Inc. Laboratories, 2009 Copyright · C. Gas Chromatography/Mass Spectrometry . Gas...

IV. Organic Analyses

A. Gas Chromatography Gas Chromatography (GC) is a powerful analytical tool used for the separation and detection of organic compounds. A typical GC system utilizes a carrier gas (usually helium or hydrogen) to transport the analytes from the injection port, through the column (which is located in a temperature-programmable oven, where separation occurs) and on to the detector where responses are observed as the specific compounds pass. Separation of multiple analytes is done by taking advantage of the differences in boiling points of the compounds in solution, as well as the differences in their affinities toward the analytical column through which they pass (e.g., polarity may influence affinity). (The higher the boiling point, the later the compound comes off, or elutes.) The solution to be analyzed is introduced to the system by either injection or purging of the solution. At this point all the compounds of interest are in a liquid state on the head of the column with carrier gas rushing by and the internal temperature is less than the boiling points of the compound to be analyzed. As an example, suppose we have a solution containing methanol (boiling point 65 °C), ethylbenzene (B.P. 136 °C) and trichloroethylene (B.P. 87 °C). Assume we are only interested in the ethylbenzene and trichloroethylene. The solution is injected onto a column with an initial oven temperature of 75 °C. At this point the ethylbenzene and the trichloroethylene will remain in the liquid state and sit at the head of the column. The methanol boils and is carried off through the column by the carrier gas. After a brief period, the oven temperature is slowly increased. As the oven temperature approaches the boiling point of the trichloroethylene, it will vaporize and be carried on to the detector. The system will continue in this manner until we have exceeded the boiling points of all of compounds of interest. In many cases, the injection port is above the boiling points of all constituents and only the column temperature is used for separation. At the end of the column is a detector (or detectors) which observes compounds based on their specific properties. Qualitative peak identification is based upon the retention times of the components in an unknown solution as compared to the retention times in a known standard. Quantitation is achieved by analyzing a known amount of a substance in a series of standards and obtaining a response factor. The magnitude of the detector response of the unknown is then compared to the calibration curve and the concentration calculated.

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B. GC Detectors Depending upon the type and nature of the chemical being measured, today's environmental chemist has several different detectors available to choose from, each with its own advantages and disadvantages. What follows is a brief introduction to the various detectors most commonly in use today and a description of their applications. In most cases, the chromatography portion of the analysis is virtually identical, using either fused silica or packed columns to provide for the separation of analytes based upon their characteristic properties - boiling points, chemical structure, etc. (For more information regarding gas chromatography, please refer to the previous section of this manual.) The mass spectrometer (MS) is by far the most powerful and flexible of the detectors used in the environmental laboratory today. Offsetting this flexibility is one of the MS systems' main drawbacks: less sensitivity than other more specific detectors such as the PID, ELCD, and ECD. Due to its complex nature, the next section of this manual has been dedicated to a description of the MS and it functionality. The methods most often associated with the MS are the EPA methods 624 and 625, and the SW-846 methods 8260 and 8270. The Electrolytic Conductivity Detector, or ELCD, is primarily used in methods for the detection of halogenated components (compounds containing chlorine, bromine, or fluorine atoms). This detector is often referred to as a Hall detector after Randy Hall, its inventor. As compounds elute from the chromatographic column, they are swept into a nickel reaction tube, which is at approximately 850-900 °C. The components are stripped of their halogenated atoms and these atoms are carried into a conductivity cell. As the concentrations of the halogens change in this cell, the measured conductivity of a solution in the cell changes proportionally. The ELCD is most commonly associated with EPA method 601 and the SW-846 method 8021. The Electron Capture Detector, or ECD, is selective in response towards electrophilic compounds such as the chlorinated hydrocarbons found in pesticides and PCB's. The detector is non-destructive, and is often used in series with other detectors such as Flame Ionization Detectors (FID). The sample is introduced into the detector through the chromatographic column and passes over a Ni63 radioactive source. This source emits beta (b) particles, which in turn causes ionization of the carrier gas and the subsequent release of electrons. These electrons are directed to a part of the detector known as the collector anode by the application of a polarizing voltage between the anode and the Ni63 source. The pulse frequency of the polarizing supply is automatically controlled to maintain a constant current and is used to form the detector output signal. This detector is most commonly used with the EPA Methods 608 and 504, and the SW-846 Methods 8081 and 8011.

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The Flame Ionization Detector or FID is one of the most widely used detectors. It is fairly non-specific and functions as a destructive detector. The effluent from the column is mixed with a fuel gas (hydrogen) and is directed into a flame. Most organic components are destroyed, creating ions. A voltage potential is applied across the gap between the burner tip and an electrode located just above the flame. The resulting current (10-12 A) is measured and is proportional to the concentration of the components present. This detector is most commonly used with EPA Method 610, SW-846 Methods 8100, and many of the petroleum related methods such as Diesel Range Organics (DRO), Gasoline Range Organics (GRO), Massachusetts Extractable Petroleum Hydrocarbons (MA-EPH) and the Florida Petroleum Range Organics (FL-PRO). The Flame Photometric Detector or FPD is typically used in the analysis of assorted air and water pollutants, some pesticides, and coal hydrogenation products. This detector is also useful in analyzing for halogens, nitrogen, and several metals, such as the organo-tins. It is highly sensitive to compounds containing sulfur and phosphorus. The column effluent is mixed with hydrogen and burned with air at a low temperature. Light emitted from the flame is passed through a lens, a filter, and into a photomultiplier tube where an electrical signal is generated. This detector offers a blend of traditional GC methods with detection technology similar to that found in ICP-AES. The Nitrogen Phosphorus Detector or NPD is a highly specific thermionic detector for organically bound nitrogen and phosphorus. The detector works by electrically heating a glass bead containing an alkali metal until electrons are emitted. These electrons are captured by stable intermediates to form a hydrogen plasma. The column effluent is ionized when directed into this plasma. A polarizing field directs these resulting ions to a collector anode creating a current. This detector's sensitivity is dependent upon the air flow, while its selectivity is affected by hydrogen flow. This detector is most commonly used for EPA Method 614, and SW-846 Methods 8140 and 8141. The Photoionization Detector or PID is most sensitive to organic compounds containing aromatic rings, double (alkenes), and triple (alkynes) carbon-carbon bonds. This is a non-destructive detector, and is commonly used in series with other detectors such as the ELCD or FID. The column effluent is ionized by ultraviolet light and the current produced by the ion flow is measured and is proportional to the concentrations of the ionized material. This detector is most commonly associated with the EPA Method 602 and the SW-846 Method 8021.

