Termisk assisteret oprensning af høfdedepotet, Høfde 42, Harboøre Tange Bilag I Rapport over Treatability forsøg – Kemron (engelsk)DENMARK THERMAL PESTICIDE STUDY HARBOØRE, DENMARK September 11, 2006 Revision 02 Prepared for: Prepared by:
Atlanta, GA 30318 Submitted By: Reviewed By: Denmark Thermal Pesticide Study Harboøre, Denmark Mr. Gorm Heron Table of Contents
LIST OF TABLES TABLE 1 – Untreated Material Characterization TABLE 2 – Titration Data TABLE 3 – Hydrolysis Batch Study – pH Data TABLE 4 – Hydrolysis Batch Study – Off-Gas Monitoring TABLE 5 – Thermal Treatment – Total Mercury Analyses LIST OF FIGURES FIGURE 1 – 70°C Test – Temperature Monitoring FIGURE 2 – 90°C Test – Temperature Monitoring FIGURE 3 – 100°C Test – Temperature Monitoring FIGURE 4 – 300°C Test – Temperature Monitoring LIST OF APPENDICES APPENDIX A - CHAIN OF CUSTODY Data contained on this sheet shall not be disclosed without prior approval from KEMRON Environmental Services, Inc. (Proprietary) Denmark Thermal Pesticide Study Revision 02 1.0 INTRODUCTIONKEMRON Environmental Services, Inc. (KEMRON) has developed this report as a presentation of the final results of the bench-scale treatability study conducted for TerraTherm, Inc. (TerraTherm). The study was conducted on a material sampled from the Cheminova Plant (the site) located in Harboøre, Denmark. Cheminova is a manufacturer of chemicals used in the agriculture industry, including pesticides, herbicides, and fungicides. The treatability study was performed in an effort to evaluate different potential full-scale remediation options selected by TerraTherm. The approaches included hydrolysis and thermal treatments designed to reduce concentrations of contaminants in soil material sampled from the site. 1.1. Scope of WorkThe objectives of the treatability study are 1) characterize the physical properties of the site materials; 2) determine the buffering capacity of the site materials, 3) evaluate degradation of the site contaminants via hydrolysis, and 4) evaluate low temperature thermal treatment of the site materials. 1.2. Report OrganizationThe Denmark Thermal Pesticide Study was completed in a phased approach. The following outlines the study phases: Untreated material characterization Buffering Capacity Determination Thermal Treatment Evaluations Throughout the course of this study KEMRON performed testing on aliquots of materials being evaluated. Testing was performed at KEMRON’s Applied Technologies Group facilities located in Atlanta, Georgia, and KEMRON’s analytical laboratory located in Marietta, Ohio. The data corresponding to these evaluations are presented in summary tables attached to this text. Complete data reports, where applicable, are included in Attachment B. Note that the majority of analytical testing conducted on the study materials was performed by Cheminova and are not included in this report. 2.0 UNTREATED MATERIAL RECEIPT AND HANDLING2.1. Untreated Material ReceiptOn 3 May 2006 KEMRON received approximately 47.5 kilograms (kg) of soil and approximately 20 liters (L) of groundwater material from the site. The materials were delivered in multiple glass containers and represent samples from varying locations and depths at the site. Upon receipt, the site materials were logged into KEMRON’s sample tracking system and placed in sec storage maintained at a temperature of 4°C. A copy of the chain of custody is presented Prior to initiating the treatability study, KEMRON developed a master soil composite using the most shallow soil materials as directed by Terratherm. Four containers identified as “5-6” were composited. The shallow soils were cooled and then combined in a stainless steel mixing basin and homogenized to ensure a uniform material for testing. Homogenization was performed by mixing the soil material, by hand, using stainless steel utensils until visually homogenous. For treatability testing, KEMRON typically removes oversized particles and debris larger than 0.5 inch in diameter in order to facilitate bench-scale testing. During homogenization, no 2.2. Material CharacterizationKEMRON collected representative aliquots of the untreated soil composite for characterization testing. The establishment of the baseline characteristics of the