“Oil Lakes” Monitoring and Assessment Report Marine and ... Technolo… · parameters (see Appendix F to Volume 2 of the “Oil Lakes” M & A Report). For a specific petroleum-contaminated

“Oil Lakes” Monitoring and Assessment Report

Marine and Coastal Monitoring and Assessment Report

Oil Lakes Volume 2, Appendix E, Annex 2:

Marine and Coastal Appendix M, Annex 2

High-Temperature Thermal Desorption Bench Test Results: “Oil Lakes”, Supratidal Sediments, and Oil Trenches

Monitoring and Assessment of the Environmental Damages and Rehabilitation in the Terrestrial Environment (Cluster 3) and in the Coastal and Marine Resources (Cluster 2)

UNCC Claims 5000432 and 5000398

27 August 2003

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Consortium of International Consultants I

TABLE OF CONTENTS 1 Introduction and Site Description...............................................1

1.1 Types of Oil Contamination............................................................. 1 1.1.1 Terrestrial Oil Contamination................................................ 1 1.1.2 Coastal Oil Contamination.................................................... 2

2 Oil-Contaminated Samples for Bench Testing...........................3

3 Treatability Study Design and Implementation ..........................4 3.1 Treatability Study Objectives........................................................... 4 3.2 Treatability System Design and Description.................................... 4

3.2.1 Bench Scale System Description/Operation......................... 4 3.2.2 Data Acquisition System....................................................... 6

3.3 Treatment Process Description ....................................................... 7 3.3.1 Sample Preparation Procedure ............................................ 8 3.3.2 Rotary Tube Furnace Treatability Test Procedures............ 10 3.3.3 Treatability Study Test Matrix ............................................. 12

3.4 Data Acquisition System Description ............................................ 13 3.4.1 Physical Parameter Measurement ..................................... 13 3.4.2 Test Real Time Parameter Measurement........................... 13

4 Data Analysis Results and Interpretation.................................14 4.1 Characterization of Contaminated Soils ........................................ 14 4.2 Summary of Measured Parameters .............................................. 14 4.3 Laboratory (Analytical Services Center) Analysis of Treated

Soils .............................................................................................. 14 4.4 Summary of Test Results.............................................................. 15

4.4.1 Analytical Parameters Measurement Results..................... 15 4.4.2 Physical Parameters Measurement Results....................... 15

5 Conclusions and Recommendations .......................................18

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Consortium of International Consultants II

LIST OF TABLES

Table 3-1 Summary of Chemical Analyses

Table 3-2 Treatability Test Matrix

Table 4-1 Moisture and Weight Losses for Terrestrial Samples

Table 4-2 Moisture and Weight Losses for Coastal Samples

Table 5-1 Summary of Bench Testing Results for Temperatures equal to or greater than 850 degrees Fahrenheit (454 degrees Celsius) and Retention Times equal to or greater than 20 minutes

Tables are bookmarked.

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Consortium of International Consultants III

LIST OF FIGURES Figure 3-1 Treatability Study Equipment Configuration

Figure 3-2 Sample Preparation Work Sheet

Figure 3-3 Laboratory Data Sheet

Figure 3-4 Daily Activity Log

Figures are located at the end of the document. Figures are bookmarked.

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Consortium of International Consultants IV

LIST OF ATTACHMENTS

Attachment A Sample Preparation Work Sheets (prepared by Therm-tec)

Attachment B High-Temperature Thermal Desorption Bench-Scale Testing/Therm-tec Laboratory Data Sheets

Attachment C Daily Activity Logs

Attachment D Data Logger Readings

Attachment E Analytical Services Center (ASC) Laboratory Results

Attachment F Chains of Custody

Attachment G Soil Sample Analyses Summary Sheet

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Consortium of International Consultants 1

1 Introduction and Site Description As part of the State of Kuwait’s Monitoring and Assessment Program, the Consortium of International Consultants reviewed technologies that are potentially applicable to the remediation program for the oil contamination resulting from Iraq’s invasion and occupation of Kuwait. The high-temperature thermal desorption (HTTD) method has been identified as one of the remediation technologies for further evaluation. This report presents the bench scale testing for a high temperature thermal desorption system. The bench scale testing was conducted as part of the evaluations to address the contamination covered in the State of Kuwait’s Fourth Instalment Claims for damage caused by terrestrial oil contamination and oil contamination of Kuwait’s coastal resources. The results provide information for the design of the treatment system and the cost estimate. 1.1 Types of Oil Contamination The different types of oil contamination addressed in the Fourth Instalment Claims are described below. Representative samples of the various categories of oil contamination were included in the bench scale testing to determine the effectiveness of using the high-temperature thermal desorption treatment method. 1.1.1 Terrestrial Oil Contamination Wet Oil Contamination – Consists of black liquid or semi-solid oil over or interspersed within oil-contaminated soil. The wet oil contamination occurs in areas where liquid oil accumulated due to microrelief and local topography. Such places include shallow depressions and drainage channels. The liquid oil surfaces may have a thin hardened layer on the surface, but this surface is not strong enough to support a person walking on it. The presence of free liquid has precluded completion of ordnance clearance in the areas where this type of contamination occurs, and the presence of free liquid also presents distinct material handling issues that will need to be addressed when remediation occurs. Dry Oil Contamination – Consists of a thin, black, moderately hard, tar-like dry surface layer (that may contain some contaminated soil material) – sometimes with a layer of oil sludge – overlying dark brown oil-contaminated soil that in turn overlies soil with no visible oil contamination. The dry oil contamination occurs in shallow depressions and flat areas, often fringing areas of wet oil contamination. Oil-contaminated piles – The piles occur where earthmoving equipment has been used to consolidate oil-contaminated soil and/or liquid oil into mounds. These piles were made in efforts to stop the spread of oil flows caused by the destruction of Kuwait’s oil wells, or to clear areas of heavy oil contamination as necessary to facilitate firefighting or subsequent Kuwait Oil Company field operations. Oil Trenches - This material consists of oil-contaminated soil associated with oil trenches constructed by Iraqi troops. This category also includes oil-contaminated soils associated with oil flows from the Iraqi pipeline and the Wadi Al Batin spill.