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C. Gas Chromatography/Mass Spectrometry Gas Chromatography/Mass Spectrometry (GC/MS) is perhaps one of the more versatile analytical techniques in the identification of organic molecules in the environmental field. Since this method employs the use of the gas chromatograph (GC) coupled to a mass spectrometer (MS or mass spec), this discussion will be limited to the description of the functions of the mass spectrometer, specifically. Please refer to the section on Gas Chromatography for a description of that part of the GC/MS system.

1. General Description of the System The mass spectrometer receives the compounds as they exit the GC analytical column. Through a process that is described more thoroughly below, the mass spec splits the compounds into ion fragments. These fragments are then separated according to molecular weight. Since the majority of organic compounds have unique fragmentation patterns, the mass spec operator can distinguish between the different parent compounds that were in the original sample. (This has been a very simplistic overview of the mass spectrometer. For a more thorough description, please continue further.)

2. A More Technical Approach Once the GC separates the constituents of the original sample, the individual components enter the mass spectrometer through an interface between the GC and the MS. The mass spec is held at extremely low pressure (such as 3-5 x 10-6 torr) by use of a specialized vacuum, which is coupled to the mass spec manifold. Within the manifold is housed the ion source. As the compounds elute from the GC column, the stream of molecules enters this source, where a metallic filament discharges electrons into the oncoming path. (This filament is similar in function and design to the filaments in standard incandescent light bulbs). When these electrons hit the stream of compounds, the compounds may split into various, predictable ionized fragments. These fragments are then accelerated through a curved magnetic field, which separates the ions based on their "mass-to-charge" ratios. "Lighter" (in simple terms) ion fragments make it through the curved pathway, while "heavier" ones would normally collide with the walls of the curved field's assembly. To affect the separating process and to allow the identification of all masses of interest, the mass spec can then manipulate the magnetic field, affording a controlled ability to "see" specific ion masses (i.e., light to heavy) by allowing the increasingly "heavier" compounds to pass this "electromagnetic filter." This single principle is what makes the mass spectrometer such a useful tool.

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3. The Mass Spectrum as a Tool Once the ion fragments have made their way through the analyzer system, the computer data system then assimilates the massive quantities of electronic signals collected from the mass spec. The computer then manipulates the data, and the operator can obtain various pieces of information about the original sample, including retention times of the separated compounds (GC data) and the mass spectrum of any given moment's-worth of the analysis (MS data). Most other non-specific detectors can produce only retention time data. So what is so important about the mass spectral data? A mass spectrum can be thought of as a graphic representation of the relative abundance of the various ionized fragments in any given moment's data (or scan) from the analyzer. Some general information that may be interpreted from the mass spectrum might be whether the compound is halogenated, aliphatic, or aromatic, or whether this compound may contain nitrogen or sulfur. It is typically possible to determine how many carbons are in this molecule. Above all, the mass spectrum gives a good indication of the original (unfragmented) compound's molecular weight. With all this information, it may be possible to determine the exact compound of interest simply by interpretation of the mass spectrum by a well-trained individual; however, this process may take hours of investigation for a single spectrum. Fortunately, most analysts have access to a massive spectral library of some 300,000 or more compounds, which the computer can then cross-reference and provide several likely choices to the analyst. However, if the analyst knows already which compounds are of interest (e.g., the EPA 624 list), this shortened mass spectra library can be searched against the sample's spectral results. Instead of searching for chromatographic peaks, and then determining their mass spectra to see what the peaks are, the computer looks for where the compounds should elute, and then sees if there are any mass spectra there that match the target compounds' mass spectra. So what happens when two different compounds elute from the column at the same time (giving one chromatographic peak, where two compounds actually exist)? If the operator were asked to look at this seemingly single compound's associated mass spectra, it would become apparent that there are, in fact, two compounds that are coming out at the same time. Since most compounds generate a unique mass spectrum (structural isomers being one exception), the analyst would see that two compounds' spectra are actually mixed. By looking at molecular fragments that are unique to each compound, the operator can now quantitatively differentiate the two compounds that would otherwise be impossible using another non-specific analyzer, like those used in most other GC methods. See Appendix A for an example of a Mass Spectrum

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4. Tentatively Identified Compounds (TIC) What about the “other peaks,” or unknowns? Most laboratories can provide some additional information regarding “tentatively identified compounds”, which consist of the unknown peaks detected in a sample analysis. Most MS system software builds a “list” of all detected peaks, then goes through and eliminates those that were identified as target constituents, surrogates, spikes and internal standards. These remaining unknown peaks are then searched for potential matches against a library of known spectra. In most cases, a partial to complete match can be made with materials present in the library. Depending upon the nature of the compound, identification by the laboratory can range from no match (“unknown”) to some sort of structural information (“unknown substituted benzene”) to positive identification (“1,2,4-trimethylbenzene”). Since the instrumentation used was not calibrated specifically for every potential unknown, concentrations are flagged as estimated, based on the compounds response relative to a known standard. Such concentrations should never be relied upon for regulatory purposes.

5. Scanning Mode vs. Selected Ion Monitoring (SIM) Mode Most environmental applications use MS systems in what is referred to as scanning mode. In this configuration, the detector “scans” through a range of masses on a periodic basis. Most systems are set up to scan such a range of masses every 0.5 to 2 seconds. Volatile analyses are most often using masses in the range of 35 to 260 atomic mass units (amu) and semivolatiles typically use masses in the range of 35 to 500 amu. Selected Ion Mode (SIM) is used to enhance the sensitivity of the GC/MS, however there is some sacrifice made as to the “confirmatory” nature of the data generated. MS data has long been touted as “better than GC” since the data user was able to obtain not only retention times and concentrations, but also mass spectral patterns allowing for the positive identification of the material. The simple explanation follows: With a mass range of 35 to 260amu and a resolution of 0.1 amu the instrument must make approximately 2200 measurements every scan in scan mode. With a scan every second, the instrument has only approximately 0.0004 seconds to spend on each measurement. (Not a long time!) SIM improves the sensitivity greatly by reducing the number of masses being measured, allowing more time for each measurement. This extra time improves the instrument’s signal-to-noise ratio, allowing the lab to reach lower detection limits. If SIM is so great, why don’t labs use SIM exclusively? The answer is two-fold, and lies in the reduction of target masses. When the instrument is in scan mode, it “sees” all masses within the scan range throughout the analysis. If a peak is detected that does not match any of the compounds in a standard, typically a library search can be performed (see Tentatively Identified Compound section above). In SIM mode, only a limited number of masses are monitored, so the unknown peaks cannot be positively identified. Also, since the number of ions being monitored is reduced,

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the chances of false positive identifications of unknown compounds as target analytes are greatly increased. An example of this would be the misidentification of cholesterol, a naturally occurring compound in many environments, as a poly-aromatic hydrocarbon. Without additional masses to confirm (or deny) the nature of the material, false positives can occur at a much higher incidence. Another drawback to the SIM mode is the lack of guidance from EPA or other regulatory agencies as to proper procedures. Should SIM data be requested from a laboratory, the data user should ensure the laboratory’s procedures are thorough and well written, and address the issues identified above. The end user should weigh the following factors prior to specifying a desired method: SIM Benefits:

• Lower detection limits possible vs. scan mode MS. • Reduced susceptibility to interferences due to background over GC or LC

procedures. • Enhanced confirmation information over GC or LC procedures.