untreated samples is important for ensuring that the materials are similar to those expected at the site and for evaluating the effectiveness of treatments applied. The following testing was conducted on aliquots of the composite soil, after homogenization, in accordance with the referenced test methods: Parameter Material pH Method EPA Method 9045 ASTM D2216 Denmark Thermal Pesticide Study Harboøre, Denmark Revision 01 2.3. Results of Untreated Characterization TestingThe results of untreated characterization testing performed by KEMRON are presented in Table 1. Complete laboratory data reports for all analytical testing performed by KEMRON in this study are included as Appendix B. The following is a summary presentation of Table 1:
Complete tables including flagging definitions are included in the Tables section of this report. Revision 02 3.0 BUFFERING CAPACITYUpon completion of untreated material characterization testing, KEMRON performed a titration test of a slurry composed of a 3:1 ratio of site soil to site groundwater. This titration was conducted to estimate the buffering capacity of the site composite material. Specifically, 60 gram The following is a graphical presentation of the BUFFERING CAPACITY 4.0 HYDROLYSIS BATCH TREATMENTKEMRON conducted the Hydrolysis Batch Treatment phase of the study on aliquots of the 3:1 site soil to groundwater slurry. Testing was conducted using four separate treatment parameters including the following: 1) decreased temperature (10 degrees Celsius (°C)) with no pH adjustment; Each of the four reactors was developed in 1 L amber glass jars equipped with a cap fitted with Testing was conducted for a period of approximately 7 days. Throughout testing, KEMRON monitored the pH of each test parameter using “mini” reactors. Specifically, KEMRON prepared 7 additional reactors for each test parameter, one for each day of the test duration. These “mini” reactors were developed in 40ml VOA vials using the protocol previously discussed. Each day the appropriate specimen was removed from testing and evaluated for material pH. The results of pH monitoring are presented in Table 3. The following is a summary of Table 3:
In addition to pH monitoring, KEMRON attempted to collect off-gas produced from treatment in Tedlar bags. To accomplish off-gas collection, a stainless steel needle was attached to a 1-liter Tedlar bag using SwageLok® compression fittings. The needles were then inserted into each reactor through the cap via the septum. It was anticipated that any off-gas created from the hydrolysis reaction would be collected in the Tedlar bags allowing for off-gas evaluations to be conducted via real-time gas monitors. However, it was observed that little or no off-gas was collected from any of the test materials. Due to this event, KEMRON performed off-gas monitoring activities within the available headspace of each reactor by connecting real-time gas meters to the stainless steel needle inserted through the septum. Specific off-gas parameters evaluated in each reactor included volatile organics, hydrogen sulfide, sulfur dioxide, oxygen, lower explosive limit, sulfur monoxide, hydrogen, methane, nitric oxide, nitrogen dioxide, carbon monoxide, and carbon dioxide. In order to evaluate all of the parameters listed above, it was necessary to use several different gas detection meters as outlined below. Note that sulfur monoxide was measured via Dragger detection tubes. Due to the fact that the gas meters operate by passing a continuous stream of air over specific sensors, it is suspected that the volume of gas contained within the headspace of the reactors may have been insufficient for complete and accurate measurements. This is noted in the summary data table associated with gas detection. Note that the evaluation of certain gases was not performed at all test intervals due to non-detected concentrations in the early stages of testing. Additionally, KEMRON was requested to monitor for phosgene gas, however, this parameter was not performed since positive pressure was not developed from the test reactors and due to the suspected insufficient gas generation in the headspace of the reactors. The results of off-gas monitoring are presented in Table 4 attached to this text.