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1.1.2 Coastal Oil Contamination Oil Deposit - This material is characterized by the presence of visibly oiled or stained sediment not located in oil trenches. Coastal oil deposits may contain some or all of the following:

• Hardened Oil sludge • Asphalt-like material • Oil contaminated sediments

The coastal oil deposit is similar in consistency to the terrestrial dry oil contamination category materials. Oil Trench - This material contains visibly oiled or stained sediment associated with Iraqi-built trenches, that may contain some or all of the following:

• Liquid oil or oil-water emulsion • Contaminated sediments • Asphalt-like material at the surface

Weathered Oil Layers - This material is generally a layer of accreted sediment and visibly oily material, asphalt-like in appearance, and occurring in discrete bands or patches. On-going Monitoring and Assessment studies continue to map the extent of this type of contamination. The coastal weathered oil layers are similar in consistency to the terrestrial tarcrete. Residual Contamination On-going Monitoring and Assessment studies continue to map the extent of coastal residual contamination. Coastal residual contamination generally takes one of two forms: Non-visible Petroleum Contamination - This contamination is at levels that are not discernable with the naked eye. Because this contamination may not be readily visible, laboratory testing results are necessary and have determined the extent of this contamination. Visible contamination in a very thin subsurface layer or band - Total petroleum hydrocarbon levels may be quite high within the thin band of subsurface tarcrete contamination. This layer may provide a physical and chemical barrier to healthy propagation of flora and fauna. When buried, accessing this material for remediation would effectively reduce concentrations to levels similar to non visible contamination. Recognizing that accessing these materials by removing associated overburden may result in more harm to the environment than good, this type of contamination has been included in the category of non-visible contamination. Monitoring and Assessment studies to fully delineate the extent of coastal residual contamination are ongoing.

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2 Oil-Contaminated Samples for Bench Testing Samples Utilized for Bench Testing Twenty samples were collected and submitted for bench testing to assess thermal treatment technology. Samples were selected to be representative of the types of contamination found in general proportion to the volume of each contamination type as described in the previous section. In the terrestrial oil contamination environment, six samples were collected from areas of dry oil contamination. These samples were collected from the Burgan and Raudhatain oil fields. Sample sites were selected based on visual observation of the degree of contamination. Samples ranged from a lightly stained sand to a mixture of tar and sand. Four samples were collected from oil-contaminated piles. Three of the four consisted of a sand and tar mix, the fourth of stained sand. Two samples of wet oil contamination were collected - one was soft and nearly liquid, and the other appeared firm. One sample was collected from an oil trench. This sample appeared to be a mixture of tar and sand.

In addition, seven oil-contaminated samples were collected from areas in the coastal environment. Two were collected from the oil deposit representing high and medium levels of contamination based on visual observations. Two samples were also collected from the oil trench - one containing liquid oil and sand, and the other containing more of a silt matrix based on field classification. Two samples were collected from weathered coastal layers. The first included a relatively thick layer of tar from the mid tidal range. The other was from a thin layer of tar from the upper tidal range. The seventh sample was collected as a composite of the upper 15 centimeters of sediment from an area with a thin layer of visible contamination at a depth of about 10 centimeters.

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3 Treatability Study Design and Implementation 3.1 Treatability Study Objectives In the design of a full scale high temperature thermal desorption system for treatment of petroleum contaminated soil, soil temperature, and soil retention time are critical parameters (see Appendix F to Volume 2 of the “Oil Lakes” M & A Report). For a specific petroleum-contaminated soil (e.g., dry oil contaminated soil), it is difficult to accurately predict the soil desorption temperature and the soil retention time analytically. Therefore, to accurately define the parameters for full-scale design, a bench scale treatability study was undertaken. As part of the study, a total of nine test conditions was established for each soil type. The nine conditions were formed from three soil temperatures and three retention times per temperature. Each combination of test conditions was run three times, resulting in a total of 27 data points per soil type. These 27 data points established the relationship between temperature and retention time for each soil type. The data points were used to determine the minimum retention time for each temperature for a given level of residual total petroleum hydrocarbons. Those temperature/retention time relationships were repeated for the various soil types, yielding a temperature/retention time relationship for the soil types. These temperature/retention time relationships were then used for the high temperature thermal desorption system preliminary design. 3.2 Treatability System Design and Description 3.2.1 Bench Scale System Description/Operation To identify the conditions required to obtain the desired treated residue characteristics, the bench scale treatability system was a rotary tube furnace system that was designed to simulate the physical, chemical, and thermal environment of the primary chamber (or desorption stage) of a rotary kiln thermal treatment system. The bench scale treatability system consisted of an electrical, rotary tube furnace that functioned as a rotary primary desorption chamber. This primary desorption furnace had heated walls and rotated to simulate full-scale operation. An additional stationary furnace provided hot gases to the desorption furnace to simulate the combustion gases which occur in the full-scale system. A schematic of the rotary tube thermal treatability test apparatus is presented on Figure 3-1. The bench scale treatability system included temperature measurement devices in the preheat furnace, the primary furnace inlet air, the primary furnace wall, and in the contaminated soil (reaction cell). The bench scale unit was designed to incorporate critical mechanical and thermal properties of a full-scale rotary kiln. These design parameters included primary temperature, solids retention time, rotational speed, primary gas velocity, primary chamber length to diameter ratio, and solids fill ratio. Each of these design parameters is discussed below. Primary Temperature: The thermal reaction chamber is heated by resistive elements and is capable of maintaining temperatures ranging from 38 degrees Celsius to 1,093

