METHOD 3545
PRESSURIZED FLUID EXTRACTION (PFE)
1.0SCOPE AND APPLICATION
1.1 Method 3545 is a procedure for extracting water insoluble or slightly water soluble semivolatile organic compounds from soils, clays, sediments, sludges, and waste solids. The method uses elevated temperature (100E C) and pressure (1500 - 2000 psi) to achieve analyte recoveries equivalent to those from Soxhlet extraction, using less solvent and taking significantly less time than the Soxhlet procedure. This procedure was developed and validated on a commercially-available, automated extraction system.
1.2This method is applicable to the extraction of semivolatile organic compounds, organophosphorus pesticides, organochlorine pesticides, chlorinated herbicides, and PCBs, which may then be analyzed by a variety of chromatographic procedures.
1.3This method has been validated for solid matrices containing 250 to 12,500 μg/kg of semivolatile organic compounds, 250 to 2500 μg/kg of organophosphorus pesticides, 5 to 250 μg/kg of organochlorine pesticides, 50 to 5000 μg/kg of chlorinated herbicides, and 1 to 1400 μg/kg of PCBs. The method may be applicable to samples containing these analytes at higher concentrations and may be employed after adequate performance has been demonstrated for the concentrations of interest (see Method 3500, Sec. 8.0).
1.4This method is applicable to solid samples only, and is most effective on dry materials with small particle sizes. Therefore, waste samples must undergo phase separation, as described in Chapter Two, and only the solid phase material is to be extracted by this procedure. If possible, soil/sediment samples may be air-dried and ground to a fine powder prior to extraction. Alternatively, if the loss of analytes during drying is a concern, soil/sediment samples may be mixed with anhydrous sodium sulfate or pelletized diatomaceous earth. The total mass of material to be prepared depends on the specifications of the determinative method and the sensitivity required for the analysis, but 10 - 30 g of material are usually necessary and can be accommodated by this extraction procedure.
1.5This method is restricted to use by or under the supervision of trained analysts. Each analyst must demonstrate the ability to generate acceptable results with this method.
2.0SUMMARY OF METHOD
2.1Samples are prepared for extraction either by air drying the sample, or by mixing the sample with anhydrous sodium sulfate or pelletized diatomaceous earth. The sample is then ground to a 100 - 200 mesh powder (150 μm to 75 μm) and loaded into the extraction cell.
2.2The extraction cell containing the sample is heated to the extraction temperature (see Sec. 7.8), pressurized with the appropriate solvent system, and extracted for 5 minutes (or as recommended by the instrument manufacturer). The solvent systems used for this procedure vary with the analytes of interest and are described in Sec. 5.5.
2.3The solvent is collected from the heated extraction vessel and allowed to cool.
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2.4The extract may be concentrated, if necessary, and, as needed, exchanged into a solvent compatible with the cleanup or determinative step being employed.
3.0INTERFERENCES
3.1Refer to Method 3500.
3.2If necessary, Florisil and/or sulfur cleanup procedures may be employed. In such cases, proceed with Method 3620 and/or Method 3660.
4.0APPARATUS AND MATERIALS
4.1Pressurized fluid extraction device
4.1.1Dionex Accelerated Solvent Extractor or Supelco SFE-400 with appropriately-
sized extraction cells. Currently, cells are available that will accommodate 10-g, 20-g and 30-g samples. Cells should be made of stainless steel or other material capable of withstanding the pressure requirements (2000+ psi) necessary for this procedure.
4.1.2Other system designs may be employed, provided that adequate performance
can be demonstrated for the analytes and matrices of interest.
4.2Apparatus for determining percent dry weight
4.2.1Oven - drying
4.2.2Desiccator
4.2.3Crucibles - porcelain or disposable aluminum
4.3Apparatus for grinding - capable of reducing particle size to < 1 mm.
4.4Analytical balance - capable to weighing to 0.01 g.
4.5Vials for collection of extracts - 40-mL or 60-mL, pre-cleaned, open top screw-cap with PTFE-lined silicone septum (Dionex 049459, 049460, 049461, 049462 or equivalent).
4.6Filter disk - 1.91 cm, Type D28 (Whatman 10289356, or equivalent).
4.7Cell cap sealing disk (Dionex 49454, 49455, or equivalent).
5.0REAGENTS
5.1Reagent grade chemicals shall be used in all tests. Unless otherwise indicated, it is intended that all reagents shall conform to the specifications of the Committee on Analytical Reagents of the American Chemical Society, where such specifications are available. Other grades may be used, provided it is first ascertained that the reagent is of sufficiently high purity to permit its use without lessening the accuracy of the determination.
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5.2Organic-free reagent water. All references to water in this method refer to organic-free reagent water, as defined in Chapter One.
5.3Drying agents
5.3.1
Sodium sulfate (granular anhydrous), Na SO .245.3.2Pelletized diatomaceous earth.
5.3.3The drying agents should be purified by heating at 400E C for 4 hours in a shallow
tray, or by extraction with methylene chloride. If extraction with methylene chloride is employed, then a reagent blank should be prepared to demonstrate that the drying agent is free of interferences.
5.4Phosphoric acid solution (see Sec. 5.5.5). Prepare a 1:1 (v/v) solution of 85% phosphoric acid (H PO ) in organic-free reagent water.
345.5Extraction solvents
The extraction solvent to be employed depends on the analytes to be extracted, as described below. All solvents should be pesticide quality or equivalent. Solvents may be degassed prior to use.
