil shale ash and/or overburden. Therefore in analysing the results of recent studies there are three questions to consider: 1. Are the biological components of the trickle filter alone responsible for the degradation of organic contaminants in retort water to CO2? 2. Is some of the oil shale ash and/or overburden carbon content being degraded to CO2? 3. Is the oil shale ash and/or overburden adsorbing (and perhaps desorbing) part of the carbon content in the retort water? Studies recently performed on the proposed trickle filter used large quantities of shale ash and overburden as the trickle flow media and thus a large quantity of solid organic carbon was present in the column. The amount of CO2 released was small compared with the amount of carbon in the column. The quantity of CO2 released (925g) in these studies was very similar to the amount of organic carbon associated with the pre-treated retort water (874g) (Clarke

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Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe

2002). However both these carbon values are very small in comparison with the amount of solid organic carbon present in the column, 4.35±0.2kg (Clarke, 2002). In order to begin to answer the above questions an investigation of the organic carbon content of the column is required. However it is difficult to analyse the organic carbon content of the column due to the nature of the overburden and the shale ash. It is very hard to obtain a homogeneous sample and thus the analysis of the TOC (Total Organic Carbon) content of the column has a standard deviation of ±0.2kg (Clarke, 2002) which is nearly one quarter of the amount of carbon released by the filter in the form of CO2. This poses a problem. A small amount of column TOC can make a significant contribution to CO2 production, which might not be detected by post solid TOC analysis due to the large uncertainty of the solid analysis. A similar problem is encountered when investigating the adsorption (or desorption) of retort water carbon by the column solids. Again the difference in the TOC content of the column before and after use might not be detected by post solid TOC analysis due to the large uncertainty of the solid analysis. Even if the solid TOC analysis is highly accurate and the amounts of carbon adsorbed are determined, the respirometry method, which measures the CO2 levels, cannot distinguish between adsorbed and native organic carbon. That is, the method may be accurate enough to say the TOC content is conserved, but it cannot be determined whether the CO2 produced comes from the soil (solids) organic matter or from the retort water. The experiments that will be performed in this investigation are designed to answer the three questions. Rather than running trickle flow tests, this study will examine batch tests using a minimum amount of overburden and shale ash as a biological seed.

By significantly

decreasing the amount of solid TOC present it should be much easier to distinguish CO2 production from the retort water and CO2 production from the solids. The overall objectives are: 1. To detect if more CO2 is being produced than is degraded from the retort water. HOW - by taking weekly measurements of both the CO2 produced and the TOC of the retort water then comparing with theoretical CO2 calculations and mass balances. 2. To detect if shale ash and/or overburden are adsorbing retort water carbon.

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Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe

HOW – by taking weekly measurements of both the CO2 produced and the TOC of the retort water then comparing with theoretical CO2 calculations and mass balances. Testing solid TOC content before and after experiments could also detect if adsorption was occurring however, sample variations are still cause for large uncertainty is this area. These objectives will be achieved by conducting a series of batch digestions, each with a different concentration of retort water. Key indicators will be: ¾ whether CO2 production is proportional to retort water concentration. ¾ whether CO2 production exceeds the equivalent carbon content of the retort water.

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Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe

2.0 Literature Review/Survey 2.1

Retort Water Characteristics and Treatment Methods 2.1.1 Introduction

Australia’s demand for oil fuel is increasing because of a growing demand for transportation fuels. It has been estimated that by 2010, Australia will rely on 55% of foreign oil imports as opposed to the 20% reliance in 1998 (Environmental Impact Assessment Study – Stage 2 Stuart Oil Shale Project). Queensland is very rich in oil shale deposits that have the capacity, if developed to their full potential, to meet all of Australia’s oil requirements and possibly even create an export market. Southern Pacific Petroleum NL (SPP/CPM), is an Australian company that specialise in the discovery and commercial development of oil shale deposits. In 1997, SPP/CPM commenced development of one of their ten oil shale deposits, the Stuart deposit. Located near Gladstone on the central Queensland coast, the Stuart deposit has a total shale oil resource of approximately 2.6 billion barrels (www.sppcpm.com). Oil produced from the Stuart deposit surpasses the world's strict environmental standards with a sulphur content much less than other crude oils. This deposit therefore will contribute greatly to the future supply of clean energy to Australia. The production of oil shale however, also creates immense quantities of liquid and solid wastes. The efficient and cost effective management of the produced wastewater is vital as the production of oil from oil shale produces 0.4m3 to 0.5m3 of wastewater per 1.0m3 of oil product (Clarke 2002). The wastewater is comprised of a combination of retort water and sour water. Retort water is produced when the shale is heated to 500-600°C in the retorting section of the process (Rhee et al., 1996). Sour water is produced in the scrubbing operations of the process where steam is indirectly used to strip S and N from the crude shale oil (Clarke 2002). For treatment of the two streams the sour water and the retort water are to be mixed and treated as one. As the mixture contains more retort water it will be referred to as retort water.

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Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe

2.1.2 Characteristics of Retort Water The exact characteristics of retort water are extremely hard to obtain as it is of a very complex nature consisting of a range of carboxylic acids, nitrogen heterocyclic compounds, phenols and ketones (Clarke 2002). The constituents of the crude oil shale and the retorting process itself will have a large impact on volumes, compositions and chemical concentrations of the retort water’s chemical constituents (Healy et al., 1985). One of the major problems is the specification of organic constituents in the retort water. Many studies have been performed trying to analyse the organic component of retort water. Dobson et al., 1985 first characterised the retort water composition produced from Stuart oil shale. He found that NH4+ characterises much of the retort water’s inorganic composition as well as sodium, calcium, magnesium, iron, potassium and inorganic carbon. To identify the organics, using the USEPA method and dichloromethane as an extraction solvent, Dobson et al., (1985) were able to extract approximately 30% of the TOC in the retort water for identification using GC-MS. Of this, over 80% were aliphatic mono-(C2-C10) carboxylic acids; the rest consisted of phenols, creosols, cycloketones and nitrogen heterocycles. Bell and Coombs (2001) also conducted this study and were able to extract approximately 40% of the TOC for molecular identification, from the Stuart retort water. The results from the analysis of the extractable TOC can be found in Table 2-1. The unidentified TOC does not contain any of the compounds listed below (Clarke 2002). Compound

Percentage contained in Extractable TOC

Acetic Acid Propanoic Acid Butyric Acid Valeric Hexanoic Acid Heptanoic Acid Octanoic Acid Nonanoic Acid Decanoic Acid m+p Cresol Phenol Pyridine Aniline 1-methyl pyrrolidine Quinoline Other methyl/ethyl/alkyl Pyridines Methyl-2-cyclopentene-1-one 3-Methyl-2-cyclopentene-2-ol Other Cyclic Ketones

