New Technologies for Site Measurement and Remediation

Transcription

1 New Technologies for Site Measurement and Remediation June 7 th, 2006 Masaaki Hosomi Tokyo University of Agriculture and Technology

2 Contents Ground Air System (GAS) for Chlorinated ethenes: Non-drilling Soil-gas Survey Kimitsu System Co. Ltd. & GAS Research Association Real-Time PCR Techniques Targeting 16S rdna of Dehalococcoides for Bioremediation of Chlorinated ethenes Kanji Nakamura et al. & Kurita Water Industries Ltd. Nakashima et al. (Kokusai Kogyo Co. Ltd.) Non-combustion technology for dioxin, PCB and POPs pesticides: Mechanochemical Process (MC) Radicalplanet Research Institute Co. Ltd.

3 Ground Air System (GAS) ~ Non-drilling Soil Gas Survey ~ Copy Right: Kimitsu System Co.Ltd International Patentee: Suzuki Yoshikazu ( info@kimitsu-system.com)

4 Ground Air System (GAS) The soil-gas is extracted by the vacuumed pressure inside the GAS vessel. Soil gas detector Sampling pump Main pump -Vacuum pump -Blower GAS Vessel : Soil gas air flow

5 Soil-gas survey Drilling system The sampling pipe is set up under the soil. High Cost Non-drilling system The device is set up on the ground level. Low difficult Floor inside of factories and buildings under operating Ground covered with concrete Possible Searching hot-spot (a heavily polluted area) by GAS High-efficiency Low cost

6 Overview of soil gas survey by GAS Gas detector Soil Gas Sampling pump Vacuum pump GAS Vessel Blower

7 To Soil Gas Sampling pump GAS Vessel Vacuum pump Blower Main pump switch cock : Air flow Pressure gauge

8 Sampling and Measuring by Gas Detector Tube Gas detector tube Sampling pump outlet

9 Connecting sampling port from GAS vessel and tetra-bag for soil gas sampling

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11 Joint Research between GAS and my Laboratory Extracted area of the soil-gas has not been understood with accuracy. Estimate extracted area of the soil-gas by the GAS. Differential pressure (DP) test Tracer test

12 Differential pressure (DP) test Estimate extracted area by the main pump. Sampling pump Main pump Manometer Measure the DP between soil and atmospheric air. Porous stone

13 Tracer test Estimate extracted area by the sampling pump. Main pump He detector Tracer gas He Sampling pump Measure the detection time of gas. Porous stone

14 Sandpit 200 cm 80 cm

15 Map of extracted area Main pump: Vacuum pump GAS 10 GAS Distance of center [cm ] Depth [cm ] Distance of center [cm ] Depth [cm ] Distribution of DP [kpa] Distribution of average transfer speed of tracer gas [cm/s] Extent of the impact of GAS is about cm vertical under GAS vessel.

16 Measurement of GAS in a Factory under Operation (MOE:Demonstration Program for Low-cost and loading type soil monitoring and remediation technologies Photo:Provided by Mitsuya Industrial Co. Ltd. ( )

17 Measurement of GASS outside a Factory under Operation (MOE:Demonstration Program for Low-cost and loading type soil monitoring and remediation technologies Provided by Mitsuya Industrial Co. Ltd. ( )

18 1 m-depth Core Boring for Soil Gas Investigation Following the Soil Investigation Manual in a Factory under Operation (MOE:Demonstration Program for Low-cost and Low-loading type Soil Monitoring and Remediation Technologies Provided by Suzuki ( )

19 1 m-depth Core Boring for Soil Gas Investigation Following the Soil Investigation Manual (Provided by Mr. Kamisuna)

20 Measurement of GAS in a Factory under Operation (MOE:Demonstration Program for Low-cost and loading type soil monitoring and remediation technologies Provided by Suzuki ( )

21 Horizontal distribution of TCE in soil gas determined by GAS without core boring(moe: Demonstration Program for Low-cost and loading type soil monitoring and remediation technologies Provided by Suzuki ( )

22 Soil-gas survey by GAS System of searching a heavily polluted area Survey on floor inside of buildings and ground covered with concrete is possible. High-efficiency and low-cost system Rapid measurement (a few minutes)