5.5.1Organochlorine pesticides may be extracted with acetone/hexane (1:1, v/v),
CH COCH /C H or acetone/methylene chloride (1:1,v/v), CH COCH /CH Cl .
33614 332 2 5.5.2Semivolatile organics may be extracted with acetone/methylene chloride (1:1,
v/v), CH COCH /CH Cl or acetone/hexane (1:1, v/v), CH COCH /C H .
3322 336145.5.3PCBs may be extracted with acetone/hexane (1:1, v/v), CH COCH /C H or
33614acetone/methylene chloride (1:1, v/v), CH COCH /CH Cl or hexane, C H .
3322 6145.5.4Organophosphorus pesticides may be extracted with methylene chloride, CH Cl 22or acetone/methylene chloride (11:1, v/v), CH COCH /CH Cl .
33225.5.5Chlorinated herbicides may be extracted with an acetone/methylene
chloride/phosphoric acid solution (250:125:15, v/v/v), CH COCH /CH Cl /H PO , or an 332234acetone/methylene chloride/trifluoroacetic acid solution (250:125:1, v/v/v),CH COCH /CH Cl /CF COOH. (If the second option is used, the trifluoroacetic acid solution 33223should be prepared by mixing 1% trifluoroacetic acid in acetonitrile.) Make fresh solutions before each batch of extractions.
5.5.6Other solvent systems may be employed, provided that the analyst can
demonstrate adequate performance for the analytes of interest in the sample matrix (see Method 3500, Sec. 8.0).
CAUTION: For best results with very wet samples (e.g., $30% moisture), reduce or
eliminate the quantity of hydrophilic solvent used.
5.6High-purity gases such as nitrogen, carbon dioxide, or helium are used to purge and/or pressurize the extraction cell. Follow the instrument manufacturer's recommendation for the choice of gases.
6.0SAMPLE COLLECTION, PRESERVATION, AND HANDLING
See the introductory material to this chapter, Organic Analysis, Sec. 4.1.
7.0PROCEDURE
7.1Sample preparation
7.1.1Sediment/soil samples - Decant and discard any water layer on a sediment
sample. Mix the sample thoroughly, especially composited samples. Discard any foreign objects such as sticks, leaves, and rocks. Air dry the sample at room temperature for 48 hours in a glass tray or on hexane-rinsed aluminum foil. Alternatively, mix the sample with an equal volume of anhydrous sodium sulfate or pelletized diatomaceous earth until a free-flowing powder is obtained.
NOTE:Dry, finely-ground soil/sediment allows the best extraction efficiency for nonvolatile, nonpolar organics, e.g., 4,4'-DDT, PCBs, etc. Air-drying may not
be appropriate for the analysis of the more volatile organochlorine pesticides
(e.g., the BHCs) or the more volatile of the semivolatile organics because of
losses during the drying process. The use of sodium sulfate as a drying
agent can lead to clogging of the frits in the cell with recrystallized sodium
sulfate. (See “Caution” following Sec. 5.5.6.)
7.1.2Waste samples - Multiphase waste samples must be prepared by the phase
separation method in Chapter Two before extraction. This extraction procedure is for solids only.
7.1.3Dry sediment/soil and dry waste samples amenable to grinding. Grind or
otherwise reduce the particle size of the waste so that it either passes through a 1-mm sieve or can be extruded through a 1-mm hole. Disassemble grinder between samples, according to manufacturer's instructions, and decontaminate with soap and water, followed by acetone and hexane rinses.
NOTE:The note in Sec. 7.1.1 also applies to the grinding process.
7.1.4Gummy, fibrous, or oily materials not amenable to grinding should be cut,
shredded, or otherwise reduced in size to allow mixing and maximum exposure of the sample surfaces for the extraction. The analyst may add anhydrous sodium sulfate, pelletized diatomaceous earth, sand, or other clean, dry reagents to the sample to make it more amenable to grinding.
7.2Determination of percent dry weight - When sample results are to be calculated on a dry weight basis, a second portion of sample should be weighed at the same time as the portion used for analytical determination.
WARNING:The drying oven should be contained in a hood or vented. Significant laboratory contamination may result from drying a heavily contaminated sample.
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%dry weight 'g of dry sample g of sample
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7.2.1Immediately after weighing the sample for extraction, weigh 5 - 10 g of the sample
into a tared crucible. Dry this aliquot overnight at 105E C. Allow to cool in a desiccator before weighing. Calculate the % dry weight as follows:
7.3Grind a sufficient weight of the dried sample from Sec. 7.1 to yield the sample weight needed for the determinative method (usually 10 - 30 g). Grind the sample until it passes through a 10 mesh sieve.
7.4Transfer the ground sample to an extraction cell of the appropriate size for the aliquot.Generally, an 11-mL cell will hold about 10 g of material, a 22-mL cell will hold about 20 g of material, and a 33-mL cell will hold about 30 g of material. The weight of a specific sample that a cell will contain depends on the bulk density of the sample and the amount of drying agent that must be added to the sample in order to make it suitable for extraction. Analysts should ensure that the sample aliquot extracted is large enough to provide the necessary sensitivity and choose the extraction cell size accordingly. Use disposable cellulose or glass fiber filters in the cell outlets.Clean sand may be used to fill any void volume in the extraction cells.
7.5Add the surrogates listed in the determinative method to each sample. Add the matrix spike/matrix spike duplicate compounds listed in the determinative method to the two additional aliquots of the sample selected for spiking.