12 11 12 19 19 20 1.4 0.8 0.1 0.6 2.5 0.1 0.1 0.1 0.1 0.3 0.2 0.3 0.4

Table 2.1 Compositions of the Extractable Fraction of Stuart Oil Shale Retort Water (Bell and Coombs, 2001)

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Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe

2.1.3 Characterisation of Oil Shale Ash and Overburden

The overburden is the mining waste that covers the oil shale in the ground and has been provided from the Stuart deposit near Gladstone. Overburden consists of a clay slate material and for these experiments has an organic carbon content of 8.7% (SD = 0.3%), (Clarke 2002). The physical and chemical properties of both the overburden and the oil shale ash are specific to the regions they are found in. The retorting process also has an effect on their properties. For these experiments the size of the overburden particles was not taken into consideration however it was crushed at the mine roughly to the size of gravel particles. It is medium to pale brown in colour and is shown below in Figure 2.1.

The oil shale ash was also provided from the Stuart deposit and is a solid waste that remains after the retorting and combustion operations in the process. Before processing, oil shale consists primarily of clays and primary silicate minerals (Clarke 1993). However in the retort section of the process, some of the clay is converted to primary silicates and a quantity of the organic carbon is removed (Clarke 2002). The organic carbon content of the shale ash used in these experiments was 6% (SD = 0.3%), (Clarke 2002). Again the size of the shale ash particles was not taken into consideration however they were also crushed roughly to gravel size. The black colour of the shale ash is demonstrated in Figure 2.1.

Figure 2.1 Shale Ash and Overburden

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Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe

2.1.4 Review of Retort Water Treatment Methods Studies have been performed for many years on various systems for the treatment of retort water. As the retort water is of a very complex nature and has a variety of organic degradabilities, it is hard to choose one treatment method. In fact, in reality a combination of treatment methods would be used to treat the retort water to a level that can be discharged to the environment. Some of the different treatment options are as follows: ¾ Physical Treatment ¾ Chemical Treatment ¾ Biological Treatment -

stripping air flotation filtration adsorption evaporation distillation Coagulation chemical oxidation wet air oxidation ion exchange activated sludge sequencing batch reactor rotating biological contractors anaerobic fermentation

This study will focus on the microbial degradation of organics in the retort water by the oil shale ash and the overburden. 2.1.5 Biodegradation Many studies have been performed on the use of microbial degradation as a treatment method for the reduction and elimination of

various contaminants in retort water that are of

environmental concern. Biological waste treatment is normally one of the most economical means of removing organic contaminants from wastewaters (Healy et al., 1985). Aerobic biodegradability of oil shale retort waters is dependent on the characteristics of the retort water. The retort water must contain sufficient ammoniac nitrogen to support growth and although phosphate level’s were not determined in the study by Healy et al., (1985), it has been mentioned that phosphate is often found to be a growth-limiting nutrient. There must also be enough oxygen supply to enable growth. This is because oxygen availability significantly influences microbial growth as it determines the type of active microorganisms,

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Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe

their roles and thus the compounds that are degraded (Hagenbach, 2000). The reactions in an aerobic biological process are as follows (Hagenbach, 2000): Organics + O2 + N + P Cells + O2

cells

New Cells + CO2 + H2O + SMP

CO2 + H2O + N + P + Non degradable Cellular Residue + SMP

Where SMP = Non-biodegradable Soluble Microbial Products In this experiment we have used an equation in order to calculate the theoretical oxygen requirement. This calculation is needed in order to ensure that there is sufficient O2 to keep aerobic conditions in the headspace of the experiment bottles. The equation was used to indicate the volume required for the experiment bottles and is as follows: O2 = Q(SO – S) – 1.42X + 4.57Q(NO – N)

(Equation 1)

Where Q = Liquid volume SO =Initial TOC S = Finial TOC X = Biomass NO = Initial N concentration N = Final N concentration Healy et al., (1985), found that despite the microbially unfavourable chemical environment of retort water there was still rapid biodegradation of some of the solutes from nine differently characterised retort waters. Again in the study by Clarke (2002), there was significant biodegradation of organics in the retort water. After passing the retort water through a trickle biological filter comprising of a 1:1 ratio of oil shale ash and overburden, Clarke (2002) found the TOC in the retort water effluent to be less than 1% of the input carbon. The accuracy of his experiment however, was not high enough to confidently say that all the organic species were degraded. Other sinks of organic carbon such as adsorption or precipitation could not be discounted and could have accounted for up to 10% removal, given the experimental accuracy. It has only been possible extract 40% of the retort water organics on a TOC basis into dichloromethane for molecular identification. Therefore, despite the uncertainties in the experiments by Clarke (2002), it can be suggested that the majority of the unidentified section of the retort water must be biodegradable.

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Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe

Although aerobic biological retort water treatment effectively degrades some of the organics, it should be used with other treatment steps in order to remove aromatic nitrogenous compounds and other biorefractory solutes. One possibility that is being investigated is the use of adsorption and biodegradation together as the main mechanisms for overall organic removal. This would work well if the inhibitants to biodegradation were adsorbed thus leaving the compounds that were compatible with biodegradation unadsorbed and free for biodegradation. Syamsiah (1993) has hypothesised that the retort water organics would adsorb, desorb and then biodegrade, thereby providing a fresh vacant adsorption site of shale ash for further adsorption. This will be discussed in the next section.

2.1.6 Adsorption Previous studies have shown that shale ash and overburden are potential adsorbents for the removal of organic compounds from retort water (Syamsiah et al., 1992). It is known that the shale ash and the overburden promote biodegradation in the biological trickle filter. However, the part played by adsorption is still to be investigated. Studies by Syamsiah et al., (1992) found that shale ash has an adsorptive capacity 50% higher than that of the overburden. They suggested this was due to a higher organic carbon content of their shale ash, which has an organic carbon content 100 times higher than their overburden. This may not be applicable to the experiments performed in this study as the organic carbon content of the shale ash and the overburden is relatively similar. Syamsiah et al., (1992) also detected that the rate of retort water adsorption by the overburden, mixed solids and shale ash was rapid during the first 5 hours of the experiments during which 40-90% of the total adsorption occurred. However the initial adsorption of the mixed solids and the overburden was unstable for a while (10-24 hours). The desorption experiments performed in the study by Syamsiah et al., (1992), found that about 70-80% of the adsorbed TOC is irreversibly retained on the solid. The desorption rate is also, rapid during the first 2 hours and then diminishes to negligible levels. Therefore it has been suggested (Syamsiah et al., 1992) that this irreversibly retained TOC allows the strongly adsorbed but less biodegradable organic compounds to remain adsorbed on the solid phase, therefore providing a longer residence time for biodegradation. However further studies into

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Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe

the adsorption and desorption equilibrium of retort water TOC by oil shale ash and overburden are needed in order to apply this to a steady state biological treatment system.