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degrees Celsius. Primary temperatures of 399 degrees Celsius (750 °F), 454 degrees Celsius (850 °F) and 510 degrees Celsius (950 °F) were chosen as the design temperatures for this study. Solids Retention Time: Any desired solids retention time could be achieved using the bench scale treatability system since the soil is contained within a reaction cell that can be loaded and extracted from the thermal reaction chamber at specified intervals. Measurement of the solids retention time began when the soils reached the desired operating temperature. Primary chamber solids retention times of 10, 20 and 30 minutes were chosen as the design retention times for this study. Rotational Speed: The rotation of a full-scale rotary kiln enhances solids mixing and transports the solids through the kiln. The motion of the solids within a full-scale kiln enhances volatilization of the contaminants by providing a uniform temperature throughout the solids bed. The bench scale treatability system simulated these parameters, with the exception of solids transport through the kiln. The rotational speed of the treatability system kiln was set to ensure that the solids in the kiln would slump (turn over) rather than veil (ride against the side of the kiln unit reaching the top and free falling through the kiln). If the material veils, an excessive amount of material will be entrained in the gas stream and carried out of the kiln. The rotational speed of the treatability unit was set at one revolution per minute for this study because visual observations of the solids in the reaction cell confirmed that 1 revolution per minute provided an acceptable solids slumping rate without causing the material to veil. Primary Gas Velocity: For the purposes of this experiment, the primary function of the kiln gas was to achieve sufficient airflow to remove moisture and volatilized contaminants with minimum transport of solids and particulate out of the reaction cell. Primary chamber gas velocities were maintained at 14.5 standard cubic feet per minute for this study. Primary Chamber Length to Diameter Ratio: The length of the quartz reaction cell was 24 inches (610 millimeters) and the inside diameter was 2-3/16 inches (56 millimeters). The bench scale length-to-diameter ratio was approximately 11:1 and was a result of the configuration of the test equipment, rather than a predetermined design value. Since continuous movement of material through the treatability unit is not a design feature, the length-to-diameter ratio does not affect the ability of the unit to achieve the desired test conditions. Since the treatability unit is a batch system, material can be maintained at the desired operating temperature for any length of time. Solids Fill Ratio: The solids fill ratio is the percentage of the interior cross sectional area of the kiln occupied by the solids bed. Typical fill ratios for full-scale rotary kilns vary from 5 to 20 percent, depending on the characteristics of the material and the desired treatment conditions. A solids fill ratio exceeding 20 percent will reduce the number of times the material slumps during each revolution of the kiln. This reduces the mixing of solids in the bed and results in uneven heating and reduced contaminant volatilization. In order to replicate the operation of a full-scale kiln, a fill ratio of 5 to 20 percent was used in this bench scale testing.

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Although actual mixing and turbulence in a full-scale rotary kiln cannot be exactly reproduced in the treatability test unit, the differences between the test apparatus and a full-scale rotary kiln should provide for conservative results because the full-scale system provides more mixing and turbulence. Therefore, adequate volatilization of organic compounds in the treatability test apparatus should provide a high probability that adequate volatilization would also be achieved in a full-scale system under similar operating conditions in terms of solids retention time at a given temperature. For the purposes of this project, it was not necessary to duplicate the performance of the secondary combustion chamber and/or the air pollution control system, which is normally part of a full-scale system, because: (1) thermal destruction of organic compounds in a secondary combustion chamber or capture of the organic compounds in a condenser/absorber is relatively independent of the primary chamber and has been demonstrated for numerous compounds at various operating conditions, and (2) the performance of the air pollution control system is extremely sensitive to the system configuration and, therefore, should not be generalized. The measured performance of the primary chamber can be combined with the proven performance of a secondary treatment system and the demonstrated contaminant removal efficiencies of a number of air pollution control systems to evaluate the impacts of the complete thermal treatment system proposed. The components of the rotary tube furnace that contact the soil were made of quartz to prevent any reactions between the furnace components and the soil. A predetermined mass of soil was placed in a quartz reaction cell. The reaction cell was fitted with quartz end caps containing holes that allowed purge gas to pass through the reaction cell. The reaction cell was placed within the quartz furnace liner. The furnace liner was mechanically rotated, turning the reaction cell at the same rate as the furnace liner. At the conclusion of the treatment cycle, the reaction cell was removed from the furnace liner and allowed to cool. The reaction cell was weighed to determine total weight loss and the treated sample was removed for analysis. The rotary tube furnace was equipped with a gas handling system in which the gases are pushed through the rotary tube by a pressure pump located upstream of all test system components. The total gas flow rate was measured on a rotometer and was held constant for the duration of the test period. Gases exiting the rotary tube furnace were drawn through a glass wool plug followed by a particulate filter designed for 99.95 percent removal efficiency for particles of more than 0.3 microns in diameter. The filter holder and exhaust tubing were insulated to maintain a minimum gas temperature of 116 degrees Celsius through the filter to prevent condensation of the water vapor and organic contaminants removed from the soil. 3.2.2 Data Acquisition System The bench scale treatability system included temperature measurement devices (thermocouples) in the preheat furnace, the primary furnace inlet air, the primary furnace wall, and in the contaminated soil (reaction cell). An electronic data logger was used to record temperatures and corresponding date/time data for the four thermocouples at 30-second intervals throughout each test. The time/temperature data were electronically stored and periodically downloaded to computer diskettes. The data on diskettes were subsequently manipulated using a personal computer and spreadsheet program. The