7.6Place the extraction cell into the instrument or autosampler tray, as described by the instrument manufacturer.
7.7Place a precleaned collection vessel in the instrument for each sample, as described by the instrument manufacturer. The total volume of the collected extract will depend on the specific instrumentation and the extraction procedure recommended by the manufacturer and may range from 0.5 to 1.4 times the volume of the extraction cell. Ensure that the collection vessel is sufficiently large to hold the extract.
7.8Recommended extraction conditions
Oven temperature:
100E C Pressure:
1500 - 2000 psi Static time:
5 min (after 5 min pre-heat equilibration)Flush volume:
60% of the cell volume Nitrogen purge:
60 sec at 150 psi (purge time may be extended for larger cells)Static Cycles: 1
7.8.1Optimize the conditions, as needed, according to the manufacturer's instructions.
In general, the pressure is not a critical parameter, as the purpose of pressurizing the extraction cell is to prevent the solvent from boiling at the extraction temperature and to ensure that the solvent remains in intimate contact with the sample. Any pressure in the range of 1500 - 2000 psi should suffice.
7.8.2Once established, the same pressure should be used for all samples extracted
for the same analysis type.
7.9Begin the extraction according to the manufacturer's instructions.
7.10Collect each extract in a clean vial (see Sec. 7.7). Allow the extracts to cool after the extractions are complete.
7.11The extract is now ready for concentration, cleanup, or analysis, depending on the extent of interferants and the determinative method to be employed. Refer to Method 3600 for guidance on selecting appropriate cleanup methods. Excess water present in extracts may be removed by filtering the extract through a bed of anhydrous sodium sulfate. Certain cleanup and/or determinative methods may require a solvent exchange prior to cleanup and/or sample analysis.
7.12 If the phosphoric acid solution in Sec. 5.5.5 is used for the extraction of chlorinated herbicides, then the extractor should be rinsed by pumping acetone through all the lines of the system. The use of other solvents for these analytes may not require this rinse step.
8.0QUALITY CONTROL
8.1Refer to Chapter One and Method 8000 for guidance on quality control procedures. Refer to Method 3500 for specific guidance on extraction and sample preparation procedures.
8.2Before processing any samples, the analyst should demonstrate that all parts of the equipment in contact with the sample and reagents are interference-free. This is accomplished through the analysis of a solid matrix method blank (e.g., clean sand). Each time samples are extracted, and when there is a change in reagents, a method blank needs to be extracted and analyzed for the compounds of interest. The method blank should be carried through all stages of the sample preparation and measurement.
8.3Standard quality assurance practices should be used with this method. Field duplicates should be collected to validate the precision of the sampling procedures. A matrix spike/matrix spike duplicate, or matrix spike and duplicate sample analysis, and a laboratory control sample should be prepared and analyzed with each batch of samples prepared by this procedure, unless the determinative method provides other guidance.
8.4Surrogate standards should be added to all samples when listed in the appropriate determinative method.
9.0METHOD PERFORMANCE
9.1Chlorinated pesticides and semivolatile organics
Single-laboratory accuracy data were obtained for chlorinated pesticides and semivolatile organics at three different spiking concentrations in three different soil types. Spiking concentrations ranged from 5 to 250 μg/kg for the chlorinated pesticides and from 250 to 12500 μg/kg for the semivolatiles. Spiked samples were extracted both by the Dionex Accelerated Solvent Extraction system and by a Perstorp Environmental Soxtec? (automated Soxhlet). Extracts were analyzed either by Method 8270 or Method 8081. Method blanks, spikes and spike duplicates were included for the low concentration spikes; matrix spikes were included for all other concentrations. The data are reported in detail in Reference 1, and represent seven replicate extractions and analyses for each sample. Data summary tables are included in Methods 8270 and 8081.
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9.2Organophosphorus pesticides and chlorinated herbicides
Single-laboratory accuracy data were obtained for organophosphorus pesticides (OPPs) and chlorinated herbicides at two different spiking concentrations in three different soil types. Spiking concentrations ranged from 250 to 2500 μg/kg for the OPPs and from 50 to 5000 μg/kg for the chlorinated herbicides. Chlorinated herbicides were spiked with a mixture of the free acid and the ester (1:1). Spiked samples were extracted both by the Dionex Accelerated Solvent Extractor and by Soxhlet for the OPPs. Extracts were analyzed by Method 8141. Spiked chlorinated herbicides were extracted by the Dionex Accelerated Solvent Extractor and by the shaking method described in Method 8151. Extracts were analyzed by Method 8151. Method blanks, spikes and spike duplicates were included for the low concentration spikes; matrix spikes were included for all other concentrations. The data are reported in detail in Reference 2, and represent seven replicate extractions and analyses for each sample. Data summary tables are included in Methods 8141 and 8151.
9.3PCBs
Single-laboratory accuracy data were obtained for PCBs from a soil sample with PCB content certified by NIST (Standard Reference Material, SRM 1939, River Sediment). A PCB-contaminated soil was purchased from a commercial source. Spiking or certified concentrations ranged from 1 to 1400 μg/kg. Samples were extracted by the Dionex Accelerated Solvent Extractor and by Soxtec?(Perstorp Environmental). Extracts were analyzed using Method 8082. Method blanks, spikes and spike duplicates were included. The data are reported in Reference 2, and represent seven replicate extractions and analyses for each sample. Data summary tables are included in Method 8082. 10.0REFERENCES
1. B. Richter, Ezzell, J., and Felix, D., "Single Laboratory Method Validation Report. Extraction
of TCL/PPL (Target Compound List/Priority Pollutant List) BNAs and Pesticides using Accelerated Solvent Extraction (ASE) with Analytical Validation by GC/MS and GC/ECD";
Document 116064.A, Dionex Corporation, June 16, 1994.