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Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe

3.0 Plan of Study 3.1

Original plan

The original plan for the experiments was to conduct CO2 and TOC measurements from the BMP bottles weekly until a declining trend in the levels of carbon being degraded/emitted was observed. More retort water would then have been added to each of the bottles in order to determine the new levels of carbon being degraded/emitted. However repeated cycles could not be performed in the timeframe. The experiments were to be performed on retort water currently being generated by Southern Pacific. However due to plant shut down, a decision was made to use old sour water that was delivered to The University of Queensland in October 2000. Experiments were run on this retort water for a total of 5 weeks. Solid testing of the overburden and shale ash TOC was scheduled to be conducted at the end of the five week period in order to compare with the initial TOC levels. However due to time constraints these results were not obtained.

3.2

Revised Plan

The revised plan for the experiments was to conduct CO2 and TOC measurements from the BMP bottles weekly for a five week period. From the weekly retort water TOC analysis, the theoretical CO2 production was to be calculated and compared with the actual data.

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Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe

4.0 Equipment and Methodology 4.1

Procedure 4.1.1 Sterilisation

¾ The bottles were left to soak in 2% Decon 90 solution overnight ¾ They were then rinsed thoroughly with water and MQ water respectively, wrapped in foil and left to dry in an oven set at 46ºC for 5 hours. ¾ The bottles and the MQ water were then autoclaved for 30 minutes at 121ºC and 150kPa. The volume of the MQ water in the bottle should not exceed 75% when autoclaving in order to prevent the possibility of boil-over. The gas space in the bottle should also be vented during autoclaving to enable the equilibration of pressure. ¾ The retort water was sterilised by filtering the water with a 0.2µm membrane filter. 4.1.2 Experimental Set-Up and Equipment The experiments were conducted in laboratories at The University of Queensland. The study was carried out under the conditions described below, with ten experimental bottles of which two were control systems. The bottles characterised as follows: ¾ Type: BMP flask with addition of glass arm for gas measurements. ¾ Volume: 500mL, this volume was chosen to ensure there is enough headspace to keep the system aerobic ¾ Other: Glass arm sealed by a butyl rubber stopper with an area for inserting syringe for CO2 measurements

Figure 4.1 Experimental Bottles The bottles in Figure 4.1 were kept in a room maintained at 24ºC ±1ºC in a Reciprocating Shaking Water Bath (model no: RW 1812) agitated at a slow setting. Too much agitation inhibits biodegradation. The operating conditions were identical for all. The control systems 12

Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe

were implemented without solids in order to investigate TOC reduction of the retort water caused by volatilisation and/or adsorption to the flask. A summary of the contents of each bottle is provided below in Table 4.1. Sample Name

Overburden (grams)

Retort Water (mL)

Ctrl/RW Ctrl/MQ

0 0

100 100 (MQ water)

OB1/RW OB2/RW OB3/RW OB4/RW

5 5 5 5

20 40 60 100

SS1/RW SS2/RW SS3/RW SS4/RW

5 5 5 5

20 40 60 100

Table 4.1 Summary of Experimental Conditions

4.2

Sample Analysis and Equipment 4.2.1 Carbon Dioxide Equipment and Sample Analysis

Gas samples were collected from the bottles every 6-7 days. This time frame was chosen in order to allow time for the biological activity to produce CO2. Samples of the gas produced in the headspace of the bottles were collected in10mL plastic syringes connected to 20-gauge needles. The sample syringes were initially flushed with air before each sample was taken. Each sample was examined for CO2 levels using a Perkin Elmer Gas Chromatographer (GC). The GC was calibrated using inert nitrogen gas and a CO2/CH4 mixture of 51.3 % +/- 0.2% CO2 with 0.806% +/- 0.016% Hydrogen, at levels of 1%, 3%, 5% and 10%. These results can be found in APPENDIX A. The GC was operated as per the operating manual with a residence time for each sample of 2.5 minutes. The gas in each bottle was analysed in triplicate in order to diminish any errors, as the GC can sometimes be sensitive. A 6-8mL sample of gas was collected from each bottle and injected into the GC. The injectoin port and the GC are shown in Figure 4.2. The results for each analysis can be found in APPENDIX B. The GC that was used is designed to use a thermal conductivity detector (TCD) to analyse the gas samples.

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Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe

Therefore it is not as sensitive as a GC that uses a flame ionisation detector (FID). In order to increase the accuracy of the calibrations at low percentages of CO2 a GC that is designed for use with aerobic systems could be used.

Figure 4.2 Gas Chromatograph (GC) Although only interested in the amount of CO2, oxygen levels were also recorded in order to ensure there was enough oxygen in the headspace of the bottles to keep aerobic conditions. No effort was made to record any other components in the gas as this investigation is only looking at the carbon mass balance.

4.2.2 Total Organic Carbon Equipment and Sample Analysis The TOC of the retort water was analysed using a Rosemount Analytical Dohrmann DC-190 TOC analyser at The University of Queensland. Approximately 2mL samples were collected from each bottle in weekly intervals and filtered using a 0.22µm Millipore filter. The samples were stored in a freezer until testing was performed. Storing the samples at a low temperature prevented any further biological activity. All samples had to be diluted to 10% for analysis. This was for two reasons; Ctrl/RW, SS3/RW, SS4/RW, OB3/RW and OB4/RW had a TOC content too high for the TOC analyser and, the TOC analyser required more than a 2mL sample for testing as autosamples were taken. Figure 4.3 shows the Analytical Dohrmann DC-190 TOC analyser.

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Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe

Figure 4.3 Dohrmann DC-190 TOC Analyser Inorganic Carbon (IC) levels in the initial retort water were tested and found to be very low (around 4ppm) and so have been considered negligible. Therefore no IC testing was performed on the samples. After obtaining the TOC data for the samples, the theoretical volume of CO2 released in the headspace could be calculated using the following equation: Vco2 = (C/M) * VrRT

(Equation 2) P

Where Vco2

=

Volume of CO2 [mL]

C

=

Degraded Retort water TOC [mg/L]

Vr

=

Volume of retort water [L]

M

=

Molecular weight of carbon [=12]

R

=

Universal gas constant [8.314 J/mole/K]

T

=

Temperature of headspace gas [298K]

P

=

Pressure of headspace gas [101.3 kPa]

These results can be found in APPENDIX C. The pressure of the headspace gas was assumed to be 101.3 kPa. This is not entirely correct, however from the data collected it has been noted that for more CO2 in the headspace, there is

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Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe

less O2 in the headspace at approximately a 1:1 ratio. Therefore this pressure was assumed to be constant and the measurements of actual CO2 production were based on the assumption of atmospheric pressure in the bottle headspace. The exact volume of the gas produced in each bottle can be determined by using a pressure difference manometer to check the pressure in the headspace of the bottle.