SIM Limitations

• Cannot perform unknown peak identifications (tentatively identified compounds) as compared to scan mode MS.

• Greater chance of false positive identifications than scan mode MS (Still better than GC or LC!)

• Costs more than GC or LC procedures (similar to MS rates) NOTE: Recent advances in GC/MS technology now allow for combined SCAN/SIM analysis in some cases. This type of analytical approach is highly complex, but allows for a customized approach to meeting varied quantitative/qualitative needs for a long list of diverse analytes in a single sample via a single analysis.

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D. Organic Sample Preparation Environmental samples must be prepared prior to analysis in such a manner to ensure representative and reproducible results. The sample preparation that is required is dependent upon not only the procedure to be performed, but also the sample itself. Some samples may require physical manipulation such as grinding (particle size reduction). Others require additional chemical manipulations in preparation for analysis. Samples to be analyzed for volatile compounds are typically introduced into the GC by a technique called purge and trap. Such samples typically do not require much preparation prior to analysis. Most samples (both solid and aqueous) are rapidly mixed to ensure representativeness, weighed out into specially designed purge tubes, and loaded onto instruments for analysis. The samples are introduced into the GC by purging the sample with an inert gas such as nitrogen, thereby stripping off the lighter, more volatile components. These are captured (or trapped) in a sorbent trap that, upon completion of the purge cycle, is flash heated to desorb the compounds and backflushed, directing a concentrated slug of organics onto the GC column. Solid or waste samples containing high concentrations of volatiles are typically prepared for analysis by extraction into methanol, with an aliquot of the resulting methanol extract being diluted with deionized water and then purged. The SW-846 method number for this procedure is 5030. In 1997, the EPA promulgated Update III to SW-846, and with it introduced a new procedure for solids preparation and analysis referred to as 5035, Closed System Purge and Trap. This procedure varies greatly from the previously used method of solids preparation in that a 5 gram solid sample is containerized either immediately upon sampling into a 40 mL vial with a preservative and stir bar, or is sampled using a sealed system such as the EnCore ™, with subsequent laboratory preparation into a vial within 48 hours of sampling. Additional details regarding the 5035 procedure can be found below. SW-846 Method 5035 provides for a variety of sample collection options according to anticipated component (concentration) levels: 1. High concentration samples can either be preserved immediately into methanol upon

collection, or collected in an appropriate container and preserved in the laboratory. 5035 allows for the high level sample portion to be collected in a two ounce jar with a teflon-lined septa lid, however some states (such as Florida) have gone beyond the EPA’s specifications to require that either an EnCore ™ or immediate field preservation in methanol be used for this sample aliquot.

2. Low concentration samples can be either preserved in the field into a preweighed 40 mL vial containing either a sodium bisulfate solution or deionized water and a stir bar, or collected using a sealed sampling system such as the EnCore ™ with subsequent laboratory preservation within 48 hours of collection. Note that each vial (or EnCore ™) submitted to the laboratory represents a discrete sample, for one use only. This is the reason multiple vials (or EnCores™) are required for each sample. Preferable containers for receipt would be two vials (or EnCores ™) for the low level procedure. Additionally, note that when deionized water is used as a preservative, the samples must be frozen to –10 deg. C within 48 hours of sample collection – simple refrigeration is not acceptable.

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3. Samples being analyzed for non-volatile components are subjected to a much wider array of preparation procedures depending upon several factors: the required sensitivity levels (detection limits), the time available for sample preparation, the amount of sample available, and the method or regulatory requirements.

Aqueous samples are typically extracted using separatory funnels, by which a sample is mechanically agitated or "shaken" with an extraction solvent to remove the components of interest. This agitation is repeated three times to ensure as complete an extraction as possible. The extract is collected after each time and the final volume is concentrated down to a final volume from 0.5 to 10 mL, depending upon the analytical technique and regulatory requirements. The SW-846 method number for this procedure is 3510. An alternative to the separatory funnel is the continuous liquid-liquid extractor, or LLE. In this apparatus, the aqueous sample is continually washed with the extraction solvent, typically for 16-24 hours. Although this is a highly effective extraction procedure, it is time-limited and tends to be used only in situations where fast turnaround times are not required. Similar to the separatory funnel procedure, the final extract is taken and concentrated to a final volume dependent upon several factors. The SW-846 method number for this procedure is 3520. Another more recent liquid-liquid extraction technique is solid-phase extraction, or SPE. In this procedure, the aqueous sample is filtered through a specially prepared membrane that selectively binds the analytes of interest. The analytes are then eluted (washed) off the membrane using a specific solvent that is dependent upon the method being performed. Advantages to the SPE method include speed of processing, reduced labor and material costs, and reduced solvent use (waste minimization). The SW-846 method number for this procedure is 3535. Solid samples are typically extracted by one of two procedures: sonication or Soxhlet. Similar to separatory extractions, the sonication technique is a serial extraction utilizing high frequency pulsed sound waves to enhance sample exposure to the solvent. The SW-846 method number for this procedure is 3550. Soxhlet extractors are similar in nature to the LLE's in that the samples are continually washed in the extraction solvent. Also, like the LLE's, the samples are extracted over a longer period, typically 16-24 hours. The SW-846 method number for this procedure is 3540. Both the sonication and Soxhlet techniques yield solvent extracts that are concentrated identically to the resulting aqueous sample extracts. Note — The only exception to this time requirement in soxhlet extractions is found in the Total Recoverable Petroleum Hydrocarbon procedure by the draft SW-846 Method 9073. In this method, samples are extracted for only four hours. (Note that this procedure only permits Soxhlet extractions — sonication is not an option!) A further note on extractions: The reason the extraction procedure is repeated three times in the separatory funnel and sonication extractions has to do with the extraction efficiency of the procedure for the components involved. With multiple successive washings, even

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components that are difficult to extract can be effectively removed and concentrated. Here is an example: assuming a 70% extraction efficiency for a component, of 100 mg present in the original sample, the first process (washing) would remove 70%, or 70 mg. The second process would remove 70% of the remaining 30 mg, or 21 mg. The final process would remove 70% of 9 mg, or 6.3 mg. In the final extract, we have now collected more than 97% of the original amount present — 70 mg + 21 mg + 6.3 mg. This explains why non-continuous extraction procedures (such as sonication or separatory funnel extractions) must be repeated, rather than just extended for a longer period. Once samples have been extracted and concentrated, analysis is typically in order. However, some samples require yet further processing to ready them for the instrumentation. If relatively high concentrations of interfering substances are present, cleanup procedures are often employed to minimize their effects.