2. B. Richter, Ezzell, J., and Felix, D., "Single Laboratory Method Validation Report. Extraction
of TCL/PPL (Target Compound List/Priority Pollutant List) OPPs, Chlorinated Herbicides and PCBs using Accelerated Solvent Extraction (ASE)". Document 101124, Dionex Corporation, December 2, 1994).
11.0SAFETY
The use of organic solvents, elevated temperatures, and high pressures in Method 3545 present potential safety concerns in the laboratory. Common sense laboratory practices can be employed to minimize these concerns. However, the following sections describe additional steps that should be taken.
11.1Extraction cells in the oven are hot enough to burn unprotected skin. Allow the cells to cool before removing them from the oven or use appropriate protective equipment (e.g., insulated gloves or tongs), as recommended by the manufacturer.
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11.2During the gas purge step, some solvent vapors may exit through a vent port in the instrument. Follow the manufacturer's directions regarding connecting this port to a fume hood or other means to prevent release of solvent vapors to the laboratory atmosphere.
11.3The instrument may contain flammable vapor sensors and should be operated with all covers in place and doors closed to ensure proper operation of the sensors. If so equipped, follow the manufacturer's directions regarding replacement of extraction cell seals when frequent vapor leaks are detected.
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December 1996METHOD 3545PRESSURIZED FLUID EXTRACTION (PFE)
METHOD 3541 AUTOMATED SOXHLET EXTRACTION 1.0SCOPE AND APPLICATION 1.1Method 3541 describes the extraction of organic analytes from soil, sediment, sludges, and waste solids. The method uses a commercially available, unique, three stage extraction system to achieve analyte recovery comparable to Method 3540, but in a much shorter time. There are two differences between this extraction method and Method 3540. In the initial extraction stage of Method 3541, the sample-loaded extraction thimble is immersed into the boiling solvent. This ensures very rapid intimate contact between the specimen and solvent and rapid extraction of the organic analytes. In the second stage the thimble is elevated above the solvent, and is rinse-extracted as in Method 3540. In the third stage, the solvent is evaporated, as would occur in the Kuderna-Danish (K-D) concentration step in Method 3540. The concentrated extract is then ready for cleanup (Method 3600) followed by measurement of the organic analytes. 1.2The method is applicable to the extraction and concentration of water insoluble or slightly water soluble polychlorinated biphenyls (PCBs) in preparation for gas chromatographic determination using either Method 8080 or 8081. This method is applicable to soils, clays, solid wastes and sediments containing from 1 to 50 μg of PCBs (measured as Arochlors) per gram of sample. It has been statistically evaluated at 5 and 50 μg/g of Arochlors 1254 and 1260, and found to be equivalent to Method 3540 (Soxhlet Extraction). Higher concentrations of PCBs are measured following volumetric dilution with hexane. 1.3The method is also applicable the extraction and concentration of semivolatile organics in preparation for GC/MS analysis by Method 8270 or by analysis using specific GC or HPLC methods. 2.0SUMMARY OF METHOD 2.1PCBs: Moist solid samples (e.g., soil/sediment samples) may be air-dried and ground prior to extraction or chemically dried with anhydrous sodium sulfate. The prepared sample is extracted using 1:1 (v/v) acetone:hexane in the automated Soxhlet following the same procedure as outlined for semivolatile organics in Sec. 2.1. The extract is then concentrated and exchanged into pure hexane prior to final gas chromatographic PCB measurement. 2.2Other semivolatile organics: A 10-g solid sample (the sample is pre-mixed with anhydrous sodium sulfate for certain matrices) is placed in an extraction thimble and usually extracted with 50 mL of 1:1 (v/v) acetone/hexane for 60 minutes in the boiling extraction solvent. The thimble with sample is then raised into the rinse position and extracted for an additional 60 minutes. Following the extraction steps, the extraction solvent is concentrated to 1 to 2 mL. CD-ROM3541 - 1Revision 0 September 1994