23 Development of Real-Time PCR Techniques Targeting 16S rdna of Dehalococcoides for Bioremediation of Chlorinated ethenes-contaminated Sites Kanji Nakamura (Tohoku Gakuin University)* Hiroaki Ishida (Kurita Water Industries Ltd.**)** Masahiro Mizumoto (Kurita Water Industries Ltd.**)**

24 How to manage and control bioremediation Field: Bioremediation of contaminated soil Contaminants: Chlorinated ethenes Tetrachloroethene (PCE) Trichlororethene (TCE) Dichloroethene (DCE) Vinyl chloride (VC) Microbe: Dehalococcoides bacteria Technology: Biostimulation

25 Pathway of anaerobic dechlorination Electron Donor:H 2 Electron Acceptor: PCE, TCE, c-dce, VC Produced from added organics C C H C C H H CC H C H C H H C C H H H PCE TCE c-dce VC ETH Proceed easily Dehalococcoides is needed Maymo-Gatell et al. (1997) : Dehalococcoides ethenogenes Hendrickson et al. (2002): assification of Dehalococcoides

26 TCE degradation in vials with soils from 14 different contaminated sites in Japan TCE with Na-acetate, N, P Soil Sample A B C Final Product ETH ETH ETH Detection of Dehalococcoides 16S rdna Detected Detected Detected D ETH Detected E ETH Detected GW F G ETH ETH Detected Detected Soil H I c-dce c-dce Not detected Not detected J c-dce Not detected K c-dce Not detected Incubated 60 days at 30 L M N c-dce TCE TCE Not detected Not detected Not detected 7/14 7/14

27 Dehalococcoides 16S rdna cloned from 7 vials (PCR amplified w/ Bact27f/1492r) GATGAACGCTAGCGGCGTGCCTTATGCATGCAAGTCGAACGGTCTTAAGCAATTAAGATAGTGGCGAACGGGTGAG TAACGCGTAAGTAACCTACCTCTAAGTGGGGGATAGCTTCGGGAAACTGAAGGTAATACCGCATGTGGTGGRCCGA CATATGTTGGTTCACTAAAGCCGTAAGGCGCTTGGTGAGGGGCTTGCGTCCGATTAGCTAGTTGGTGGGGTAATGGC CTACCAAGGCTTCGATCGGTAGCTGGTCTGAGAGGATGATCAGCCACACTGGGACTGAGACACGGCCCAGACTCCT ACGGGAGGCAGCAGCAAGGAATCTTGGGCAATGGGCGAAAGCCTGACCCAGCAACGCCGCGTGAGGGATGAAGGC TTTCGGGTTGTAAACCTCTTTTCATAGGGAAGAATAATGACGGTACCTGTGGAATAAGCTTCGGCTAACTACGTGCC AGCAGCCGCGGTAATACGTAGGAAGCAAGCGTTATCCGGATTTATTGGGCGTAAAGTGAGCGTAGGTGGTCTTTCA AGTTGGATGTGAAATTTCCCGGCTTAACCGGGACGAGTCATTCAATACTGTTGGACTAGAGTACAGCAGGAGAAAA CGGAATTCCCGGTGTAGTGGTAAAATGCGTAGATATCGGGAGGAACACCAGAGGCGAAGGCGGTTTTCTAGGTTGT CACTGACACTGAGGCTCGAAAGCGTGGGGAGCGAACAGAATTAGATACTCTGGTAGTCCACGCCTTAAACTATGGA CACTAGGTATAGGGAGTATCGACCCTCTCTGTGCCGAAGCTAACGCTTTAAGTGTCCCGCCTGGGGAGTACGGTCGC AAGGCTAAAACTCAAAGGAATTGACGGGGGCCCGCACAAGCAGCGGAGCGTGTGGTTTAATTCGATGCTACACGA AGAACCTTACCAAGATTTGACATGCATGTAGTAGTGAACTGAAAGGGGAACGACCTGTTAAGTCAGGAACTTGCAC AGGTGCTGCATGGCTGTCGTCAGCTCGTGCCGTGAGGTGTTTGGTTAAGTCCTGCAACGAGCGCAACCCTTGTTGCT AGTTAAATTTTCTAGCGAGACTGCCCCGCGAAACGGGGAGGAAGGTGGGGATGACGTCAAGTCAGCATGGCCTTTA TATCTTGGGCTACACACACGCTACAATGGACAGAACAATAGGTTGCAACAGTGCGAACTGGAGCTAATCCCCAAAG CTGTCCTCAGTTCGGATTGCAGGCTGAAACCCGCCTGCATGAAGTTGGAGTTGCTAGTAACCGCATATCAGCATGGT GCGGTGAATACGTTCTCGGGCCTTGTACACACCGCCCGTCACGTCATGAAAGCCGGTAACACTTGAAGTCGATGTG CCAACCGCAAGGAGGCAGTCGCCGAGGGTGGGACTGGTAATTGGGACG (Position148:AorG) A dominant type of Dehalococcoides existing in Japan