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time/temperature data were then printed to hard copy. In addition, all four thermocouple temperature measurements were recorded manually. Gas flow data, measured with a rotometer, and furnace rotation speed were recorded manually by the technicians on the Laboratory Data Sheet (Figure 3-3) for each run. The data logger provided a readout of hours, minutes and seconds that was used to by the technicians to determine the length of each run. 3.3 Treatment Process Description The overall treatment process/experimental procedure consisted of the following steps:

1. A 100-gram portion of each soil sample was analyzed for the following pre-treatment parameters (20 samples): a. Soil moisture content (percent) b. Soil energy content (kilocalories per kilogram) c. Soil contamination level (total petroleum hydrocarbons) d. Asphaltenes e. Soil grain size distribution f. Bulk density

2. The remaining portion of each soil sample was then divided into nine samples of

about 100 grams each. 3. Each sample was treated in the primary desorption chamber at a given temperature

for each retention time until tests for the nine combinations of temperature and retention time were completed.

4. After each run (consisting of a target temperature and target retention time) was

completed, the soil sample was removed from the primary chamber and cooled. Each treated soil sample (there were approximately 540 samples in total) was individually weighed and shipped to the Ecology & Environment, Inc. Analytical Services Center and analyzed for: a. Soil moisture content (percent) b. Soil contamination level (total petroleum hydrocarbons) c. Asphaltenes d. Bulk density

Table 3-1 summarizes the analytical testing performed.

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Table 3-1 Summary of Chemical Analyses

Analysis Initial

Testing

Pre-Burn Test2

Post-Burn Test2

Analytical Test Method

Volatile Organics X EPA Method 8260B Semivolatile Organics X EPA Method 8270C ICP Metals X EPA Method 6010B British Thermal Units (Heat Content) X X Method D240-92 Chloride X EPA Method 300 pH X EPA Method 9045C Specific Conductance X EPA Method

9050A-M n-Hexane Extractables (total petroleum hydrocarbons)

X X X SW9071B

Asphaltenes (TEM –HEM)

X X X3 SW9071B

Percent Organics X ASTM Method D2974

Percent Moisture X X X ASTM Method D2216

Bulk Density X X X3 SM2710F Particle Size Distribution X ASTM = American Society for Testing and Materials

1 Testing was performed by Ecology & Environment, Inc., Analytical Services Center in Lancaster, NY. 2 20 pre-burn samples; 540 post-burn samples 3,Analyses run on samples from the lowest temperature/shortest retention time and the highest temperature/longest

retention time (40 total samples) 4`Note: With the exception of the volatile organic sample, which was collected into two, 120-milliliter glass jars

with a Teflon-lined lid, all samples were collected in one 8-ounce glass jar with a Teflon lined lid. 3.3.1 Sample Preparation Procedure Shipping containers of untreated soil were received at the study laboratory (Therm-tec) from the Ecology & Environment, Inc. Analytical Services Center. Each container was checked against the shipping manifest and sample chain of custody form and any exceptions were noted. The shipping containers were then placed in refrigerated storage. The following describes the procedures and equipment used. Containers of contaminated soil were retrieved from refrigerated storage as needed. Only one container of soil was open at any time in the treatability study laboratory. Additional containers of soil were not opened until the contents of the previous container were exhausted. A Sample Preparation Worksheet (Figure 3-2), was then completed for each container of soil used. The number and weight of each shipping container, as well as any irregularities, were noted on the worksheet before the seal was broken. The sample container was opened within a laboratory fume hood and its entire contents were transferred to a stainless steel mixing bowl. The sample was thoroughly homogenized and any oversized material in excess of one-quarter inch (6 millimeters) in diameter was removed. Any oversized material, which could not easily be reduced in size, was weighed and placed in a labeled soil-shipping container designated for unused soil material. Sample Preparation Work Sheets prepared by Therm-tec for each run are presented in Attachment A.

After the sample was homogenized and the oversized materials were removed, a representative sample was collected for conducting pre-treatment chemical and physical analyses. Samples were collected and placed in the appropriate sample containers in

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accordance with needs of the analytical test methods to be performed. Table 3-1 presents the summary of pre-treatment analyses that were performed for this project. Prior to the start of the treatability study, a single pre-test charge of soil was processed at each of the proposed test conditions. The total volume and mass reduction for each treatment condition were recorded. The results of these pre-test charges determined the total mass loading to be used for each treatment batch and the total number of batches that were required under each test condition. The treated sample from these pre-test charges was placed in an empty soil-shipping container for subsequent return to the lab. After determination of the nominal mass for each set of test conditions, the contents of each shipping container were divided into separate batches and stored in an appropriately sized glass jar with a Teflon-lined screw-on lid. Each jar was labeled with the number of the shipping container, the mass of the contents, the total mass of the full jar, and the operating conditions for which it was prepared. In addition, the number and mass of each charge jar were recorded on the Sample Preparation Worksheet. The charges required for each test condition (plus a contingency) were prepared at one time. These jars were placed in refrigerated storage until processed. A 500-gram representative sample of the soil was collected from each shipping container and maintained in refrigerated storage until the conclusion of the test. The above procedure was repeated for each set of test conditions. All sampling equipment was decontaminated between test conditions. The equipment and materials required for sample preparation were as follows:

1. fume hood 2. sample preparation forms 3. supply of charge jars with Teflon-lined lids 4. sample container labels showing:

• date • sampling technician • soil type • identification number • test condition and charge number

5. stainless steel mixing bowl and trowels 6. analytical balance (accurate to 0.1 grams) 7. health and safety equipment

• gloves and lab apron • safety glasses • other personal protective equipment as required

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3.3.2 Rotary Tube Furnace Treatability Test Procedures The furnace was turned on and the temperature within the thermal reaction chamber was allowed to stabilize at the desired set point. During the processing of samples, the thermal reaction chamber temperature deviated above the set point due to the variations in the energy content of the soil samples. The thermal reaction chamber temperature was measured at the outlet of the furnace, outside of the furnace liner wall, and in the middle of the heated zone of the thermal reaction chamber. Once the temperature had stabilized in the thermal reaction chamber, the treatment process began. A Laboratory Data Sheet, as shown on Figure 3-3, was used to record process test parameters and sample conditions. To start the test, a pre-weighed, loaded reaction cell was loaded into the thermal reaction chamber. This time was identified as “charge in” on the laboratory data sheet. At this time, a thermocouple was positioned into the soil solids bed and the reaction cell exit, such that the solids temperature and exit air temperature could be measured and recorded. An electronic data logger was used to record all temperature data at 30-second intervals. The airflow through the cell and rotation of the cell were initiated. This period was identified as “air on” on the laboratory data sheet. When the solids temperature reached the desired operating condition, the time was entered on the laboratory data sheet as “start time”. The start time initiated the start of the specified retention time period. Rotation and airflow through the reaction cell continued throughout the specified retention time. At the end of the specified retention time, the airflow through the reaction cell was stopped and the time was entered as the “end time/air off” time on the laboratory data sheet. Since the reaction cell and contents were still exposed to the thermal environment of the thermal reaction chamber while the soil thermocouples were being extracted, the end time of the run was defined as the time that the reaction cell was actually extracted from the thermal reaction chamber. This time was identified as the “charge out” time on the laboratory data sheet. Once the reaction cell with the sample had been removed from the thermal treatment apparatus, it was placed on a cooling stand with an identification tag and allowed to cool. The cell was then sealed with rubber stoppers until its final weight was determined and visual observations were made. Once the weight observations were recorded on the Laboratory Data Sheet, and a post-test sample volume extracted, the sample was placed into the appropriate pre-weighed and pre-labeled sample jars. The jars were labeled, sealed, and placed in refrigerated storage overnight. The samples were typically shipped, via overnight delivery, to the laboratory on the day following production. A Daily Activity Log (Figure 3-4) of test activities was maintained throughout the treatability test period. The activities of each day’s testing were recorded by the technicians. The following procedure was used for cleaning the reaction cells between operating conditions.

1. Rinsing the thermal reaction chamber with tap water three times. 2. Washing with soap and a brush, and then rinsing with water.

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3. Cleaning with kitchen oven cleaner to remove baked-on residue. 4. Rinsing with tap water. 5. Brushing out with soap and water. 6. Rinsing three times with water. 7. Air drying. 8. Ready for use.

Below is a listing of the components and specific equipment used to perform the treatability tests:

1. Combustion air supply • vacuum air pump • inlet air filter (optional) • combustion air ducting (tubing) • rotometer

2. Thermal reaction chamber

• rotary tube furnace and controller • soil temperature thermocouple • exit gas temperature thermocouple • particulate filter exit gas thermocouple • condenser exit gas thermocouple • reaction cell and end caps • vent hood

3. Electronic data logger for the following:

• preheat furnace thermocouple • primary furnace inlet air thermocouple • primary furnace wall thermocouple • contaminated soil (reaction cell) thermocouple

4. Personal computer 5. Quartz furnace liner 6. Furnace liner drive and motor 7. Laboratory data sheets 8. Glass charge jars and appropriately sized residue sample jars with Teflon-lined

lids 9. Sample containers labels showing the:

• date and sampling technician • soil type • sample number of shipping container

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• treatability operating condition • mass of treated sample • treatment conditions

10. Miscellaneous reaction cell handling equipment 11. Analytical balance 12. Health and safety equipment

• gloves and lab apron • safety glasses • air purifying respirator (if required) with organic, acid gas, HEPA (High

Efficiency Particulate Air) cartridges • other personal protective equipment as required

13. Alconox soap, brushes

3.3.3 Treatability Study Test Matrix Table 3-2 presents the treatability study test matrix used for the 20 soils. The matrix was designed to represent the range of time and temperature operating conditions documented for full-scale rotary thermal units processing similar soils.