主要发达国家环保产业发展概况 一、美国 （一）产业分类情况 美国环保产业分为环保服务、环保设备和环境资源三大类。 （二）产业发展概况 美国现在也在面临和处理一系列挑战，包括水方面、气候变化、细菌、污染、负氧，以及水供应。美国环保局现在也在动用自己的力量重整整个水资源系统，不管是学术界还是市民，都参与到了环保的行业当中。没有人能够再袖手旁观了。
美国环保技术和设备可以帮助解决水跟土壤的问题，其实最主要的是淤泥积土。每一次下雨的时候，空气当中的污染物都会进入到的水中，包括河流，包括大江，而随着水的流动，所有的这些分子，还有污染物都会流向其他地方，所以美国现在的环保部对于处理水污染方面的技术是的重点。要减排，减少能源的消耗，同时要解决这些水方面的问题。 美国技术和设备方面的优势。美国现在已经成为全球在环境保护技术和设备方面领先的国家，美国的研发工作做得非常到位，美国使用目前的研发成果来开发新的技术，例如水资源处理，还有其他诊断和探寻设备，还有在细菌、濒危物种、化肥、杀虫剂等方面的一些技术和设备。其实，目前中国的发展也非常快，在环境方面也解决了很多的问题。面临着新一代的环境系统，在基础设施建设方面也有着更多的优势，所以创新是一个很好的推动力量，只有创新才能推动经济的长远发展，中国和全球各个国家都已经意识到了这一点。 在现代经济当中，各个国家都在鼓励新技术的创新，新技术同时也推动了经济发展，新技术是经济发展的燃料剂和助推剂，可以影响到每个人，也会影响到每天的商业决策。目前有很多数据讲的都是一些新兴企业的产品、市场、知识产权的保护，这些议题是所有全球企业都面临的议题，而同时在这样的环境当中，美国有不断的技术、产品和服务推陈出新，同时美国有着新的体系、新的标准、新的数据，还有新的发现、分析的结果，这些能够更好的保护隐私和安全。关于气候变化和天气管理的政府机构都会对进行评估，对大气、水资源等去进行环评。另外很多企业和国家都面临着非常严峻的供应链的挑战，都会考虑所有的这些环境因素，未来发展的能力已经到了一个临界点，甚至现在天灾也会带来非常严重的后果，例如地震等，另外还有全球一些地区的冲突，所以货物在运输时所造成的损失也越来越频繁，每年因为这些因素导致的货物损失高达数亿美元，有
美国EPA通用土壤筛选值
美国EPA通用土壤筛选值
CAS 号污染 物 土壤（mg/kg） 地下 （μg/L 居 住 备 注 工 业 备 注 基于 地下 水保 护 饮用 水 1 +04 E+0 5 +00 +04 75-86- 5 丙酮氰 醇 2.0E +02 n 2.1 E+0 3 n 1.2E -02 5.8E +01 75-05- 8 乙腈 8.7E +02 n 3.7 E+0 3 n 2.6E -02 1.3E +02 98-86- 2 乙酰苯 7.8E +03 ns 1.0 E+0nms 1.1E +00 3.7E +03
CAS 号污染 物 土壤（mg/kg） 地下 （μg/L 居 住 备 注 工 业 备 注 基于 地下 水保 护 饮用 水 -8 -01 E-0 1 -06 -02 79-06- 1 丙烯酰 胺 2.3E -01 c 3.4 E+0 c 9.1E -06 4.3E -02 79-10- 7 丙烯酸 3.0E +04 n 2.9 E+0 5 nm 3.7E +00 1.8E +04 107-13 -1 丙烯腈 2.4E -01 c* 1.2 E+0c* 9.9E -06 4.5E -02
CAS 号污染 物 土壤（mg/kg） 地下 （μg/L 居 住 备 注 工 业 备 注 基于 地下 水保 护 饮用 水 60-8 +00 E+0 1 -04 +00 116-06 -3 涕灭威 6.1E +01 n 6.2 E+0 2 n 9.1E -03 3.7E +01 1646-8 8-4 涕灭威 砜 6.1E +01 n 6.2 E+0 2 n 8.0E -03 3.7E +01 309-00 -2 艾氏剂 2.9E -02 c* 1.0 E-0 c 6.5E -04 4.0E -03
美国环境保护制度 篇一：环保：美国的垃圾管理机制 环境产业研究 第19期 20XX年7月27日全国工商联环境服务业商会 美国垃圾管理机制 ——商业模式下的系统化垃圾管理 作为经济大国的美国同样也是一个消费大国，持续增长的垃圾排放对其环境质量也造成了极大地威胁。据美国环境署最新公布数字显示，20XX年，美国城市固体垃圾产量达2.5亿吨，如果用卡车运送这些垃圾，组成的车队足以绕地球6圈。但是，在清晰的垃圾管理战略的指导下，美国垃圾处理产业得到了快速的发展，目前已经形成了系统化的垃圾管理商业模式，足以应对日益增长的垃圾排放量。 一、美国垃圾管理概况 （一）垃圾管理战略 美国确定的固体废弃物治理战略方针是实施源头控制政策，从生产阶段抑制废物的产生，减少使用成为污染源的物质；最大限度地实施废物资源回收，通过堆肥、焚烧热能回收利用实现废物资源、能源的再生利用，最后进行卫生填埋。 近年来，美国一直坚持垃圾减量、分流和再利用这个主题，以废物变
资源、废物变能源（焚烧和生物制肥）作为垃圾治理的主导方向，制定的20XX年的垃圾处理目标是：回收利用（包括直接回收、路边分类、堆肥、综合利用等）50%，填埋40%，焚烧10%。 为实现这些目标，美国各州普遍采取垃圾源头控制和减量措施，提出垃圾分流的概念，将食品垃圾、庭院垃圾和餐厨垃圾等按类别作为分流目标，直接进入适用的处理程序，既促进了不同成分垃圾的分类处理，也促进了资源的循环再生，垃圾处理已经形成了比较系统的模式。美国垃圾管理战略已取得了明显的成效：垃圾填埋已经从1980年的89%降为20XX年的54%，而垃圾资源回收再利用则从1980年的9.6%提高到了20XX年的33.4%，垃圾焚烧处理从1980年的1.8%上升到了20XX年的12.6%。 （二）垃圾处理方式的演变 全美国1988年共有垃圾填埋场7924个，1999年为2514个，20XX 年下降到1767个，20XX年又降为1654个，总体上呈下降趋势。垃圾焚烧厂数量从1997年的131座下降到20XX年的101座，包括焚烧和生物制能的废物变能源工厂。20XX年全美国共有废物定点回收场地12694个，路边资源垃圾分类回收项目也从1989年的1042个增长 到20XX年的7689个，成为废物资源回收的重要组成部分。 目前在美国的不同地区，垃圾处理方式的比例各不相同。如：新英格兰地区的填埋占36%，回收占33%，焚烧占31%。美国西部的填埋
9066 1 CD-ROM Revision 0 Date September 1986 METHOD 9066PHENOLICS (COLORIMETRIC, AUTOMATED 4-AAP WITH DISTILLATION) 1.0SCOPE AND APPLICATION 1.1This method is applicable to the analysis of ground water and of drinking, surface, and saline waters. 1.2The method is capable of measuring phenolic materials from 2 to 500ug/L in the aqueous phase using phenol as a standard. 2.0SUMMARY OF METHOD 2.1This automated method is based on the distillation of phenol and subsequent reaction of the distillate with alkaline ferricyanide (K Fe(CN)) and 364-amino-antipyrine (4-AAP) to form a red complex which is measured at 505 or 520 nm. 3.0INTERFERENCES 3.1Interferences from sulfur compounds are eliminated by acidifying the sample to a pH of < 4.0 with H SO and aerating briefly by stirring. 243.2Oxidizing agents such as chlorine, detected by the liberation of iodine upon acidification in the presence of potassium iodide, are removed immediately after sampling by the addition of an excess of ferrous ammonium sulfate (5.5). If chlorine is not removed, the phenolic compounds may be partially oxidized and the results may be low. 3.3Background contamination from plastic tubing and sample containers is eliminated by filling the wash receptacle by siphon (using Kel-F tubing) and using glass tubes for the samples and standards. 4.0APPARATUS AND MATERIALS 4.1Automated continuous-flow analytical instrument: 4.1.1 Sampler : Equipped with continuous mixer.4.1.2 Manifold .4.1.3 Proportioning pump II or III .4.1.4 Heating bath with distillation coil .4.1.5Distillation head .