4.3

Error Analysis 4.3.3 CO2 Measurements

Errors associated with the analysis of the gas samples for CO2 were limited by conducting each gas sample analysis in triplicate. Possible errors that may be associated with the CO2 measurements could originate from the calibration of the GC. Each percentage of CO2 was calibrated 3-5 times before every group of testings were performed and the calibration graphs, found in Appendix A, indicate minimal errors. Therefore it can be assumed that the error associated with the measurements of CO2 would be less than ±5%. 4.3.4 TOC Measurements Possible errors associated with the TOC analysis can be mainly attributed to the dilution of the samples before testing. The pipettes that were used to perform the dilutions only have an accuracy of ±5%. The dilutions were necessary however as the TOC analyser required samples that were larger than 2mL. Calibrations of the Dohrmann TOC analyser showed that the error associated with the TOC sample analysis was minimal, consistently producing a standard deviation of less than ±2%.

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Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe

5.0 Results Calculated CO2 production and actual CO2 production results for the experiments are presented in the following figures. Figure 5.1 and Figure 5.2 represent the TOC degradation expressed as CO2 of the overburden and shale ash experiments respectively. O v e r b u r d e n E x p e r im e n ts : C a lc u la te d V o l% o f C O 2 200

Percentage CO2 (by volume)

180 160 140

O O O O

120 100 80

B B B B

1 /R 2 /R 3 /R 4 /R

W W W W

60 40 20 0

1 1 -A p r

1 6 -A p r

2 1 -A p r

2 6 -A p r

1 -M a y

6 -M a y

1 1 -M a y

1 6 -M a y

D a te

Figure 5.1 Degraded TOC Expressed as CO2 of Overburden Experiments

S h a le A s h E x p e r i m e n t s : C a l c u l a t e d V o l % o f C O 2

Percentage CO2 (by volume)

200 180 160 140 S S 1 /R W S S 2 /R W S S 3 /R W S S 4 /R W

120 100 80 60 40 20 0 1 1 -A p r

1 6 -A p r

2 1 -A p r

2 6 -A p r

1 -M a y

6 -M a y

1 1 -M a y

1 6 -M a y

D a te

Figure 5.2 Degraded TOC Expressed as CO2 of Shale Ash Experiments The early peaks of the overburden as opposed to the delayed peaks of the shale ash should be noted and will be examined in depth in the discussion.

17

Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe

C o n tr o l E x p e r im e n ts : C a lc u la te d V o l% o f C O 2

Percentage CO2 (by volume)

50 40 30 C tr l/R W C tr l/M Q

20 10 0 1 1 -A p r

1 6 -A p r

2 1 -A p r

2 6 -A p r

1 -M a y

6 -M a y

1 1 -M a y

1 6 -M a y

-1 0 D a te

Figure 5.3 Degraded TOC Expressed as CO2 of Control Experiments Figure 5.3 represents the TOC degradation expressed as CO2 of the control experiments. The negative value of the Ctrl/RW can be attributed to error in the TOC analysis of the retort water. Figure 5.4 shows the actual CO2 concentration of the control experiments. A possible reason for the data will be discussed in section 6.0.

Percentage CO2 (by volume)

CO2 Concentration of Control Experiments 4%

3%

Ctrl/RW 2%

Ctrl/MQ

1%

0%

11-Apr

16-Apr

21-Apr

26-Apr

1-May

6-May

11-May 16-May

Date Measured

Figure 5.4 Measured CO2 Concentration for Control Experiments

18

Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe

O v e r b u r d e n E x p e r im e n t s C O 2 P r o d u c t io n

Production of CO2 (Vol%)

12 10 8

O B 1 /R W O B 2 /R W O B 3 /R W O B 4 /R W

6 4 2 0 1 1 -A p r

1 6 -A p r

2 1 -A p r

2 6 -A p r

1 -M a y

6 -M a y

1 1 -M a y

1 6 -M a y

D a te M e a s u re d

Figure 5.5 Measured CO2 Concentration for Overburden Experiments Figures 5.5 and 5.6 represent the measured CO2 concentrations in the overburden and shale ash experiments respectively. These graphs will be examined in detail in the discussion section. S h a le A s h E x p e rim e n ts C O 2 P ro d u c tio n 10 Production of CO2 (Vol %)

9 8 7 S S 1 /R W S S 2 /R W S S 3 /R W S S 4 /R W

6 5 4 3 2 1 0 1 1 -A p r

1 6 -A p r

2 1 -A p r

2 6 -A p r

1 -M a y

6 -M a y

1 1 -M a y

D a te M e a s u re d

Figure 5.6 Measured CO2 Concentration for Shale Ash Experiments

19

1 6 -M a y

Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe

Table 5.1 is a summary of the overall decrease in the TOC of the retort water, for each different condition, over the time of the experiments. Sample Name Ctrl/RW Ctrl/MQ OB1/RW OB2/RW OB3/RW OB4/RW SS1/RW SS2/RW SS3/RW SS4/RW

23.97 % 132.9 % 87.55 % 83.66 % 73.15 % 66.86 % 87.31 % 88.23 % 80.53 % 68.02 %

Table 5.1 Overall TOC Degradation of the Retort Water

20

Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe

6.0 Discussion 6.1

Overburden versus Shale Ash

From Figures 5.1 and 5.2 the different trends exhibited by the overburden and shale ash degradation of the retort water TOC are clearly visible. Initially the overburden significantly degrades the TOC of the retort water and then decreases its rate of biodegradation. Whereas the shale ash appears to have a hold-up before it to commences to considerably degrade the TOC. The shale ash also degrades the TOC for a longer period. Initially OB3/RW and OB4/RW noticeably degrade more of the retort water TOC than SS3/RW and SS4/RW. However Table 5.1 indicates that SS3/RW and SS4/RW actually degrade more of the retort water TOC. This could be due to the longer period the shale ash is degrading the retort water TOC. However, due to errors in the TOC analysis of ±7% no conclusion can be made. At the lower concentrations of retort water (OB1/RW, OB2/RW, SS1/RW and SS2/RW) both the overburden and the shale ash degrade the TOC of the retort water at similar levels. There are a few possibilities as to the reason for the differences listed above. 1. One possibility for the hold-up of degradation by the shale ash, could be the difference in adsorptive capacities between the shale ash and the overburden. Findings from Syamsiah et al (1992) show that shale ash has an adsorptive capacity 50% higher than that of overburden. 2. It was also suggested that adsorption may perhaps increase the residence time of the organics and consequently produce slower microbial degradation. If this is true it could be a reason for the delayed, but marginally longer, period of biodegradation of the retort water TOC by the shale ash. It must be noted however, that the mechanisms and role of adsorption in biodegradation are very complex and therefore no conclusions have been made from these hypothetical scenarios.