E. Sample Cleanup Procedures Depending upon the final analysis procedure, many different cleanup techniques are available to the analyst to help address difficult matrix issues. The most common environmental sample cleanup procedures have been detailed below.

1. SW-846 Method 3520 -- Florisil Cleanup Florisil is a magnesium silicate with basic properties, most commonly used in pesticide analyses to separate the target components from interfering substances. It is also used in the separation of nitrogen compounds from hydrocarbons, the separation of aromatics from aliphatic/aromatic mixtures, and similar use with fats, oils, and waxes. One of the properties of Florisil is its ability to allow for the selective elution of components based on the elution solvent used. As such, complex mixtures of pesticides and PCB's can be fractionated to allow for complete identification of individual pesticides.

2. SW-846 Method 3630 -- Silica Gel Cleanup Silica gel is a regenerative adsorbent of silica with weakly acidic properties. This procedure provides cleanup utilizing solid-phase extraction cartridges for pentafluorobenzyl bromide-derivatized phenols, organochlorine pesticides and polychlorinated biphenyls (PCB’s). As with Florisil, component elution off the silica gel cartridge is dependent upon the elution solvent used. In many cases, separation of desired compounds from background interferences is possible. The silica gel can also be used to separate non-polar from polar hydrocarbons, as in the FL-PRO and TRPH procedures.

3. SW-846 Method 3640 – Gel Permeation Cleanup (GPC) GPC is a size exclusion procedure using organic solvents and hydrophobic gels to separate synthetic macromolecules. The packing gel is porous and is characterized by the

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range or uniformity of that pore size. GPC operates on the principle of loading all components in an extract on the gel bed, then selectively removing the components of larger molecular size. This procedure provides for the efficient separation of typical semivolatile and pesticide components from lipids, polymers, proteins, natural resins, and various higher molecular weight compounds.

4. SW-846 Method 3660 – Sulfur Cleanup Elemental sulfur is encountered in many sediments, industrial effluents, and samples containing biological material such as algae. Sulfur, if not removed, presents an interference in many organic analysis procedures, especially pesticide analysis using an ECD detector. Sample extracts are mixed with either a copper or tetrabutylammonium sulfite (TBA) powder. Both complex out any sulfur present. The extract is then transferred to a fresh vial for analysis.

5. SW-846 Method 3665 – Sulfuric Acid/Permanganate Cleanup This cleanup procedure is primarily used in the analysis of PCB’s, where many other single component pesticides such as aldrin, dieldrin, endrin, and so forth can provide interferences. The sample extract is treated with either concentrated sulfuric acid or potassium permanganate, which oxidizes, or breaks down the unwanted organics present. The extract is then transferred to a fresh vial for analysis.

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F. Organic Methods The next section provides information for the most common organic methods of analysis. This information should be used as a guide in selecting the appropriate procedure based on instrument sensitivity, cost, and required data quality. (Example: Although the pesticide Lindane can be analyzed by GC/MS method 8270, it is typically not sensitive enough to meet required regulatory criteria. In addition, the cost of an analysis by GC/MS vs. GC is roughly three times as much. However, in a difficult matrix with high concentrations of background interferences, GC/MS may be the only approach to meet project-specific criteria for data quality or sensitivity.

And now for the disclaimers: 1) Throughout this text, target detection limits have been listed. These limits are based on

those levels that are easily obtained while processing relatively clean samples. When a sample matrix contains background levels of a contaminant that interferes with the analysis, detection levels will be higher than those listed.

2) The sample volume requirements contained throughout this text are based on standard

operating procedures. In most cases it is possible to use less sample than that listed, but the detection levels are usually affected; i.e., if only one-tenth of the required volume is provided then normally the detection level will be increased 10 fold.

3) Most of the organic methods require that residual chlorine be neutralized at the time of

sampling. This statement refers primarily to those drinking water supplies that have been chlorinated. Groundwater or soil samples typically need not worry about residual chlorine.

4) In several areas of the text, regulatory levels have been indicated. Due to the nature of

the regulations, these levels may not be current, depending upon the relative age of this document at the time you are reading this. In no instance will Environmental Conservation Laboratories, Inc. be responsible for decisions made based upon the levels indicated in this manual. Should you have questions regarding current regulatory levels, please contact either the appropriate regulatory agency (DEP, EPA, etc.) or our laboratory.

5) Although many methods of analysis are included in this text, not all are available from

Environmental Conservation Laboratories. This document is meant as a guide to environmental chemistry, not a marketing brochure. However, it should be noted that many of the component lists shown for the various organic procedures do reflect our implementation.

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EPA Method 504/504.1/ SW-846 Method 8011

1,2-Dibromoethane (EDB) 1,2-Dibromo-3-chloropropane (DBCP) 1,2,3-Trichloropropane (504.1 only)

METHOD SUMMARY: 35 mL of water is extracted with hexane and analyzed on a gas chromatograph equipped with an electron capture detector (ECD). DETECTION LEVEL: 0.02 µg/L (20 parts per trillion) - water SAMPLING Because of the components’ volatile nature, sampling should be performed with the same consideration as other volatile parameters (ex: 8021/8260). Samples should be kept on ice from the time of sampling to analysis. PRESERVATIVE Neutralize any residual chlorine present with 80 mg/L sodium thiosulfate. HOLDING TIME: Samples must be extracted and analyzed within 28 days (14 days for Method 504.1). COMMENTS Care should be taken in the sampling to avoid excessive aeration. This method is also extremely sensitive to interferences from trihalomethanes (bromodichloromethane, bromoform, chloroform, and dibromochloromethane), commonly associated with chlorinated water supplies. PREFERRED SAMPLING CONTAINER: 40-mL vial, 2 or 3 per site

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EPA Method 601/ SW-846 Method 8021 VOLATILE HALOCARBONS