METHOD 8318 N-METHYLCARBAMATES BY HIGH PERFORMANCE LIQUID CHROMATOGRAPHY (HPLC) 1.0SCOPE AND APPLICATION 1.1Method 8318 is used to determine the concentration of N-methylcarbamates in soil, water and waste matrices. The following compounds can be determined by this method: _______________________________________________________________________________ Compound Name CAS No.a ________________________________________________________________________________ Aldicarb (Temik) 116-06-3 Aldicarb Sulfone 1646-88-4 Carbaryl (Sevin) 63-25-2 Carbofuran (Furadan) 1563-66-2 Dioxacarb 6988-21-2 3-Hydroxycarbofuran16655-82-6 Methiocarb (Mesurol) 2032-65-7 Methomyl (Lannate)16752-77-5 Promecarb 2631-37-0 Propoxur (Baygon) 114-26-1 ________________________________________________________________________________ a Chemical Abstract Services Registry Number. 1.2The method detection limits (MDLs) of Method 8318 for determining the target analytes in organic-free reagent water and in soil are listed in Table 1. 1.3This method is restricted to use by, or under the supervision of, analysts experienced in the use of high performance liquid chromatography (HPLC) and skilled in the interpretation of chromatograms. Each analyst must demonstrate the ability to generate acceptable results with this method. 2.0SUMMARY OF METHOD 2.1N-methylcarbamates are extracted from aqueous samples with methylene chloride, and from soils, oily solid waste and oils with acetonitrile. The extract solvent is exchanged to methanol/ethylene glycol, and then the extract is cleaned up on a C-18 cartridge, filtered, and eluted on a C-18 analytical column. After separation, the target analytes are hydrolyzed and derivatized post-column, then quantitated fluorometrically. 2.2Due to the specific nature of this analysis, confirmation by a secondary method is not essential. However, fluorescence due to post-column derivatization may be confirmed by substituting the NaOH and o-phthalaldehyde solutions with organic-free reagent water and reanalyzing the sample. If
METHOD 3520C CONTINUOUS LIQUID-LIQUID EXTRACTION 1.0SCOPE AND APPLICATION 1.1This method describes a procedure for isolating organic compounds from aqueous samples. The method also describes concentration techniques suitable for preparing the extract for the appropriate determinative steps described in Sec. 4.3 of Chapter Four. 1.2This method is applicable to the isolation and concentration of water-insoluble and slightly soluble organics in preparation for a variety of chromatographic procedures. 1.3Method 3520 is designed for extraction solvents with greater density than the sample. Continuous extraction devices are available for extraction solvents that are less dense than the sample. The analyst must demonstrate the effectiveness of any such automatic extraction device before employing it in sample extraction. 1.4This method is restricted to use by or under the supervision of trained analysts. Each analyst must demonstrate the ability to generate acceptable results with this method. 2.0SUMMARY OF METHOD 2.1 A measured volume of sample, usually 1 liter, is placed into a continuous liquid-liquid extractor, adjusted, if necessary, to a specific pH (see Table 1), and extracted with organic solvent for 18 - 24 hours. 2.2The extract is dried, concentrated (if necessary), and, as necessary, exchanged into a solvent compatible with the cleanup or determinative method being employed (see Table 1 for appropriate exchange solvents). 3.0INTERFERENCES 3.1Refer to Method 3500. 3.2The decomposition of some analytes has been demonstrated under basic extraction conditions required to separate analytes. Organochlorine pesticides may dechlorinate, phthalate esters may exchange, and phenols may react to form tannates. These reactions increase with increasing pH, and are decreased by the shorter reaction times available in Method 3510. Method 3510 is preferred over Method 3520 for the analysis of these classes of compounds. However, the recovery of phenols may be optimized by using Method 3520 and performing the initial extraction at the acid pH. 4.0APPARATUS AND MATERIALS 4.1Continuous liquid-liquid extractor - Equipped with polytetrafluoroethylene (PTFE) or glass connecting joints and stopcocks requiring no lubrication (Kontes 584200-0000, 584500-0000, 583250-0000, or equivalent). CD-ROM3520C - 1Revision 3 December 1996