21

Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe

6.2

Actual Results vs. Calculated Results

It is difficult to draw any conclusions from the experiments by comparing the actual results with the calculated results. The actual CO2 production that was measured was several orders of magnitude lower than the calculated results. The actual CO2 production was in fact low enough to assume that the experimental BMP bottles were not airtight. For example, when studying Table 5-1 and Figures 5-5 and 5-6, the following observations were made: ¾ OB1/RW initially increased to produce 2% CO2 by the 24-April and then declined again to under 1%. Around 85% of the organic carbon degraded according to assays on the leachate. ¾ SS2/RW did not produce any CO2 during the 5 week experiment yet when in contact with the shale ash around 83% of the TOC in the retort water degraded. ¾ OB2/RW also produced negligible CO2, while according to the TOC assays around 82% of the organic carbon in the retort water was removed when in contact with the overburden. The ‘o-ring’ sealing the bottles, was made of hard plastic and evidently did not seal the bottles very well causing the gas to escape. Variations in the different concentrations of CO2 in the bottles suggest a different sealing capability of each particular ‘o-ring’. Other explanations for the results could be: ¾ Adsorption of the retort water TOC by the oil shale ash or overburden. This however can not wholly account for such significantly low levels of CO2 as there were only 5 grams of oil shale ash or overburden in each bottle. This is supported through findings by Clarke (2002), that the TOC adsorption capacity of the Stuart shale ash and overburden is only 1.0 mg/g and 1.5 mg/g respectively. ¾ Volatilisation of the retort water TOC by the bottle. From the control experiments it can be seen that this is not significant enough to cause such a decrease in CO2 levels. Even if both adsorption and volatilisation occurred, these processes would only account for a small amount of the ‘missing’ carbon from the above examples. Therefore it can be hypothesised that an unknown portion of the CO2 escaped from the bottles.

22

Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe

7.0 Suggestions for Further Work The major problem that occurred during these experiments was the leakage of CO2. There are a couple of ways this could be avoided in the future. One way would be to invert the bottles, using the liquid in the bottles as a seal. This would be very effective in retaining all of the CO2 however, a different sized shaker bath would be required. Another idea would be to use a more effective type of seal. There still may be the possibility of leakage with this option. In order for these experiments to be conclusive they would need to be conducted for a much longer period of time. This would enable a trend to begin with the TOC content of the retort water decreasing over time with respective CO2 emissions being measured also decreasing. If more retort water is then repeatedly added and both the CO2 levels increase again (and then decrease at approximately the same rate), it could be inferred that there is no input from the solid organic carbon in the CO2 emissions. Another task that should be performed, if this experiment was to be repeated, would be to take a liquid sample, to test for TOC from the bottles approximately five hours after the initial addition of the retort/MQ water. According to Syamsiah et al (1992) the rate of retort water adsorption by shale ash and overburden is rapid during these first five hours during which 4090% of the total adsorption occurs. Performing a TOC analysis of the retort water/MQ water solution before and after these first five hours would have given better insight into the amount of TOC adsorption by the solid materials. The GC that was used is designed for use in anaerobic testing using TCD, so it is not generally used to detect low levels of CO2. Therefore to increase the accuracy of the calibration and thus the gas sample results at low percentages of CO2, a GC that is designed for use with aerobic systems could be used. A GC that generally analyses the gas samples of aerobic systems uses a methaniser and a flame ionisation detector (FID) instead of a TCD.

23

Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe

8.0 References Bell, P.R.F. & Coombs, S. 2001, Contract Agreement A/99/52, Uniquest, The University of Queensland. Clarke, W.P. 2002, “Respirometry Study of a Shale Ash and Overburden Trickle Filter for Treating Sour Water, Final Report”, Department of Chemical Engineering, The University of Queensland Clarke, W.P. 1993, “Modelling Leachate Composition from Oil Shale Wastes”, PhD Thesis, The University of Queensland. Day, D.R., Desai, B.O., Liberick Jr., W.W 1983, “ The Treatability of Wastewaters Produced During Oil Shale Retorting”, in Proceedings of the 16th Colorado School, Oil Shale Symposium Proceedings, 512-533. Dobson, K.R., Stephenson, M., Greenfield, P.F. Bell, P.R. 1985, “Identification and Treatability of Organics in Oil Shale Retort Water”, Water Res, 19, 849-856. Hagenbach, A. 2000, “Initial Set-up of a Pilot Scale Column fro the Treatment of Retort Water on Stuart Oil Shale Ash and Overburden”, Undergraduate Thesis, The University of Queensland. Healy Jr., J. B., Langlois, G. W., Daughton, C.G. 1985, “Biooxidation of organic solutes in oil shale wastewaters.” Water Res 19, 1429-1435. Levy, J.H., Reactions in Clay Minerals in the Processing of Australian Oil Shales, in Proceedings of the Fifth Australian Workshop on Oil Shale, Lucas Heights, Sydney, Australia, pp 183-188, 1989 Rhee, S.K., Lee, K.Y., Chung, J.C., Lee, S.T. 1997, “Degradation of Pyridine by Nocardioides sp. strain OS4 isolated from the oxic zone of a spent shale column”, Canadian Journal of Microbiology, 43, 205-209. Rogers, J. E., Riley R.G., Li, S.W., Mann D.C., Wildung, R.E. 1981, “Microbiological Degradation of Organic Components in Oil Shale Retort Water: Organic Acids.” Appl. Envir. Microbiol, 42, 830-837. Sinclair Knight Merz Pty Ltd, Draft Environmental Impact Statement - Stuart Oil Shale Project, Southern Pacific Petroleum (Development) Pty Ltd, 1999. Southern Pacific Petroleum NL and Central Pacific Minerals NL , 1999 [Online], Available: http://www.sppcpm.com [2002, April 10] Syamsiah, S., Krol, A., Sly, L., Bell P.1993, “Adsorption and microbial degradation of organic compounds in oil shale retort water”, Fuel, 72, 855-8611

24

Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe

APPENDIX A CALIBRATION DATA

25

Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe

Date: 18 April Calibration of 1% CO2 2mL 51.3% CO2 gas and Trial no.