Table 3-2 Treatability Test Matrix Number of Replicates per Operating Condition

Soil Temperature

Run Number Retention

Time (minutes)399 degrees

Celsius 454 degrees

Celsius 510 degrees

Celsius 10 1 1 1 20 1 1 1 1

(Initial Run) 30 1 1 1 10 1 1 1 20 1 1 1 2

(Replicate No.1) 30 1 1 1 10 1 1 1 20 1 1 1 3

(Replicate No.2) 30 1 1 1 Total Number of

Tests per Soil 9 9 9

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3.4 Data Acquisition System Description 3.4.1 Physical Parameter Measurement Prior to the start of each run, the soil to be tested was visually observed and a description written on the Laboratory Data Sheet. The untreated soil was placed in the quartz reaction cell and the soil and the cell were weighed. The weight of the cell was subtracted from the combined weight of the cell and soil to determine the charge weight before treatment. After treatment in the test apparatus, the combined weight of the cell and soil was measured. The soil was then removed from the cell and the cell and reweighed. The weight of the cell was subtracted from the combined weight of the cell and soil to determine the charge weight after treatment. 3.4.2 Test Real Time Parameter Measurement Prior to the start of each test, the furnace air preheater and primary furnace temperatures were set manually and allowed to reach the desired temperature. The rotation speed of the primary furnace and the airflow were also set manually. Once the desired temperature was reached, the soil was inserted into the primary furnace and test began. During the test, the technicians manually recorded the time and temperature readings when the charge was inserted, the preheat air was turned on, the start and end of the test, and the time the charge was removed. These real time readings were obtained from the data logger readout and recorded on the Laboratory Data Sheets prepared by Therm-tec that are provided in Attachment B.

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4 Data Analysis Results and Interpretation 4.1 Characterization of Contaminated Soils The first column of Table 3-1 lists the parameters for which each of the post-burn soil samples was tested by the Ecology & Environment, Inc. Analytical Services Center. The 27 post-burn soil samples from each soil type except one, as discussed below (a total of 515 post-burn samples), were analyzed for n-hexane extractables and percent moisture content. The n-hexane extractables procedure provides a measure of the total petroleum hydrocarbons present in the soil. Two post-burn soil samples from each soil type (a total of 40 post-burn samples) were analyzed for asphaltenes and bulk density. The two post-burn soil samples from each soil type were from the following test conditions: 1) Run 1, 399 degrees Celsius (750 °F) and 10-minute retention time, and 2) Run 1,510 degrees Celsius (850 °F) and 30-minute retention time. These test conditions were selected to bracket the full range of time and temperatures tested. The only sample that was not tested 27 times was sample T251-13, which was a sample of thick, wet, oil-contaminated soil from the Burgan oilfield. During the first test run at a temperature of 510 degrees Celsius, the sample ignited due to its high total petroleum hydrocarbons content, causing some damage to the test apparatus. A second run was attempted at a lower temperature of 399 degrees Celsius; however the sample again ignited. To prevent further damage to the test apparatus, further testing of this soil was suspended. Therefore, only two laboratory analyses were available on this soil. The results of the testing of the initial samples, collected in January and February 2003, that were used to characterize the contaminated soils are contained in Attachment G. In general, the 20 soil types were relatively low in volatile and semivolatile compounds. Heat content, measured as British thermal units, ranged from below detection levels to 18,100 British Thermal Units (10,056 kilocalories per kilogram). Total petroleum hydrocarbons, as measured by n-hexane extractable materials, ranged from 677 milligrams per kilogram to 431,500 milligrams per kilogram. Asphaltenes ranged from 926 milligrams per kilogram to 400,000 milligrams per kilogram. Percent moisture ranged from 0.796 percent to 40.5 percent. 4.2 Summary of Measured Parameters Sample Preparation Work Sheets, prepared by Therm-tec, are provided in Attachment A. Attachment B provides high temperature thermal desorption Bench Scale Testing/Therm-tec Laboratory Data Sheets prepared for each of the 515 test runs. Daily Activity Logs are provided in Attachment C. The data logger readings from each test run are provided as Attachment D. 4.3 Laboratory (Analytical Services Center) Analysis of Treated

Soils The laboratory data sheets are provided in Attachment E and chain of custody forms are included as Attachment F.

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4.4 Summary of Test Results 4.4.1 Analytical Parameters Measurement Results Attachment G provides the complete bench scale soil sample analyses results for all 20 soils (515 runs) which were treated. These results are summarized in Table 4-8 and Table 4-9 in Appendix E, which present the average total petroleum hydrocarbons concentration measured for all nine operating conditions. Table 4-8 of Appendix E presents the results of testing from the 13 terrestrial samples, while Table 4-9 of Appendix E presents the results of the testing from the 7 coastal samples. The pre-burn total petroleum hydrocarbon results are also presented and are the averages of the initial soil samples results and soil samples taken prior to thermal treatment. In general, these analyses show that for all soil types, with the exception of soils T251-13 and C41-01, minimum operating conditions of 850 degrees Fahrenheit (454 degrees Celsius) and 20 minutes retention time yielded, on average, hydrocarbon removal efficiencies of 98.8 percent. Soil T251-13 was not treated at this condition and soil C41-01 had a pre-burn total petroleum hydrocarbon value of 400 milligrams per kilogram and a post-burn non-detect value (less than 200 milligrams per kilogram). 4.4.2 Physical Parameters Measurement Results In addition to the total petroleum hydrocarbons and asphaltene content on the bench scale treated soil, soil physical parameters were also measured before and after treatment. Table 4-1 and Table 4-2 present the results of the moisture content measurements and weight loss. 4.4.2.1 Soil Moisture Content Table 4-1 and Table 4-2 show that for the tested soils, the remaining moisture content after treatment ranged from 0.00 percent to 0.69 percent. This compares to the values for untreated soil which ranged from 1.06 percent to 41.8 percent. In most cases, it can be concluded that under the bench scale treatment conditions of 399 degrees Celsius (750 degrees Fahrenheit) to 510 degrees Celsius (950 degrees Fahrenheit) treated soils will have negligible remaining moisture content.