28 Detection of Dehalococcoides 16S rdna by block PCR Groundwater A Groundwater B Groundwater C Groundwater D Groundwater A Groundwater B Groundwater C Groundwater D bp 628 bp Primer pair A Loffler et al. (2000). Primer pair B (De624f and De1232r) This study

29 Real-Time PCR by LightCycler Dehalococcoides 16S rdna concentration (copies/ml) PCR Cycle Number that amplified a certain amount of DNA

30 Detection of Dehalococcoides 16S rdna by Real-Time PCR Chlorinated ethenes & Ethene (mg/l) De-16S rdna c-dce 10 7 VC 10 6 ETH Time (days) De-16S rdna (copies/ml)

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32 Dehalococcoides 16S rdna (copies/ml) Full scale biostimulation Initial Dehalococcoides 16S rdna concentrations in groundwater at a contaminated site No.1 No.2 No.3 No.4 No.5 No.6 No.7 No.8 Monitoring wells in bioremediation area The result showed the feasibility of biostimulation

33 Change of De-16S rdna concentrations in groundwater Intermittent addition of organics and nutrients from multiple wells w/o circulation 1.0E+08 Significant increase was observed in 3 months 16S rdna (copies/ml) 1.0E E E E E E E E Time (days)

34 The increase of Dehalococcoides population led the decrease of chlorinated ethenes in the field Dehalococcoides 16S rdna (copies/ml) Chlorinated Ethenes (µg/l) 1.0E E E E E E E E Time (days) De 16S rdna All field data showed this correlation TCE c-dce VC Target value for c-dce

35 Conclusions 1.Dehalococcoides population was needed for complete dechlorination. 2.A certain type of Dehalococcoides was dominant in Japan. 3.Real-Time PCR targeting 16S rdna of Dehalococcoides was successfully used to manage the full scale biostimulation.

36 Non-combustion technology for dioxin, PCB and POPs pesticides: Mechanochemical Process (MC) Radicalplanet Research Institute Co. Ltd. & Hosomi Laboratory

37 Background for Non-combustion Technologies POPs Convention requires disposal techniques to be in environmentally sound manner and not produce other POPs byproducts in the national implementation plan. Environmental and health concerns about release of POPs by-products like dioxins from incineration plants have triggered the development of alternative destruction technologies.

38 PCB problems in Japan PCB wastes including transformers, capacitors and carbonless copy paper have been stored for about 30 years because construction of incineration plant as PCB disposal facility has not been accepted publicly. In order to manage the risk of PCB release into the environment during long-term PCB storage, the central government established the evaluation system of emerging and alternative destruction technologies in 1996, i.e., non-combustion technologies.

39 Development of non-combustion technologies Private sectors have demonstrated the performance and effectiveness of non-combustion technologies for destruction of PCB wastes. Most of non-combustion technologies include chemical dehalogenation process with liquid phase reaction. (i.e., minimization of off-gas generated and easiness of verification of PCB degradation) Definition of non-combustion technologies: alternative destruction technologies of incineration

40 Approval of non-combustion technologies The committees organized by the central government have reviewed these demonstration data in terms of treatment performance, by-products, final products, operation conditions and environmental concerns and confirmed several alternative technologies as officially approved PCB-disposal technologies.