潜在致癌剂的危害等 级 致癌性是筛选优先污染物的重要依据之一，下表列出了美国EPA公布的200种致癌剂的危害等级。其中的参数含义为： 1、证据的充分程度（Degree of Evidence） 化学品对人体的致癌性证据之充分程度可以分为下列几类。 （1）证据充分，指致癌剂和人体癌症之间有因果关系。 （2）证据有限，指能提供一些可信的致癌性证据，但证据尚有限，还需作进一步补充。 （3）证据不充分，可能有3种情况，①能获取的致癌性数据很少；②与证据有关的研究尚不能排除偶然性、误差及混淆等情况；③研究结果无致癌性证据。 根据动物实验取得的致癌性证据的充分程度可分4级。 1级，致癌性证据充分。 2级，致癌性证据有限。 3级，致癌性证据不充分。 4级，无致癌性证据。 2、IARC标准分组 国际癌症研究所 （International Agency for research on cancer，简称IARC）将人类的肿瘤风险分为3组。 1组：列在此组内的化学品属致癌物，流行病学和暴露实验均已肯定，基致癌证据是充分的。 2组：化学品可能对人体有致癌性。其中有的对人体的致癌性证据几乎是“充分的”，另一类的证据不够充分。证据程度较高的为A组，较低的为B 组。例如，2A指对人体的致癌性至少存在着有限证据。当动物证据充分而人体数据不充分时，归入2B。 3组：列在本组中的化学品对人类没有致癌性。
3、潜力因素值F（Potency Factor Estimate） 潜力因素值F定义为1/ED 10。ED 10 等于10%终身致癌风险的致癌剂剂量。 F可以和致癌性的确认证据一起，用来划分化学品潜在致癌性的危险等级。 4、潜力因素分组（Potency factor Grouping） 由于潜力因素值F可表示致癌危险性的相对大小，因而，可将潜在致癌剂的相对潜力因素分为4组。潜力因素最高的化学品分在1组，中等潜力因素的为2组，低潜力因素的为3组，最低潜力因素的为4组。 5、致癌危害等级（Cancer Hazard Ranking） 根据人和动物试验所取得的致癌性证据，结合潜力因素分组数据，可将化学品致癌危害等级分为高、中、低3级。
DETERMINATION OF ETHYLENE THIOUREA (ETU) IN WATER USING GAS CHROMATOGRAPHY WITH A NITROGEN-PHOSPHORUS DETECTOR Revision 1.0 December 1992 D.J. Munch and R.L. Graves T.M. Engel and S.T. Champagne Battelle, Columbus Division ENVIRONMENTAL MONITORING SYSTEMS LABORATORY OFFICE OF RESEARCH AND DEVELOPMENT U.S. ENVIRONMENTAL PROTECTION AGENCY CINCINNATI, OHIO 45268 509-1
DETERMINATION OF ETHYLENE THIOUREA (ETU) IN WATER USING GAS CHROMATOGRAPHY WITH A NITROGEN-PHOSPHORUS DETECTOR 1.0SCOPE AND APPLICATION 1.1This method utilizes gas chromatography (GC) to determine ethylene thiourea (ETU, Chemical Abstracts Registry No. 96-45-7) in water. 1.2This method has been validated in a single laboratory during development. 1 The method detection limit (MDL) has been determined in reagent water and is listed in Table 2. Method detection limits may vary among laboratories, depending upon the analytical instrumentation used and the experience of the analyst. In addition to the work done during the development of this method and its use in the National Pesticide Survey, an interlaboratory method validation study of this method has been conducted. 1.3This method is restricted to use by or under the supervision of analysts experienced in the use of GC and in the interpretation of gas chromatograms. Each analyst must demonstrate the ability to generate acceptable results with this method using the procedure described in Section 9.3. 1.4When a tentative identification of ETU is made using the recommended primary GC column (Section 6.7.1), it must be confirmed by at least one additional qualitative technique. This technique may be the use of the confirmation GC column (Section 6.7.2) with the nitrogen-phosphorus detector or analysis using a gas chromatograph/mass spectrometer (GC/MS). 2.0SUMMARY OF METHOD 2.1The ionic strength and pH of a measured 50 mL aliquot of sample are adjusted by addition of ammonium chloride and potassium fluoride. The sample is poured onto an Extrelut column. ETU is eluted from the column in 400 mL of methylene chloride. A free radical scavenger is then added in excess to the eluate. The methylene chloride eluant is concentrated to a volume of 5 mL after solvent substitution with ethyl acetate. Gas chromatographic conditions are described which permit the separation and measurement of ETU with a nitrogen-phosphorus detector (NPD). 3.0DEFINITIONS 3.1Artificial Ground Water -- An aqueous matrix designed to mimic a real ground water sample. The artificial ground water should be reproducible for use by others. 509-2
1,2-DIBROMOETHANE (EDB), 1,2-DIBROMO-3-CHLORO-PROPANE (DBCP), AND 1,2,3-TRICHLOROPROPANE (123TCP) IN WATER BY MICROEXTRACTION AND GAS CHROMATOGRAPHY Revision 1.1 Edited by J.W. Munch (1995) T. W. Winfield - Method 504, Revision 1.0 (1986) T. W. Winfield - Method 504, Revision 2.0 (1989) James W. Eichelberger - Method 504.1, Revision 1.0 (1993) NATIONAL EXPOSURE RESEARCH LABORATORY OFFICE OF RESEARCH AND DEVELOPMENT U.S. ENVIRONMENTAL PROTECTION AGENCY CINCINNATI, OHIO 45268 504.1-1