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Table 4-1 Moisture and Weight Losses for Terrestrial Samples

Moisture Content

(percent)

Weight Loss

(percent) Sample ID Type of Soil Description Pre* Post* Post* T251-01 Oil Trenches Oil Trench 8.83 0.03 19.9 T251-02 Oil Contaminated

Soil Piles North Pile 1 9.53 0.07 20.5

T251-03 Oil Contaminated Soil

North Oil Field Light

1.86 0.54 5.9

T251-04 Oil Contaminated Soil Piles

North Pile 2 6.50 0.03 17.4


North Oil Field Dark

3.22 0.01 7.3


Burgan Dark 0.82 0.09 4.4


Burgan Light 3.87 0.03 6.7


Burgan Tar + Soil

4.16 0.03 15.9


Burgan Pile 1 1.06 0.03 10.1

T251-12 Wet Oil Contamination

Burgan Thin 41.8 0.29 59.6

T251-13 Wet Oil Contamination

Burgan Thick 2.80 0.41 90.1


Burgan Soil + Tarcrete

1.71 0.02 9.5


Burgan Pile 2 3.28 0.00 10.9

* “Pre” signifies concentrations before treatment; “Post” signifies concentrations after treatment.

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Table 4-2 Moisture and Weight Losses for Coastal Samples

Moisture Content

(percent) Weight Loss

(percent) Sample ID Type of Soil Description Pre* Post* Post*

T1219 Oil Trench Clay/Oil - Trench

21.55 0.01 26.0

T1220 Coastal Oil Deposits

Sand/Oil - Trench

12.60 0.04 21.9


Sand/Tarcrete- Supratidal

2.35 0.04 21.4


Stained Sand - Supra

13.72 0.00 16.3

C41-01 Coastal Weathered Oil Layers

Khiran Tarcrete 12.8 0.69 14.6

C41-02 Coastal Residual Contamination

Khiran Subsurface

15.65 0.03 17.6

C41-03 Coastal Weathered Oil Layers

Pipeline Beach 7.22 0.10 14.7

* “Pre” signifies concentrations before treatment; Post” signifies concentrations after treatment.

4.4.2.2 Soil Weight Loss Table 4-1 and Table 4-2 show that weight loss in the treated soils ranged from 4.4 percent to 90.1 percent. In general, the data in Attachment G shows that

• The greatest soil weight loss occurs at the highest operating temperature, 950 degrees Fahrenheit (510 degrees Celsius), and the longest retention time (30 minutes).

• Most soil weight loss is attributable to the loss of moisture and the loss of total

petroleum hydrocarbons and asphaltenes during the high temperature desorption process.

• In some cases the weight loss also is attributable to the loss of organic material or

compounds in the soil that were destroyed during the desorption process (in addition to the loss of moisture, total petroleum hydrocarbons and asphaltenes).

In the case of the full scale high temperature thermal desorption, the moisture in the soil will be lost in discharge through the system exhaust stack, while the total petroleum hydrocarbons, asphaltenes and other organics will be destroyed in the flame of the rotary dryer or in the thermal oxidizer. 4.4.2.3 Soil Physical Appearance In general, for the higher temperatures and the longer retention times, the treated soil appearance approaches that of the “virgin” uncontaminated soil. However, in some cases the treated soil will appear lighter colored or “whiter” than the “virgin” soil. This is usually due to the lack of moisture in the treated soil. Field experience has shown that replenishing the moisture to the soil will restore the soil to the approximate original color. The treated soils exhibited no odor and flowed freely.

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5 Conclusions and Recommendations The results of the bench scale testing show that high temperature thermal desorption can treat all of the types of contamination encountered in both the terrestrial and coastal areas. At a temperature of 850º Fahrenheit (454º Celsius) and a retention time of 20 minutes, a full scale high temperature thermal desorption system can treat the Kuwait contaminated soils to the levels required (no visible contamination). In particular, the results of the portion of the bench testing that are summarized in Table 5-1 show that at a temperature of 850 degrees Fahrenheit (454 degrees Celsius) and a retention time of 20 minutes, approximately 92 percent of the soil samples whose untreated total petroleum hydrocarbon value was less than 75,350 milligrams per kilogram had a post-treatment total petroleum hydrocarbon concentration of less than or equal to 500 milligrams per kilogram. Only three of the 39 such soil samples tested at this temperature and retention time continued to exceed 500 milligrams per kilogram after treatment. There were 23 cases of non-detect (less than or equal to 200 milligrams per kilogram), and the average value of treated soil for all cases was 268 milligrams per kilogram.

Table 5-1 Summary of Bench Testing Results for Temperatures equal to 850 degrees Fahrenheit (454 degrees Celsius) and Retention Times equal to 20 minutes (for soils with pre-treatment total petroleum concentrations less than or equal to 75,350 milligrams per kilogram)

Total Petroleum Hydrocarbons

Total Number of Cases 39

Number of cases that exceed 500 milligrams per kilogram total petroleum hydrocarbons

3 (534, 614, 850)

Number of cases of non-detect

23

Average value of all cases, in milligrams per kilogram

268

The results in Table 5-1 were presented for contaminated soils of less than or equal to 75,350 milligrams per kilogram because this approximates the total petroleum

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hydrocarbon limit for which the full-scale high temperature thermal desorption system has been designed (70,000 milligrams per kilogram). Twenty-six cases of sampled soils with a total petroleum hydrocarbon concentration of less than 75,350 milligrams per kilogram were tested at a temperature of 850 degrees Fahrenheit (395 degrees Celsius) and a retention time of 20 minutes for changes in asphaltenes. These samples had pre-treatment asphaltene concentrations that ranged from 926 to 30,600 milligrams per kilogram. The test results for these 26 cases showed that at this temperature and retention time, the asphaltene concentrations in 25 cases were reduced to less than 500 milligrams per kilogram, with 15 non-detect results and an average asphaltene concentration of 194 milligrams per kilogram. Actually, the results in Table 5-1 from the High Temperature Thermal Desorption Bench Test provide a conservative estimate of full-scale high temperature thermal desorption system performance. The results for the full-scale system are expected to provide improved total petroleum hydrocarbon desorption efficiency. This is due to the following:

1. Although the bench test reproduces the temperature and retention time of a full-scale system, it does not provide a combustion flame. The presence of a combustion flame in a rotary dryer improves total petroleum hydrocarbon desorption and destruction, and the use of a combustion flame substantially increases the destruction efficiency of asphaltenes.