METHOD SUMMARY: This is a purge and trap gas chromatographic method. An inert gas is bubbled through a 5 mL water sample or 1-5 g soil sample contained in a specially designed purging chamber. Aqueous samples are purged at ambient temperature, while soils must be heated to approximately 55°C. The volatile halocarbons are efficiently transferred from the aqueous phase to the vapor phase. The vapor is swept through a sorbent trap where the halocarbons are trapped. After purging is completed, the trap is backflushed with the inert gas to desorb the halocarbons onto a gas chromatographic column. The gas chromatograph is temperature programmed to separate the halocarbons that are then detected with an Electrolytic Conductivity Detector (ELCD), a halide-specific detector. DETECTION LEVEL: 1-10 µg/L or 5-50 µg/Kg (component specific) SAMPLING: Aqueous samples must be collected in 40-mL VOC vials. Aqueous samples, once in the vial, should contain no air bubbles. All samples must be iced or refrigerated from the time of collection until analysis. Soil samples should be collected in 2-4 oz glass jars with Teflon lined septum tops with minimal headspace. PRESERVATIVE: None required HOLDING TIMES: 14 days COMMENTS Samples are very sensitive to improper sampling and storage. Aqueous samples must be taken in duplicate or triplicate 40 mL VOC vials with no air bubbles (headspace) present. The same sample may be used for the analysis of the 602 parameters, depending upon the equipment configuration. Most laboratories run the 601 & 602 methods as a combination. Note that the full 8021 analysis contains a substantially higher number of components than the typical 601/602 combination, and can be requested for either the halocarbons, aromatics, or full component list. PREFERRED SAMPLING CONTAINER:

Aqueous: 40 mL VOC vials (2 or 3 per sample) Soils: For areas not requiring 5035 analysis: 2 oz. Septa lid jar.

For areas requiring 5035: • Florida sites: 2 x 5 g. Encores™ (or DI-preserved 5 g aliquots in

preweighed vials), one methanol preserved aliquot for high level analysis, plus an additional aliquot for percent solids.

• Non-Florida sites: 2 x 5 g Encores™ (or 5g aliquots in preweighed vials, plus a 2 oz. Septa jar.

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EPA Method 602/ SW-846 Method 8021 VOLATILE AROMATICS

METHOD SUMMARY: The sample is introduced on to the gas chromatograph as described in the EPA 601 method. The GC is typically configured to analyze the EPA 602 parameters and the EPA 601 parameter list in series. The EPA 602 or volatile aromatics are analyzed with a photoionization detector (PID). This detector responds to aromatic rings or double bonds. It is a non- destructive detector, which allows compounds to pass through and proceed to the ELCD detector for the analysis of the EPA 601 compounds. DETECTION LEVEL: 1-10 µg/L or 5-50 µg/Kg (component specific) PRESERVATIVE: Aqueous: None required to 7 days, HCl to pH < 2 will allow for 14 days. Solids: None COMMENTS Samples are very sensitive to improper sampling and storage. Samples must be taken in duplicate or triplicate 40 mL VOC vials with no air bubbles (headspace) present. The same sample may be used for the analysis of the 601 parameters. ENCO Laboratories' volatile instrumentation is typically configured to run both 601 and 602 compounds in series. Note that the full 8021 analysis contains a substantially higher number of components than the typical 601/602 or 8010/8020 combination, and can be requested for either the halocarbons, aromatics, or full component list. PREFERRED SAMPLING CONTAINER:




• Non-Florida sites: 2 x 5 g Encores™ (or 5g aliquots in preweighed vials, plus a 2 oz. Septa jar. ENCO La

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EPA Method 601/602/8021/SM6230D cont.

Component 601 or 8021/halo.

602 or 8021/arom.

8021 SM6230 D

1,1,1,2-Tetrachloroethane X X 1,1,2,2-Tetrachloroethane X X X 1,1,1-Trichloroethane X X X 1,1,2-Trichloroethane X X X 1,1-Dichloroethane X X X 1,1-Dichloroethene X X X 1,1-Dichloropropene X X 1,2,3-Trichlorobenzene X X 1,2,3-Trichloropropane X X 1,2,4-Trichlorobenzene X X 1,2,4-Trimethylbenzene X X 1,2-Dibromo-3-chloropropane X X 1,2-Dibromoethane (EDB) X * X X 1,2-Dichlorobenzene X X X X 1,2-Dichloroethane X X X 1,2-Dichloropropane X X X 1,3,5-Trimethylbenzene X X 1,3-Dichlorobenzene X X X X 1,3-Dichloropropane X X 1,4-Dichlorobenzene X X X X 2,2-Dichloropropane X X 2-Chlorotoluene X X 4-Chlorotoluene X X Benzene X X X Bromobenzene X X Bromochloromethane X X Bromodichloromethane X X X Bromoform X X X Bromomethane X X X Carbon tetrachloride X X X Chlorobenzene X X X X Chloroethane X X X Chloroform X X X Chloromethane X X X cis-1,2-Dichloroethene X X X cis-1,3-Dichloropropene X X X Dibromochloromethane X X X Dibromomethane X X Dichlorodifluoromethane X X X

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EPA Method 601/602/8021/SM6230D cont.

Component 601 or 8021/halo.

602 or 8021/arom.

8021 SM6230 D

Ethylbenzene X X X Hexachlorobutadiene X X Isopropyl Ether X * Isopropylbenzene X X Methyl tert butyl ether (MTBE) X X Methylene Chloride X X X Naphthalene X * X X n-Butylbenzene X X n-Propylbenzene X X p-Isopropyl Toluene X X sec-Butylbenzene X X Styrene X X tert-Butylbenzene X X Tetrachloroethene X X X Toluene X X X Trans-1,2-Dichloroethene X X X Trans-1,3-Dichloropropene X X X Trichloroethene X X X Trichlorofluoromethane X X X Vinyl chloride X X X m-Xylene & p-Xylene X X X o-Xylene X X X

* = Available by special request only.

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EPA Method 603/ SW-846 Method 8031 ACROLEIN AND ACRYLONITRILE

Acrolein Acrylonitrile

METHOD SUMMARY: This is a purge and trap gas chromatographic method as described in the EPA 601 and 602 method. The detector is a flame ionization detector. DETECTION LIMIT: 100 µg/L or 500 µg/Kg SAMPLING Same as in EPA 601/602 PRESERVATIVE: Adjust pH to 4 - 5 HOLDING TIME: 14 days COMMENTS: Many laboratories can analyze for these components by Method 8260, a GC/MS method. Due to the infrequency of requests for these specific compounds, the client should verify the lab's ability prior to submitting samples for analysis by either 603 or 8030. PREFERRED SAMPLING CONTAINER:

Aqueous: 40 mL VOC vials (2 or 3 per sample) Soils: 2 oz septa top widemouth jars or VOC vials.