98mL N2 gas

Residence time Peak Area 1 2 3 4 5

Average

Peak Height 60599 55624 71311 53819 55667

1.225 1.183 1.434 1.114 1.156

59404

1.222

Date: 24 April Calibration of 1% CO2 1mL 51.3% CO2 gas and 49mL N2 gas Trial no.

Residence time 1 2 3

1.840 1.843 1.843

Peak Area 62265 317051 64671

1.310 1.489 1.330 1.376

Average

Calibration of 3% CO2 3mL 51.3% CO2 gas and 47mL N2 gas Trial no. Residence time 1 2 3 4 Average

Peak Height

1.820 1.807 1.813 1.803

Peak Area

Peak Height

310154 270860 276727 284128

5.659 5.088 5.316 5.354 5.354

Date: 24-Apr Calibration of 5% CO2 5mL 51.3% CO2 gas and 45mL N2 gas Trial no.

Residence time 1 2 3

1.793 1.790 1.797

Average

1

Peak Area 548338 575073 499107

Peak Height 9.584 9.678 8.856 9.373

Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe Date: 2 May Calibration of 1% CO2 1mL 51.3% CO2 gas and 49mL N2 gas Trial no.

Residence time 1 2 3

Peak Area

1.813 1.827 1.827

Peak Height 68220 80158 69967

Average

1.401 1.538 1.500 1.480

Calibration of 3% CO2 3mL 51.3% CO2 gas and 47mL N2 gas Trial no.

Residence time 1 2 3

Peak Area

1.793 1.800 1.800

263520 272362 298497

Average

Peak Height 5.132 5.127 5.594 5.284

Calibration of 5% CO2 5mL 51.3% CO2 gas and 45mL N2 gas Trial no.

Residence time 1 2 3

Peak Area

1.777 1.777 1.780

530421 521886 799580

Average

Peak Height 9.226 9.171 9.990 9.462

Calibration of 10% CO2 10mL 51.3% CO2 gas and 40mL N2 gas Trial no.

Residence time 1 2 3

Peak Area

1.737 1.733 1.730

Average

2

1080572 1084695 1126343

Peak Height 16.732 16.967 17.457 17.052

Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe Date: 9 May Calibration of 1% CO2 1mL 51.3% CO2 gas and 49mL N2 gas Trial no.

Residence time 1 2 3

Peak Area

1.807 1.817 1.807

Peak Height 66909 69555 73212

1.352 1.424 1.519 1.432

Average Calibration of 3% CO2 3mL 51.3% CO2 gas and 47mL N2 gas Trial no.

Residence time 1 2 3 4 5

Peak Area

1.787 1.780 1.783 1.787 1.787

292389 319782 343755 290238 312585

Peak Height 5.511 5.991 5.970 5.460 5.840 5.754

Average Calibration of 5% CO2 5mL 51.3% CO2 gas and 45mL N2 gas Trial no.

Residence time 1 2 3 4

Peak Area

1.770 1.763 1.760 1.770

515796 543341 549517 492368

Peak Height 9.147 9.425 9.736 9.080 9.347

Average Calibration of 10% CO2 10mL 51.3% CO2 gas and 40mL N2 gas Trial no.

Residence time 1 2 3 4 5

Peak Area

1.720 1.723 1.720 1.713 1.720

1386945 1455893 1391087 1157471 1163591

Peak Height 17.771 18.408 17.766 18.222 17.781 17.990

Average

3

Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe Date: 15 May Calibration of 1% CO2 1mL 51.3% CO2 gas and 49mL N2 gas Trial no. Residence time Peak Area Peak Height 1 2 3

1.813 1.787 1.843

68220 77843 317051

1.401 1.515 1.489 1.468

Average Calibration of 3% CO2 3mL 51.3% CO2 gas and 47mL N2 gas Trial no. Residence time Peak Area 1 2 3

1.770 1.793 1.767

285874 263520 304795

Peak Height 5.294 5.318 5.547 5.386

Average Calibration of 5% CO2 5mL 51.3% CO2 gas and 45mL N2 gas Trial no. Residence time Peak Area 1 2 3

1.743 1.777 1.750

544350 530153 565289

Peak Height 9.557 9.338 9.811 9.569

Average Calibration of 10% CO2 10mL 51.3% CO2 gas and 40mL N2 gas Trial no. Residence time Peak Area 1 2 3 4 5

1.687 1.693 1.700 1.697 1.693

1643556 1331666 1180502 1545692 1549453

Peak Height 20.618 19.951 18.147 19.637 19.546 19.580

Average Calibration Graphs - Data Percentage 0.00% 1.03% 3.08% 5.13% 10.26% -

24-Apr

2-May

9-May

0.000 1.376 5.354 9.373

0.000 1.480 5.284 9.462 17.052

0.000 1.432 5.754 9.347 17.990

4

Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe

Calibration for CO2 Analysis 10 y = 185.48x - 0.2561

Peak Height of Data

8

24-Apr

6

Linear (24-Apr) 4

2

0 0%

1%

2%

3%

-2 Percentage of CO2

1

4%

5%

6%

Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe Calibration for CO2 Analysis 20 18

y = 168.71x + 0.0779

Peak Height of Data

16 14 12 2-May

10

Linear (2-May)

8 6 4 2 0 0%

2%

4%

6% Percentage of CO2

2

8%

10%

12%

Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe Calibration for CO2 Analysis 20 y = 177.15x - 0.002

18 16

Peak Height of Data

14 12 10

9-May Linear (9-May)

8 6 4 2 0 0% -2

2%

4%

6% Percentage of CO2

3

8%

10%

12%

Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe

Calibration 15-May 25

Peak Height of Data

20

y = 193.16x - 0.3302

15 15-May Linear (15-May) 10

5

0 0%

2%

4%

6% Percentage of CO2

4

8%

10%

12%

Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe

APPENDIX B MEASURED CO2 DATA

33

Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe Date: 18/4/02 Run Sample Name CO2 Residence Time Peak Area Peak Height O2 Residence Time Peak Area Peak Height 26 Ctrl/RW 0.603 597680 27.445 25 Ctrl/MQ 0.597 460009 26.166 19 17 22 24

OB1/RW OB2/RW OB3/RW OB4/RW

1.857 1.86 1.743 1.807

40141 299627 1298515 341414

0.858 0.613 19.226 6.319

0.603 0.607 0.597

523566 429929 258666

26.599 25.392 17.287

18 16/ 21 20 23

SS1/RW SS2/RW

1.8 -

493375 -

8.842 -

0.603 0.6

189219 477285

12.357 26.38

SS3/RW SS4/RW

1.767 1.83

1021669 150613

15.809 2.957

0.607 0.603

148690 289685

10.145 19.718

0.603

464295

26.044

Air Calibration Equation y = 185.48x - 0.2561 CO2 Concentration Ctrl/RW Ctrl/MQ OB1/RW OB2/RW OB3/RW OB4/RW SS1/RW SS2/RW SS3/RW SS4/RW