41 Approved PCB Treatment Technologies Decomposition technologies of liquid PCB waste Chemical dehalogenation -Base catalyzed decomposition -Metallic sodium dispersion process -UV irradiation -Pd/C catalytic hydrogenation reduction -t-c 4 H 9 OK chemical extractive decomposition Molten metal decomposition Plasma decomposition Hydrothermal decomposition and Supercritical water oxidation Mechanochemical process (officially granted by the notification (No.25, April 1, 2004) Washing and separation technologies of PCB waste Vacuum thermal separation Solvent/oil washing

42 Why do we focus on MC process? Non-heating process osed system High Safety + On-site treatment by mobile equipment Lower cost and remove anxiety without transfer of pollutants Community and Public acceptance MC is applicable to remediation of small site

43 CaO Target substance CaO Rotation (700rpm) Stainless steel pot steel balls Rotating Disk Revolution (700rpm) Mechanochemical (MC) treatment with a planetary ball mill

44 Total chlorine ratio (%) Milling time (h) Chlorine ratio in remaining 4CB Chloride ions ratio Chlorine balance during MC treatment of 4-chlorobiphenyl (4CB)

45 Time dependence of the molar ratio of degradation products during MC treatment of 4CB. Molar ratio [%] CB Biphenyl Cyclohexylbenzene Terphenyl Quarterphenyl Total Milling time [h]

46 Dechlorination * Radically H ydrogenate -reduction - Polym erization R a d ic a lly * * Polymerization Polym erization ** Q uaterphenyls Terphenyls Hydrogenate-reduction * D e c o m p o s itio n to lo w e r m o le c u la r c o m p o u n d s M ineralization? Proposed degradation pathways of 4CB by the MC treatment. (*, not detected; **, detected, but not confirmed by spike test

47 conc. (pg) T4CDDs P5CDDs H6CDDs H7CDDs O8CDD Milling time (min) Degradation of OCDD and by-products during MC treatment of OCDD

48 Milling time (min) T4CDFs P5CDFs H6CDFs H7CDFs O8CDF Degradation of OCDF and by-products during MC treatment of OCDF

49 Dechlorination rates [%] based on analyses of chloride ions after MC treatment of OCDD and OCDF for 2 h showed 99.9% and 99.3%, respectively. Nomura and Hosomi (2005) Elucidation of degradation mechanism of dioxins during mechanochemical treatment, Env. Sci. Tech., 39, Note that this is the first study to demonstrate 100% dechlorination of dioxins by measuring the amount of chloride ions produced during the MC treatment of OCDD/OCDF. No remaining dioxins or no other organochlorine compounds were detected, which confirms the complete dechlorination of OCDD/F.

50 What is Japanese Stockpile? MOAFF put out the notice of collecting unused POPs pesticides in shed of end users through NOKYO and burying collected pesticides underground in 1972 because of their toxicity and adverse effects on human health. Buried POPs pesticides are defined as Japanese Stockpile. MOAFF has started to identify quantity and location of buried POPs pesticides since adoption of POPs convention and reported that total amount of buried POPs is about 4000 t and there are about 200 sites through sending out questionnaires to local governments and NOKYO. Buried POPs pesticides mainly consist of BHC, DDT, Chlordane, Dieldrin, Endrin, Aldrin, and Heptachlor.

51 Employed Technologies in MOAFF s Project 2000 fiscal year Mechanochemical process 2001 fiscal year Hydrothermal decomposition Vacuum thermal decomposition Geo-Melt vitrification 2002 fiscal year Metallic sodium dispersion process Base catalyzed decomposition Supercritical water oxidation

52 Dechlorination ratio reached 100 % in treatment of target compounds No organochlorine compound was detected as degradation products by the GC-MS analysis Feasibility of treating POPs Pesticides using MC process Target compounds for treatment H H H H Heptachlor γ-hch NO 2 PCNB additives CaO:2 g target compound: 50 mg Rotational speed:700 rpm Milling time :2 h Chloride ions extracted by hot water and ultrasonic cleaning for milled mixtures were measured by ion chromatography. Target compound Heptachlor γ-hch PCNB Dechlorination ratio(%) ( Dechlorination ratio: the amount of chloride ions / chlorine in a target compound added to the system )

53 Degradation mechanism of γ-hch during MC treamtment Experimental condition Additives : Amounts : HCH and CaO 1:10 molar ratio with respect to chlorine bound γ- HCH to calcium as CaO Milling time : 120 min Toward to elucidate the degradation behavior of γ- HCH Ion chromatograph for analysis of chloride ions in milled mixtures GC-MS for analysis of HCH and the degradation products in milled mixtures