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EPA Method 604/ SW-846 Method 8041 PHENOLS

4-Chloro-3-Methylphenol 2-Nitrophenol 2-Chlorophenol 4-Nitrophenol 2,4-Dichlorophenol Pentachlorophenol 2,4-Dimethylphenol Phenol 2,4-Dinitrophenol 2,4,6-Trichlorophenol 2-Methyl-4,6-dinitrophenol

METHOD SUMMARY: One liter of water or 30 g of soil is acidified and extracted with methylene chloride using separatory funnel, sonication, or Soxhlet extraction techniques. The extract is dried and concentrated to a volume of 10 mL or less. Matrix interferences may be caused by contaminants that are co-extracted from the sample. A cleanup step is routinely employed in order to overcome many of these interferences, however the recoveries of the target compounds may be reduced. The analysis is typically done with a flame ionization detector (FID), but can be performed on an electron capture detector (ECD) for lower detection limits on the chlorinated components. DETECTION LIMIT: 1-100 µg/L or 33-3300 µg/Kg (varies by component) SAMPLING: Samples must be collected in glass containers. Many of the parameters in this method are light sensitive (degrade under UV light), so the samples should be collected in amber jars. PRESERVATIVE: Samples should be kept at 4°C from time of sampling to analysis. HOLDING TIME: Aqueous samples must be extracted within 7 days (soils within 14 days) and the extract analyzed within 40 days of extraction. COMMENTS: Because the detector used in this analysis is non-specific, the client should be aware of the potential for false positives. This method is a GC screening procedure. All positive responses should be confirmed either through a second column or through GC/MS. PREFERRED SAMPLING CONTAINER: 1 L amber glass bottle for aqueous samples, or 4 oz amber jar for solids.

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EPA Method 606/ SW-846 Method 8061 PHTHALATE ESTERS

Bis(2-ethylhexyl) phthalate Butylbenzyl phthalate Di-n-butyl phthalate Diethyl phthalate Dimethyl phthalate Di-n-octyl phthalate

METHOD SUMMARY: A 1 liter water sample or 30 g soil sample is solvent extracted with methylene chloride. The methylene chloride extract is concentrated to a volume of 10 mL or less. The sample is then analyzed on a gas chromatograph using a flame ionization detector (FID). DETECTION LEVEL: 10 µg/L or 330 µg/Kg SAMPLING: Samples must be collected in glass containers. DO NOT rinse the bottle with sample prior to filling. PRESERVATIVE: The sample should be kept on ice from sampling to analysis. HOLDING TIME: Aqueous samples must be extracted within 7 days, soil samples must be extracted within 14 days, and all extracts must be analyzed within 40 days of extraction. COMMENTS: Analysis for phthalates is especially complicated by their ubiquitous occurrence in the environment. Extreme care must be taken throughout the sampling and analytical process in order to prevent contamination. It should also be noted that these compounds have been recognized by the testing industry as common laboratory contaminants, which should be taken into consideration when using the data generated by this method. ENCO Laboratories makes every attempt to include a quality assurance notice (a data qualifier explaining the problems of analyzing phthalates) with projects in which phthalates have been reported. PREFERRED SAMPLING CONTAINER: 1-L amber glass bottle for aqueous samples, 4-8 oz glass jar for solids.

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EPA Method 607/ SW-846 Method 8070 NITROSAMINES

N-Nitrosodimethylamine N-Nitrosodi-n-propylamine N-Nitrosodiphenylamine

METHOD SUMMARY: A 1 liter water sample or 30-g soil sample is solvent extracted with methylene chloride using a separatory funnel or Soxhlet extractor. The methylene chloride is washed with dilute HCl to remove free amines, dried and concentrated to a volume of 10 mL or less. The sample is then analyzed using a gas chromatograph equipped with a nitrogen-phosphorous detector (NPD). DETECTION LEVEL: 1 ug/L or 33 ug/Kg SAMPLING: Grab samples must be collected in amber glass jars. DO NOT rinse the bottles with sample prior to filling. PRESERVATIVE: Neutralize any residual chlorine that may be present with 80 mg of sodium thiosulfate per liter. The samples should be kept on ice from sampling to analysis. If diphenylnitrosamine is to be determined, adjust pH to 7 to 10. HOLDING TIMES: Aqueous samples must be extracted within 7 days (soils within 14 days) and analyzed within 40 days of extraction. COMMENTS: The constituents under this analysis are more commonly analyzed by GC/MS procedures, such as 625 or 8270. PREFERRED SAMPLING CONTAINER: 1 L amber glass bottle.

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EPA Method 608/ SW-846 Method 8081/8082 ORGANOCHLORINE PESTICIDES AND PCBs

METHOD SUMMARY: A 1 liter water sample or a 30 g soil sample is extracted with methylene chloride. The methylene chloride extract is dried and brought to a volume of 5 mL or less, then exchanged into hexane as a final solvent. The extract is then concentrated to a final volume of 5-10 mL and analyzed using a gas chromatograph equipped with an electron capture detector (ECD), a halogen-specific detector. DETECTION LEVEL: 0.05-2 µg/L (aqueous) or 1.65-66 µg/Kg (solids) SAMPLING: Grab samples must be collected in glass containers. DO NOT rinse the bottle with sample prior to filling. PRESERVATIVE: Samples should be kept on ice from sampling to analysis. HOLDING TIMES: Aqueous samples must be extracted within 7 days, soil samples must be extracted within 14 days, and all extracts must be analyzed within 40 days of extraction. For PCB-only analysis, the holding time for extraction and analysis for wastewater is 365 days. For soil, water and waste, PCB holding times are not specified for the SW-846 methods. PREFERRED SAMPLING CONTAINER: 1-L amber glass bottle for aqueous samples, 4 oz glass jar for solids. COMMENTS: This is a GC screening method only, all positive responses should be confirmed through either a second column or GC/MS; however, GC/MS may not provide the low-level detection of the GC/ECD method. SW-846 has previously included all organochlorine pesticides and PCB's together in one method: 8080. The most recent update to SW-846 separates the organochlorine pesticides into method 8081, and the PCB's into 8082.