2. Although the bench scale unit rotates the soil, the rotation of the soil in the full-scale unit provides a higher degree of heat transfer due to “veiling” which causes the hot gases to contact the contaminated soil particles.

The combination of a combustion flame and “veiling”, which are difficult to reproduce in a bench test, will provide greater heat transfer between the soil and the hot gases in the full-scale system, resulting in improved total petroleum hydrocarbon desorption and destruction.

Therefore, based on the above, the following design parameters are recommended for the full scale high temperature thermal desorption unit for treating hydrocarbon-contaminated terrestrial soils, supratidal sediments and oil trench soils: Primary Chamber Temperature = 850 degrees Fahrenheit (454 degrees Celsius) or greater. At a soil temperature of 850 degrees Fahrenheit (454 degrees Celsius), total petroleum hydrocarbons removal efficiency is maximized for achieving residual total petroleum hydrocarbons target levels of less than 500 milligrams per kilogram. Primary Chamber Retention Time = 20 minutes. At a temperature of 850 degrees Fahrenheit (454 degrees Celsius) or greater and a retention time of 20 minutes, total petroleum hydrocarbons removal efficiency is optimized. Rotary Dryer Rotational Speed = 1 revolution per minute. This is representative of full-scale conditions required for increasing soil exposure to the hot gases and flame. Primary Chamber Gas Velocity = less than 1,400 feet per minute (427 meters per minute). This value of gas flow was maintained during the bench scale treatability testing and allows the venting of hydrocarbons from the primary chamber without the excessive carryover of dust particles.

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Solids Fill Ratio = less than 20 percent. This value of solids fill ratio was maintained throughout the bench scale testing and is representative of the full-scale high temperature thermal desorption fill ratio required to provide efficient heat transfer to the soil.

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JR7

JR7

Figure 3-1 Treatability Study Equipment Configuration

FIGURE 3-2. SAMPLE PREPARATION WORK SHEET

SAMPLE PREPARATION WORK SHEET KUWAIT HTTD TREATABILITY STUDY

Therm Tec, Inc. - under contract to Ecology & Environment, Inc.

CHAIN OF CUS TODY Shipping Container Information Seal Broken Information

Seal No.: Date: Label Information: Time: Total Weight: grams Operator: Condition: Soil Weight: grams

COMMENTS/OBSERVATIONS

SAFETY PROCEDURES

HANDLING PROCEDURES

HOMOGENIZATION OF CONTENTS Material >0.25 in diameter: Y / N Weight of Soil Removed: grams Material Description:

TRANSFER PROCEDURE DATE: Container No. ---à Transferred to ---à Container No. Soil Weight (g) Use PreBurn Analysis Test Condition 1 Test Condition 2 Test Condition 3 Test Condition 4 Test Condition 5 Test Condition 6 Test Condition 7 Test Condition 8 Test Condition 9 Contingency

COMMENTS

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FIGURE 3-3. LABORATORY DATA SHEET

LABORATORY DATA SHEET KUWAIT HTTD TREATABILITY STUDY

Therm Tec, Inc. – under contract to Ecology & Environment, Inc. Date: Sample Type:

Operator: Sample ID #:

Project No.: Electronic File #:

RUN CONDITIONS

FURNACE AIRFLOW SOIL Temp (degrees Fahrenheit): *Temp (degrees Fahrenheit): Retention Time (minutes):

Furnace Setting (degrees Celsius): (*maintain between 450-550 degrees Fahrenheit (232 to 288 degrees Celsius))

Temp (degrees Fahrenheit):

Rotation Speed (revolutions per minute): Airflow (Standard Cubic Feet per Minute): Charge Volume (cubic centimeters) Start:

Furnace Preheat Setting: Charge Volume (cubic centimeters) End:

Fill Ratio:

WEIGHT MEASUREMENTS Sample Verification #: Tag Wt. grams Actual Weight: grams

UNTREATED TREATED

Cell w/ Charge Tare grams Cell w/ Charge Tare grams

Cell Tare: grams Cell Tare: grams

Charge Weight grams Charge Weight grams

BURN CONDITIONS / TIME Hour Min Sec Set

degrees Celsius

TC-D degrees

Fahrenheit

Air In degrees

Fahrenheit

Comments

Charge In

Air On

Start Time

End Time/ Air Off

Charge Out

NOTES

DESCRIPTION OF UNTREATED SAMPLE TREATED SAMPLE

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FIGURE 3-4. DAILY ACTIVITY LOG

DAILY ACTIVITY LOG KUWAIT HTTD TREATABILITY STUDY

Therm Tec, Inc. - under contract to Ecology & Environment, Inc. Operator: Date:

VISITORS ON-SITE

DEVIATIONS FROM WORK PLAN

SUMMARY OF DAY’S ACTIVITIES

COMMENTS

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Documents

“Oil Lakes” Monitoring and Assessment Report Marine and ... Technolo… · parameters (see Appendix F to Volume 2 of the “Oil Lakes” M & A Report). For a specific petroleum-contaminated