54 100% dechlorination accomplished, and Degraded to lower molecular compounds including Carbon! Degradation pathway of γ-hch by MC treatment H H Dehydrochlorination (-H) HCH H H 2,3,4,5,6-pentachlorohexene (PCCH) H Dehydrochlorination (-H) Dehydrochlorination (-H) H H H 1,2,4-TriCB Major > 1,2,3-TriCB H H H 1,3,5-TriCB dechlorination dechlorination dechlorination 1,2-DCB 1,4-DCB 1,2-DCB 1,3-DCB 1,3-DCB dechlorination

55 Conclusions Dechlorination ratio reached 100 % in treatment of heptachlor, HCH and PCNB, and no organochlorine compound was detected by GC-MS analysis. These results confirmed the feasibility of treating POPs pesticides. Dechlorination ratio in the MC treatment of HCH increased with milling time, and reached 100 % in 120 min. Chlorobenzenes and 2, 3, 4, 5, 6-pentachlorocyclohexene (PCCH) were identified as the major degradation products of the MC treatment of HCH. The degradation of HCH proceeds via dehydrochlorination and the dechlorination of degradation products.

56 Schematic Profile of Commercial MC plant motor MC reactor Planet E-200 powder collecting equipment Radicalplanet Research Institute Co. Ltd.

57 Commercial MC plant owned by Radicalplanet Research Institute Co. Ltd. Produced by Sumitomo Heavy Industries Techno-Fort Co.,Ltd. E-200 Type

58 Transportability of MC Plant (Planet E-200) Radicalplanet process consists of the Planet E-200, a motor and powder collecting equipment. These equipments are simple, compact, separated and are transportable by trailers.

59 Skematic Mechanochemical Plant by Radicalplanet Research Institute Co. Ltd. Top Plate Direction of Each Reaction Pot Rotation Pot Axis Reaction Pot Base Plate Base Axis Direction of Base Plate Rotation Pot Plate

60 PCB-contaminated Soil Destruction Treatments PCB-contaminated soil PCB oil and mixed oil T im e (h rs)p C B (m g/kg) 0 1, N D (<0.01) DXNs(pg- TEQ/ g) PCDDs+PCDFs Co- PCB Total

61 PCB(Fluorescent Ballast containing PCB Oil) Destruction Treatments Fluorescent Ballast PCB oil and mixed oil T im e (h rs)p C B (m g/kg) 0 1, N D (<0.01) 32 N D (<0.01) 64 N D (<0.01) DXNs(pg- TEQ/ g) PCDDs+PCDFs Co- PCB Total

62 γ-bhc Destruction by MC Treatments 50,000 40,000 46,827ppm γ-b H C (ppm ) 30,000 20,000 10,000 10,146ppm D Es(%) > DREs(%)> DXNs(pg-TEQ /g)=0.031 γ-bhc (liquid) TIM E(hrs)

63 PCP Destruction by MC Treatments 8,000 6,000 6,652ppm (67%PC P) PCP (ppm ) 4,000 2,000 0 D E s(% ) > D R E s(% ) > DXNs(pg-TEQ /g)= PCP (Pentachlorophenol) -2,000 TIM E(hr)

64 Chlordane Destruction by MC Treatments 5,000 4,000 3,986ppm (40%) Chlordane (ppm ) 3,000 2,000 1,000 Des(%)> DREs(%)> D XN s (pg-teq /g) = TIM E(hrs) Chlordane

65 MC Destruction of Mixed Agricultural Chemicals DDT Powder Results o f D istruction (Unit:mg/ kg) BHC Powder DDT BHC op'ddt pp'ddt pp'ddd pp'dde α BHC β BHC γ BHC δ BHC Endrin 8 H rs A fter <0.001 <0.001 < <0.001 <0.001 <0.001 <0.001 <0.001 Admixture of Powder Endrin Powder POPs Wastes Weights : 20~80kg / Charge

66 POPs Wastes Treated by MC (1) Concrete and Soil Plastic Masks othe and Work Gloves Protective clothing (Tyvex)

67 Pieces of PP and PVC Pipes and Can made of Metal POPs Wastes Treated by MC (2) Chipped Wood Cardboard

68 Destruction Treatment of Mixed Wastes Mixed Wastes in Reaction Pot MC Destruction Powder after MC Treatment

69 Summary GAS is very promising and time- and cost-saving technology for soil gas survey in urban area including operating factory with concrete floor. High-sensitive real-time PCR techniques targeting 16S rdna of Dehalococcoides give valuable information on applicability of biostimulation in small sites. MC process is applicable to remediation in small sites contaminated by pretty high-strength POPs.