0% 0% 0.601 % 0.469 % 10.504 % 3.545 % 4.905 0.000 8.661 1.732

1

% % % %

Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe Date: 24-April Run

Sample Name

Residence Time

Peak Area

Peak Height

-

-

-

0.593

26648

2.491

-

-

-

0.603

536684

27.072

-

-

-

0.603

528156

26.848

Average

0

0

0

Ctrl/MQ

-

-

-

-

-

-

0.603

525861

26.755

-

-

-

0.597

522517

26.848

Average

0

0

0

Air (Ambient)

-

-

-

0.597

656975

27.600

Ctrl/RW

CO2

OB1/RW

-

Peak Area

-

Peak Height

-

1.833

179476

3.312

0.603

443671

23.443

141082

2.684

0.603

536684

27.072

1.833

164126

2.954

0.603

421036

23.206

2.983 -

-

-

0.603

528949

26.856

-

-

-

0.603

557656

27.093

-

-

-

0.597

443720

25.598

Average

0

OB3/RW

1.773

722160

12.128

0.600

237900

14.134

1.781

689707

11.789

0.607

250522

14.767

1.780

731170

12.055

0.603

254974

14.908

Average OB4/RW

Residence Time

1.830 Average OB2/RW

O2

11.991 -

0.590

27690

2.695

1.830

194049

3.615

0.603

484847

24.904

1.833

168391

3.196

0.603

467530

24.886

Average

-

3.406

2

Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe

SS1/RW

1.843

70426

1.531

0.603

522039

25.825

1.840

50318

1.084

0.597

381621

23.695

1.840

98368

1.837

0.600

545982

26.028

Average SS2/RW

1.484 -

-

-

0.593

163861

13.163

-

-

-

0.603

559367

27.076

-

-

-

0.600

468364

26.145

Average

0

SS3/RW

1.847

58073

1.192

0.600

594014

26.913

1.847

46720

1.001

0.600

537555

26.477

1.850

29786

0.739

0.600

514189

26.335

Average

0.977

SS4/RW

1.797

467646

8.244

0.603

282112

17.633

1.790

623181

10.513

0.603

344553

18.599

1.790

572461

9.841

0.600

346515

18.715

Average

9.533 CO2 Concentration

Calibration Equation

Ctrl/RW

0%

Ctrl/MQ

0%

y=185.48x - 0.2561 CO2 Concentration

OB1/RW

1.747 %

SS1/RW

0.938 %

OB2/RW

0.000 %

SS2/RW

0.000 %

OB3/RW

6.603 %

SS3/RW

0.665 %

OB4/RW

1.974 %

SS4/RW

5.278 %

3

Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe Date: Run

2-May Sample Name Ctrl/RW

Average

CO2

Residence Time

Peak Area

Peak Height

-

-

-

0.593

511848

26.905

-

-

-

0.600

550883

27.139

-

-

-

0.593

480985

26.219

-

-

-

O2

Residence Time

Peak Area

Peak Height

-

-

-

0.590

540351

26.694

-

-

-

0.597

575966

27.090

-

-

-

0.597

518248

26.842

Average

-

-

-

Air (Ambient)

-

-

-

0.590

663820

27.667

Ctrl/MQ

OB1/RW

1.817

47354

0.996

0.587

206004

15.807

1.813

129279

2.550

0.593

423192

23.553

1.820

150468

2.872

0.600

467798

24.134

Average OB2/RW

2.711 -

1.840

24879

-

-

-

Average OB3/RW

0.593

488008

26.275

0.593

548150

26.889

0.593

560117

26.923

0.340 1.773

542122

9.201

0.593

191574

13.582

1.760

855857

13.762

0.600

256034

14.508

1.767

816431

13.250

0.603

236870

14.250

Average OB4/RW

0.340

13.506 1.797

386368

6.872

0.597

377459

20.403

1.793

725723

7.385

0.593

376555

20.233

1.797

419973

7.223

0.597

393892

20.390

Average

7.160

4

Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe SS1/RW

1.823

113552

2.301

0.600

497944

24.887

1.823

94250

1.926

0.593

457840

24.425

1.827

126083

2.424

0.600

539402

25.217

Average SS2/RW

2.217 -

-

-

0.590

415746

25.145

-

-

-

0.597

556348

26.882

-

-

-

0.597

570393

26.953 27.177

Average SS3/RW

0 -

-

-

0.597

598241

-

-

-

0.590

586444

27.106

0.593

582697

27.028

1.843

34322

Average

0.380 1.820

SS4/RW

136295

2.654

0.597

538747

26.143

1.813

99957

1.966

0.590

459190

25.382

1.823

429732

3.049

0.597

607551

27.115

Average NOTE: Values that are highlighted have been disregarded

0.38

2.556 CO2 Concentration

Cal ibration Equation

Ctrl/RW

0%

Ctrl/MQ

0%

y=168.71x + 0.0779

OB1/RW

1.561 %

SS1/RW

1.268 %

OB2/RW

0.155 %

SS2/RW

0.000 %

OB3/RW

7.959 %

SS3/RW

0.179 %

OB4/RW

4.198 %

SS4/RW

1.469 %

CO2 Concentration

5

Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe Date: 9-May Run

Sample Name Ctrl/RW

bad

CO2

Residence Time

Peak Area

Peak Height

O2

Residence Time

Peak Area

Peak Height

-

-

-

0.590

555577

27.205

-

-

-

0.587

568825

27.142

-

-

-

0.597

544147

26.930

Average

-

-

-

Ctrl/MQ

-

-

-

0.587

527980

26.862

-

-

-

0.593

521126

26.786

-

-

-

0.590

523973

26.737

Average

-

-

-

Air (Ambient)

-

-

-

0.593

570911

27.114

Air (Sparge)

-

-

-

0.597

560346

27.082

OB1/RW

1.817

44798

0.761

0.593

534351

26.603

baseline CO2

1.823

334255

1.191

0.597

520044

26.431

1.823

32084

0.696

0.593

525852

26.312

Average OB2/RW

0.729 -

-

-

0.590

523384

26.790

-

-

-

0.593

549011

27.019

-

-

-

0.590

539796

26.964

Average OB3/RW

0 1.797

218722

3.856

0.590

497836

25.601

1.800

145952

2.730

0.590

379993

23.551

1.800

202728

3.831

0.593

494364

25.519

0.590

388823

23.715

Average OB4/RW

3.472 1.803

108617

1.807

173973

3.276

0.597

547783

26.344

1.797

38711

1.175

0.583

273707

19.779

6

2.122

Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe Average SS1/RW

2.191 -

-

-

0.590

568231

26.681

-

-

-

0.590

571279

27.510

-

-

-

0.587

543636

26.757

Average SS2/RW

0 -

-

-

0.587

531964

26.869

-

-

-

0.593

565959

27.160

-

-

-

0.597

602291

27.370

Average SS3/RW

0 -

-

-

0.593

596754

27.210

-

-

-

0.587

385007

24.339

-

-

-

0.593

569804

27.075

0.590

579606

26.976

Average

0 1.82

SS4/RW

22993

0.452

-

-

-

0.587

384689

24.207

-

-

-

?