At the conclusion of testing, aliquots of the liquid fraction of each test material were removed for analytical testing at Cheminova. Additionally, KEMRON performed the client specified extraction procedure on the solids portion of the test materials. Specifically, the extraction procedure was performed using the following protocol: 1. 1.0 gram of the test soil was placed in a 40ml VOA vial. Following completion of the extraction procedure, the liquid fraction and the soil extract from each reactor was forwarded to Cheminova for analytical testing. Due to complications during shipment, many of the sample extracts were lost due to breakage. Unextracted soil aliquots were then shipped to Cheminova for on-site extraction and analysis. 5.0 THERMAL TESTINGThermal treatment testing was performed to evaluate the potential destruction of pesticides under elevated temperatures using hot water, steam, or heat alone. Specifically, thermal treatment was conducted at temperatures including 70, 90, 100, and 300 °C. Testing was conducted on the site materials prepared by combining the composite site soil and the site groundwater at a soil to groundwater ratio of 3:1. Because of the elevated moisture content of the test material, KEMRON performed thermal testing using a stainless steel box instead of the column which was proposed in the initial study design. Immediately prior to adding the untreated site composite material to the reactor, aliquots of the test materials were removed for analytical testing. Specifically, a portion of the Time-0 material was forwarded to KEMRON’s analytical laboratory located in Marietta, Ohio for mercury analyses; and a fraction of the untreated test material was subjected to the project specific extraction method previously outlined in this text. This extract was then forwarded to Cheminova for additional analytical testing; however similar complications with the extract occurred as stated in section 4.0 of this report. Accordingly, soil aliquots were sent to Cheminova as stated in section 4.0 above. As previously stated, a stainless steel reactor measuring approximately 8 inches in length, 4 inches in width, and 3 inches deep was used to hold the untreated composite material during heating. The thermal reactor was closed with a stainless steel lid equipped with a high pressure carbon gasket. The lid was fitted with ports for temperature monitoring as well as ports for inflow and outflow gas lines. Prior to initiating thermal testing, the reactor with the site composite was placed into a Fisher Scientific Series 750 muffle furnace capable of reaching temperatures as high as 2,100 °F. Additionally, where necessary, a second drying oven was used to heat site groundwater or deioized water in a second reactor. The goal of the second drying oven/reactor system was to produce heated water or steam which was injected into the soil reactor. The following sections present the protocol used during each thermal investigation. 5.1. 70°C TestThe 70°C test was performed using a dual oven set-up. A drying oven was utilized to preheat groundwater which was pumped into the treatment reactor. The treatment reactor was placed into a Fisher Scientific brand muffle furnace. Both ovens were operated at a temperature of approximately 70°C. A reactor filled with groundwater from the site was placed into the drying oven for heating. A peristaltic pump introduced additional groundwater into the reactor at a rate of approximately 0.5 milliliters per minute (ml/min). A heated stainless steel line allowed the preheated groundwater to be transferred to the soil treatment reactor at a consistent temperature of approximately 70°C. This was accomplished by covering the stainless steel line with electrical heating tape adjusted to approximately 70°C. The water transfer was assisted with presurrized breathing air applied to the groundwater reactor. Pressure was applied at a rate of approximately 50 ml/min. Although air was not directly injected into the soil reactor, it is possible that a portion of the air may have acted as a carrier for the water. An off-gas system was utilized during treatment to remove vapors from the treatment reactor and to prevent potential harmful constituents from being introduced into the environment. This off-gas system w attached to a port in the top of the soil reactor which included a condenser, high volume vacuum pump and carbon scrubber. Treatment was conducted for a period of approximately 7 days. Throughout this test duration approximately 6 liters of groundwater were passed through the soil test reactor. At the conclusion of the treatment period the test system was disassembled. The treated soil material was cooled and then extracted using the extraction method previously outlined. Additionally, aliquots of the treated soil material and condensate collected from testing were also submitted to KEMRON’s analytical laboratory for total mercury analysis. As stated above, additional soil aliquots were collected and shipped to Cheminova for extraction and analysis due to loss of sample extract during the initial delivery. 5.2. 90°C TestThe 90°C test was completed as an additional test to the initial three thermal evaluations proposed. This occurred inadvertently due to difficulty with the thermocouple measuring the oven temperature which was made apparent at the conclusion of the test. After scrutinizing the temperature data, KEMRON concluded that the soil had been treated at an average temperature of approximately 90°C for a large portion of the treatment duration. Additionally, 5.3. 