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EPA Method 608/8081/8082, cont. Component

608

8081

8082

TCL

PP

TTO

App. II

App. IX

α-BHC (alpha) X X X X X X X β-BHC (beta) X X X X X X X δ-BHC (delta) X X X X X X X γ-BHC (Lindane) (gamma) X X X X X X X 4,4'-DDD X X X X X X X 4,4'-DDE X X X X X X X 4,4'-DDT X X X X X X X Aldrin X X X X X X X Chlordane (Tech. Grade) X X X X X X α-Chlordane (alpha) X X X γ-Chlordane (gamma) X X X Chlorobenzilate X X Diallate X Dieldrin X X X X X X X Endosulfan I X X X X X X X Endosulfan II X X X X X X X Endosulfan sulfate X X X X X X X Endrin X X X X X X X Endrin Aldehyde X X X X X X X Endrin Ketone X X Heptachlor X X X X X X X Heptachlor epoxide X X X X X X X Hep. Epox. (α Isomer) X Hep. Epox. (β Isomer) X Isodrin X X X Kepone X X Methoxychlor X X X X X Mirex X PCB-1016 X X X X X X X PCB-1221 X X X X X X X PCB-1232 X X X X X X X PCB-1242 X X X X X X X PCB-1248 X X X X X X X PCB-1254 X X X X X X X PCB-1260 X X X X X X X Toxaphene X X X X X X X

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PCBs in Oil

PCB-1016 PCB-1248 PCB-1221 PCB-1254 PCB-1232 PCB-1260 PCB-1242

METHOD SUMMARY A 1-10 g aliquot of the sample oil is diluted 1:10 in hexane. The sample is subjected to several clean-up steps and analyzed on a gas chromatograph equipped with an electron capture detector (ECD). DETECTION LEVEL: 5 mg/Kg (5 parts per million) SAMPLING: Samples should be collected in glass containers. PRESERVATIVE: None required HOLDING TIME: Not listed COMMENTS This is the EPA preferred method for the determination of polychlorinated biphenyls (PCBs) in waste oils. The EPA has assigned no method number. The document number for this method is EPA-600/4-82-045, Sept. 1982. The laboratory should be warned of any samples submitted for analysis that are suspected to contain PCBs. Due to the relatively high costs associated with PCB waste disposal, the laboratory will typically return any samples found to contain PCB's to the generator for disposal. PREFERRED SAMPLING CONTAINER: 1 to 2 40 mL VOC vials, 75% full.

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EPA Method 609/ SW-846 Method 8091 NITROAROMATICS AND CYCLIC KETONES

2,4-Dinitrotoluene Isophorone 2,6-Dinitrotoluene Nitrobenzene

METHOD SUMMARY: The sample extraction and concentration steps in this method are essentially the same as in method 606, 608, 610, 611 and 612. Isophorone and Nitrobenzene are measured by a flame ionization detector (FID), and the dinitrotoluenes are measured by an electron capture detector (ECD). DETECTION LEVEL: Nitrobenzene 20 ug/L (20 parts per billion) -water

Isophorone 20 ug/L (20 parts per billion) -water 2,6-Dinitrotoluene 1 ug/L (1 part per billion) - water 2,4-Dinitrotoluene 1 ug/L (1 part per billion) - water

SAMPLING Grab samples must be collected in glass containers. DO NOT rinse the bottles with sample prior to filling. PRESERVATIVE: Samples should be kept on ice from time of sampling to analysis. HOLDING TIMES: All aqueous samples must be extracted within 7 days and analyzed within 40 days from time of extraction. COMMENTS: This is a GC screening method only. All positive responses should be confirmed via a second column or GC/MS. PREFERRED SAMPLING CONTAINER: 1 L amber glass bottle.

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EPA Method 610/ SW-846 Method 8100 POLYNUCLEAR AROMATIC HYDROCARBONS

Acenaphthene Acenaphthylene Anthracene Benzo (a) anthracene Benzo (a) pyrene Benzo (b) fluoranthene Benzo (g,h,i) perylene Benzo(k)fluoranthene Chrysene Dibenzo (a,h)anthracene Fluoranthene Fluorene Indeno (1,2,3-c,d) pyrene 1-Methylnaphthalene 2-Methylnaphthalene Naphthalene Phenanthrene Pyrene

METHOD SUMMARY: A 1 liter water sample or 30 g soil sample is extracted with methylene chloride, dried and concentrated to 10 mL or less. The sample is then analyzed using a gas chromatograph equipped with a flame ionization detector (FID). DETECTION LEVEL: 10 µg/L (aqueous) or 330 µg/Kg (Solids) SAMPLING: Samples must be collected in glass container. DO NOT rinse the bottle with sample prior to filling. PRESERVATIVE: Neutralize any residual chlorine present with 80 mg of sodium thiosulfate per liter. Samples should be kept on ice from time of sampling to extraction. HOLDING TIMES: Aqueous samples must be extracted within 7 days, soil samples must be extracted within 14 days, and all extracts must be analyzed within 40 days of extraction. COMMENTS: Because this method employs a non-specific detector, it is quite possible to obtain false positives, especially with highly contaminated samples. Positive detector responses should be confirmed via a second column or GC/MS. Naphthalene is also an EPA 8021 listed compound, which can be used as an economical confirmation technique (for relatively clean water matrices only). EPA Method 610 also allows for analysis via HPLC, however most commercial laboratories cite SW-846 Method 8310 to avoid confusion of analytical techniques. Note that the typical 610/8100 analysis from ENCO will contain all of the components above. Depending upon the regulatory program, several of the components may not be required (example: 1-methylnaphthalene in North Carolina). Please specify the particular component list required when submitting samples for analysis. PREFERRED SAMPLING CONTAINER: 1-L amber glass bottle for aqueous samples, 4oz glass jar for solids.

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EPA Method 611/ SW-846 Method 8111 HALOETHERS

Bis(2-chloroethyl) ether Bis(2-chloroethoxy) methane Bis(2-chloroisopropyI) ether 4-Bromophenyl phenyl ether 4-Chlorophenyl phenyl ether

METHOD SUMMARY: A 1 liter water or 30 g soil sample is extracted with methylene chloride. The extract is then dried and concentrated to 10 mL or less. The sample is the analyzed using a gas chromatograph equipped with an electron capture detector. DETECTION LEVEL: 10 µg/L (aqueous) or 330 µg/Kg (Solids) SAMPLING: Samples must be collected in glass container. DO NOT rinse the bottle with sample prior to filling. PRESERVATIVE: Neutralize any residual chlorine present with 80 mg of sodium thiosulfate per liter. Samples should be kept on ice from time of sampling to extraction. HOLDING TIMES: Aqueous samples must be extracted within 7 days, soil samples must be extracted within 14 days, and all extracts must be analyzed within 40 days of extraction. COMMENTS: The sample extraction and concentrating steps in this method are essentially the same as in methods 606, 608, 609, 610 and 612. Thus, a single sample may be extracted to measure the parameters included in the scope of each of these methods. PREFERRED SAMPLING CONTAINER: 1-L amber glass bottle for aqueous samples, 4oz glass jar for solids.