?

?

Average

0.452 CO2 Concentration

Cal ibration Equation

Ctrl/RW

0%

Ctrl/MQ

0%

y=177.151x - 0.002

OB1/RW

0.412 %

SS1/RW

0.00 %

OB2/RW

0.000 %

SS2/RW

0.00 %

OB3/RW

1.961 %

SS3/RW

0.00 %

OB4/RW

1.238 %

SS4/RW

0.26 %

CO2 Concentration

7

Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe Date: 9-May Run

Sample Name Ctrl/RW

CO2

Residence Time

Peak Area

Peak Height

O2

Residence Time

Peak Area

Peak Height

-

-

-

0.587

577635

27.302

-

-

-

0.587

620690

27.367

-

-

-

0.583

640961

27.329

Average

-

-

-

Ctrl/MQ

-

-

-

0.583

549672

26.964

-

-

-

0.587

607321

27.272

-

-

-

0.587

615119

27.356

Average

-

-

-

Air (Ambient)

-

-

-

0.583

620077

27.466

Air (Sparge)

-

-

-

OB1/RW

1.793

23415

0.491

0.580

280682

20.050

1.8

53084

1.133

0.583

539159

25.960

1.803

57495

1.161

0.590

545989

26.121

Average OB2/RW

1.147 -

-

-

0.587

576881

27.044

-

-

-

0.587

570260

26.987

-

-

-

0.590

574013

26.760

0.583

382682

22.751

Average OB3/RW

0 1.777

180948

3.579

1.777

119687

2.400

0.580

270142

19.308

1.773

205834

3.905

0.583

398378

23.113

0.587

490866

23.855

Average OB4/RW

3.742 1.777

255819

4.691

1.780

432003

3.086

0.580

327697

21.344

1.780

537269

5.149

0.587

543193

24.709

8

Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe Average

4.920

SS1/RW

1.807

43199

0.675

0.587

555869

26.609

1.803

83218

0.661

0.583

595657

26.728

1.81

22740

0.503

0.587

574022

26.733

Average SS2/RW

0 -

-

-

0.590

578017

27.077

-

-

-

0.583

360861

23.584

-

-

-

0.587

588892

27.152

0.269

0.587

565541

26.810

0.587

550767

26.722

0.349

0.583

677772

27.078

0.587

585157

25.909

Average

0 1.817

SS3/RW

14272

-

1.817

16564

Average

0.309 1.803

SS4/RW

88362

1.464

1.8

71348

1.315

0.587

586849

25.991

1.8

319188

1.523

0.583

643833

27.134

Average

1.434 CO2 Concentration

Cal ibration Equation

Ctrl/RW

0%

Ctrl/MQ

0%

y=x193.16 - 0.3302 CO2 Concentration

OB1/RW

0.765 %

SS1/RW

0.171 %

OB2/RW

0.000 %

SS2/RW

0.00 %

OB3/RW

2.108 %

SS3/RW

0.331 %

OB4/RW

2.718 %

SS4/RW

0.913 %

9

Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe

APPENDIX C

RETORT WATER TOC MEASUREMENTS

42

Individual Inquiry 4006 The Role of Soil Organic Matter in the Degradation of Organic Contaminants in Retort Water Susie Taaffe TOC Data Values in mg/L Initial Theoretical TOC Concentration (mg/L) Sample Name

11-Apr 18-Apr

24-Apr

2-May

15-May

11-Apr

Ctrl/RW Ctrl/MQ OB1/RW OB2/RW OB3/RW OB4/RW

3976 4.28 830.8 1637 2484 3814

3168 0 222.1 191 388.2 396

3179 -17.26 165.6 408.1 855.9 1453

3313 -27.15 119.2 291.7 719.7 1292

3023 -1.406 103.4 267.5 667 1264

Ctrl/RW Ctrl/MQ OB1/RW OB2/RW OB3/RW OB4/RW

3976 4.28 795.2 1590.4 2385.6 3976

SS1/RW SS2/RW SS3/RW SS4/RW

861.5 1477 2476 3787

89.82 273 1354 2803

176.4 366.4 809.4 1675

113.6 244.3 547.7 1401

109.3 173.8 482 1211

SS1/RW SS2/RW SS3/RW SS4/RW

795.2 1590.4 2385.6 3976

Not very good results for 18/4 thus 18/4 results will be disregarded. Equation - VCO2 = ((C/M)*vRT)/P CO2 volume prediction

Know predicted mL of CO2 therefore

Sample Name

18-Apr

24-Apr

2-May

Ctrl/RW

164.7

162.44

-27.3112

Ctrl/MQ

0.872

4.3902

2.015728

OB1/RW

124.1

135.58

OB2/RW

294.7

250.47

OB3/RW

427.2

OB4/RW

696.6

15-May

calculate predicted % of CO2 per 400mL headspace 11-Apr

18-Apr

24-Apr

2-May

15-May

59.10628 mL

0

41.17

40.61

-6.83

14.78 %

-5.24701 mL

0

0.22

1.10

0.50

-1.31 %

9.457004

3.220273 mL

0

31.02

33.89

2.36

0.81 %

23.72404

4.932317 mL

0

73.68

62.62

5.93

1.23 %

331.83

27.75957

10.74104 mL

0

106.79

82.96

6.94

2.69 %

481.21

32.81417

5.706813 mL

0

174.16

120.30

8.20

1.43 % 0.00

SS1/RW

157.3

139.63

12.79957

0.876403 mL

0

39.32

34.91

3.20

0.22 %

SS2/RW

245.4

226.36

24.88578

14.36894 mL

0

61.35

56.59

6.22

3.59 %

SS3/RW

228.6

339.59

53.33832

13.39063 mL

0

57.15

84.90

13.33

3.35 %

SS4/RW

200.6

430.52

55.84524

38.7248 mL

0

50.15

107.63

13.96

9.68 %

1