100°C TestThe 100°C test was performed in a similar manner and set-up to the 70°C test; however, rather than preheated groundwater, steam was pumped through the soil reactor. To produce steam, KEMRON injected deionized water via a peristaltic pump into a second reactor placed inside a drying oven operating at a temperature of approximately 120°C. Similar to other set-ups, breathing quality air assisted in the transfer of the steam to the soil reactor located inside the muffle furnace. The operating temperature of the muffle furnace was approximately 100°C. After the 7-day treatment period, the test reactor was disassembled and test material allowed to cool. The treated material was subjected to the project specific extraction method, and total mercury analysis. Additionally, an aliquot of the condensate material was also subjected to total mercury analysis. As stated above, additional soil aliquots were collected and shipped to Cheminova for extraction and analysis due to loss of sample extract during the initial delivery. 5.4. 300°C TestUnlike the previous tests, the 300°C test was performed using a single oven. The soil reactor was placed inside a Fisher muffle furnace set at an operating temperature of approximately 305°C. Breathing quality air was introduced into the reactor at a rate of approximately 50 milliters/min. As with the previous thermal evaluations, an off-gas condensing system was also utilized for this test. Following a 7-day retention period, the treated soil material was subjected to the project specific extraction method as well as total mercury analyses. As with the other treatments, an aliquot of the condensate was submitted for total mercury analysis. As stated above, additional soil aliquots were collected and shipped to Cheminova for extraction and analysis due to loss of sample extract during the initial delivery. 5.5. DiscussionAs indicated by the temperature data for the 100°C test, the temperature of the soil did not stay consistently at 100°C but was off on an average of about 5%. Additionally, the treated soils collected at the conclusion of the test were wet. The design of the system was such that the stea was directed toward the bottom of the reactor containing the test material to ensure that steam percolated through the test sample. It is likely that the weight of the test material may Graphical presentations of temperature monitoring conducted during all thermal evaluations are included as figures attached to this text. Additionally, the results of total mercury analyses performed by KEMRON are included as Table 5. The following is a summary of Table 5.
Total pore volume was calculated to be 671.2 cc. section of this report. Supporting data is attached in the Laboratory Reports 6.0 DISCLAIMERWhen performing treatability studies, KEMRON Environmental Services is typically provided with samples from a given site. These samples usually have been collected by site personnel an are intended to be representative of site materials. The treatability study, however, is only KEMRON has applied our best technical and scientific knowledge to the performance of the work under the economic parameters of this study. The information contained in this report in no way guarantees the same results in full-scale adaptation and is only intended as an estimate of potential site conditions. Finally, note that many treatment reagents and approaches are covered by various patents. However, KEMRON has not researched any patent issues associated with the treatment evaluations presented herein. KEMRON can make no claims as to the relevance or applicability of any patents to the treatment evaluations presented herein. TABLESData contained on this sheet shall not be disclosed without prior approval from KEMRON Environmental Services, Inc. (Proprietary) KEMRON ENVIRONMENTAL SERVICES, INC. TERRATHERM DENMARK THERMAL PESTICIDE STUDY TABLE 1 Untreated Material Characterization
* TerraTherm provided specific gravity of soil KEMRON Environmental Services, Inc. Applied Technologies Group KEMRON ENVIRONMENTAL SERVICES, INC. TERRATHERM DENMARK THERMAL PESTICIDE STUDY TABLE 2
NOTES: The untreated composite was prepared using 60g of soil and 20g of water KEY KEMRON ENVIRONMENTAL SERVICES, INC. TERRATHERM DENMARK THERMAL PESTICIDE STUDY Table 3
KEMRON Environmental Services, Inc. Applied Technologies GroupDENMARK THERMAL PESTICIDE TREATABILITY STUDY TERRATHERM, INC. Table 4 Summary of Hydrolysis Study Gas Analyses
KEMRON ENVIRONMENTAL SERVICES, INC.TERRATHERM
|
SAMPLEID | THERMAL TREATMENT TEMPERATURE |
RESULTS | |||||||
Treated Soil | Condensate | ||||||||
Mercury (mg/Kg) |
Solids Content (%) | Mercury (mg/L) | |||||||
Control 70 l°C + GW 90°C + GW 100°C + Steam 300°C |
- 70°C 90°C 100°C 300°C |
42.9 86.5 45.0 42.7 6.0 |
77.5 84.5 98.4 83.4 99.6 |
- 0.00348 0.00593 0.0120 0.718 |
FIGURE 1
Thermal Treatment @ 70°C + Groundwater
Summary of Temperature Monitoring
FIGURE 2
Thermal Treatment @ 90°C + Groundwater
Summary of Temperature Monitoring
FIGURE 3
Thermal Treatment @ 100°C + Steam
Summary of Temperature Monitoring
FIGURE 4
Thermal Treatment @ 300°C
Summary of Temperature Monitoring
Version 1.0 Oktober 2007, © Miljøstyrelsen.