1,2-DIBROMOETHANE (EDB), 1,2-DIBROMO-3-CHLOROPROPANE (DBCP), AND 1,2,3-TRICHLOROPROPANE (123TCP) IN WATER BY MICROEXTRACTION AND GAS CHROMATOGRAPHY 1.0SCOPE AND APPLICATION 1-3 1.1This method is applicable to the determination of the following compounds in finished drinking water and groundwater: Chemical Abstract Services Analyte Registry Number 1,2-Dibromoethane106-93-4 1,2-Dibromo-3-Chloropropane96-12-8 1,2,3-Trichloropropane96-18-4 1.2For compounds other than the above mentioned analytes, or for other sample sources, the analyst must demonstrate the usefulness of the method by collecting precision and accuracy data on actual samples and provide qualitative confirmation of results by gas chromatography/mass spectrometry (GC/MS).4 5 1.3The experimentally determined method detection limits (MDL) for EDB and DBCP were calculated to be 0.01 μg/L and the MDL for 123TCP was calculated to be 0.02 μg/L. The method has been useful for these analytes over a concentration range from approximately 0.03-200 μg/L. Actual detection limits are highly dependent upon the characteristics of the gas chromatographic system used. 2.0SUMMARY OF METHOD 2.1Thirty-five mL of sample are extracted with 2 mL of hexane. Two μL of the extract are then injected into a gas chromatograph equipped with a linearized electron capture detector for separation and detection. Analytes are quantitated using procedural standard calibration (Section 3.12). 2.2The extraction and analysis time is 30-50 minutes per sample depending upon the analytical conditions chosen. 2.3Confirmatory evidence should be obtained for all positive results. This data may be obtained by using retention data from a dissimilar column, or when concentrations are sufficiently high by GC/MS. Purge and trap techniques using Methods 502.2 or 524.2 may also be used. Confirmation of all positive results of EDB are especially important, because of the potential for misidentification of dibromochloromethane (DBCM) as EDB. 504.1-2
METHOD 9012B TOTAL AND AMENABLE CYANIDE (AUTOMATED COLORIMETRIC, WITH OFF-LINE DISTILLATION) 1.0 SCOPE AND APPLICATION 1.1 This method is used to determine the concentration of inorganic cyanide (CAS Registry Number 57-12-5) in wastes or leachate. This method detects inorganic cyanides that are present as either soluble salts or complexes. It is used to determine values for both total cyanide and cyanide amenable to chlorination. The "reactive" cyanide content of a waste is not determined by this method. Refer to 40 CFR 261.23 for information on the characteristic of reactivity. 2.0 SUMMARY OF METHOD 2.1 The cyanide, as hydrocyanic acid (HCN), is released from samples containing cyanide by means of a reflux-distillation operation under acidic conditions and absorbed in a scrubber containing sodium hydroxide solution. The cyanide ion in the absorbing solution is then determined by automated UV colorimetry. 2.2 In the automated colorimetric measurement, the cyanide is converted to cyanogen chloride (CNCl) by reaction with Chloramine-T at a pH less than 8 without hydrolyzing to the cyanate. After the reaction is complete, color is formed on the addition of pyridine-barbituric acid reagent. The concentration of NaOH must be the same in the standards, the scrubber solutions, and any dilution of the original scrubber solution to obtain colors of comparable intensity. 3.0 INTERFERENCES 3.1Interferences are eliminated or reduced by using the distillation procedure. Chlorine and sulfide are interferences in this method. 3.2Oxidizing agents such as chlorine decompose most cyanides. Chlorine interferences can be removed by adding an excess of sodium arsenite to the waste prior to preservation and storage of the sample to reduce the chlorine to chloride which does not interfere. 3.3Sulfide interference can be removed by adding an excess of bismuth nitrate to the waste (to precipitate the sulfide) before distillation. Samples that contain hydrogen sulfide, metal sulfides, or other compounds that may produce hydrogen sulfide during the distillation should be treated by the addition of bismuth nitrate. 3.4High results may be obtained for samples that contain nitrate and/or nitrite. During the distillation, nitrate and nitrite will form nitrous acid, which will react with some organic compounds to form oximes. These compounds once formed will decompose under test conditions to generate HCN. The possibility of interference of nitrate and nitrite is eliminated by pretreatment with sulfamic acid just before distillation. Nitrate and nitrite are interferences when present at levels higher than 10 mg/L and in conjunction with certain organic compounds.