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EPA Method 612/ SW-846 Method 8121 CHLORINATED HYDROCARBONS

2-Chloronaphthalene 1,2-Dichlorobenzene 1,3-Dichlorobenzene 1,4-Dichlorobenzene Hexachlorobenzene Hexachlorobutadiene Hexachlorocyclopentadiene Hexachloroethane 1,2,4-Trichlorobenzene

METHOD SUMMARY: A 1 liter liquid sample or 30 g soil sample is extracted with methylene chloride. The extract is concentrated to 10 mL or less and analyzed using a gas chromatograph equipped with an electron capture detector (ECD). DETECTION LEVEL: 10 µg/L (aqueous) or 330 µg/Kg (Solids) SAMPLING: Samples must be collected in glass container. DO NOT rinse the bottle with sample prior to filling. PRESERVATIVE: Neutralize any residual chlorine present with 80 mg of sodium thiosulfate per liter. Samples should be kept on ice from time of sampling to extraction. HOLDING TIMES: Aqueous samples must be extracted within 7 days, soil samples must be extracted within 14 days, and all extracts must be analyzed within 40 days of extraction. COMMENTS: Several of the listed compounds here are on the 502.2 list. This is an economical confirmation method for clean aqueous matrices. The sample extraction and concentration steps in this method are essentially the same as in methods 606, 608, 609, 610, and 611. Thus, a single sample may be extracted to measure the parameters included in the scope of each of these methods. PREFERRED SAMPLING CONTAINER: 1-L amber glass bottle for aqueous samples, 4oz glass jar for solids.

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EPA Method 614/ SW-846 Method 8141 ORGANOPHOSPHORUS PESTICIDES

METHOD SUMMARY: A 1 liter water sample or 30 g soil sample is extracted with methylene chloride and concentrated to a final volume of 10 mL or less. The sample is exchanged into hexane and analyzed on a gas chromatograph equipped with either a nitrogen-phosphorous detector (NPD) or an electrolytic conductivity detector (ELCD). DETECTION LEVEL: 0.5 - 10 µg/L - Water

17 - 330 µg/Kg - Soil SAMPLING Samples must be collected in glass containers. DO NOT rinse the bottles with sample prior to filling. PRESERVATIVE: Neutralize any residual chlorine present with 80 mg of sodium thiosulfate per liter. Samples should be kept on ice from time of sampling to analysis. HOLDING TIMES: Aqueous samples must be extracted within 7 days, soil samples must be extracted within 14 days, and all extracts must be analyzed within 40 days of extraction. COMMENTS: Although the method calls for either an NPD or ELCD detector, the samples can be analyzed using an electron capture detector (ECD), which is halide-specific. The detection levels will be somewhat higher. PREFERRED SAMPLING CONTAINER: 1-L amber glass bottle for aqueous samples, 4 oz glass jar for solids.

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EPA Methods 614/8141, cont.

Component 614 8141 *App. II *App. IX Aspon Azinphos methyl X X Bolstar X Carbofenthion Chlorfenvenfos Chlorpyrifos X X Chlorpyrifos methyl X Coumaphos X Demeton-O X X Demeton-S X X Diazinon X X Dichlorofenthion X Dichlorvos X Dimethoate X X X Disulfoton (Dy-syston) X X X X EPN X Ethion X X Ethoprop X Famphur X Fensulfothion X Fenthion X Malathion X X Merphos X Mevinphos (Phosdrin) X Monocrotophos X Naled (Dibrom) X Parathion X X Parathion, methyl- X X X X Parathion, ethyl- X X X Phorate (Thimet) X X X ENCO La

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EPA Methods 614/8141, cont.

Component 614 8141 *App. II *App. IX Ronnel X Stirophos (Tetrachlorvinphos) X Sulfotepp X X TEPP X Thionazin (Zinophos) X X Tokuthion (Protothiofos) X Trichloronate (Agritox) X * NOTE – It is common for Organophosphorus compounds to be included in the analytical lists for semivolatiles analysis by GC/MS (Method 625 or 8270).

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EPA Method 615/ SW-846 Method 8151 CHLORINATED HERBICIDES

METHOD SUMMARY: A 1 liter water sample or 30 g soil sample is acidified. The acid herbicides and their esters and salts are extracted with ethyl ether. The derivatives are hydrolyzed and then converted to their methyl esters using diazomethane as the derivatizing agent. Excess reagent is removed, and the esters are determined with an electron capture detector (ECD). DETECTION LEVEL 0.5-5 µg/L — water, 17-170 µg/Kg — soil SAMPLING: Samples should be collected in amber glass, fitted with screw caps lined with Teflon. Aluminum foil may be substituted for Teflon if the sample is not corrosive. PRESERVATIVE: None. Samples should be kept on ice from time of sampling to extraction. HOLDING TIMES: Aqueous samples must be extracted within 7 days, soil samples must be extracted within 14 days, and all extracts must be analyzed within 40 days of extraction. PREFERRED SAMPLING CONTAINER: 1-L amber glass bottle for aqueous samples, 4oz glass jar for solids. EPA Methods 615, 8151 cont.

Component 615 8151 App. II App. IX 2,4-D X X X X 2,4-DB X X 2,4,5-T X X X X 2,4,5-TP (Silvex) X X X X 3,5-DCBA X Acifluorfen X Bentazon X Chloramben X Dacthal X Dalapon X X Dicamba X X Dichloroprop X X Dinoseb (DNBP) X X X X MCPA X X MCPP X X 4-Nitrophenol X X Pentachlorophenol X X Picloram X

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EPA Method 624/ SW-846 Method 8260 PURGEABLE ORGANICS

METHOD SUMMARY: This is a purge and trap gas chromatographic/mass spectrometric method applicable to the determination of volatile organic compounds. An inert gas is bubbled through a 5 mL water sample or a 1-5 g soil sample which is contained in a specially designed purging chamber at ambient temperature (waters) or 40 °C (soils). The purgeables are efficiently transferred from the aqueous phase to the vapor phase. The vapor is swept through a sorbent trap where the purgeables are trapped. After purging is complete the trap is heated and backflushed with the inert gas to desorb the purgeables onto a CC column where they are separated and detected using a mass spectrometer. DETECTION LIMIT: 1-100 µg/L waters, 1-500 µg/Kg soils (component specific) SAMPLING: Aqueous samples must be collected in 2-3 40 mL VOC vials with no air bubbles present; soils should be collected in either 2 preweighed, DI-preserved vials (or 5g. EnCore™) plus a two oz. Jar for percent solids and midlevel analyses, or 2 preweighed, DI-preserved vials (or 5g. EnCore™), 1 methanol preserved preweighed vial, plus an additional container for percent solids. (Contact your Project Manager prior to sample collection to confirm proper containers.) PRESERVATIVE: Neutralize residual chlorine with 10 mg of sodium thiosulfate per 40 mL. All samples should be kept on ice from time of sampling to analysis. Aqueous samples should be preserved with 1:1 HCl. If solid samples are collected into preweighed vials, samples must be frozen to –10 C within 48 hours of collection. HOLDING TIMES: Aqueous samples must be analyzed within 14 days of sampling date if HCl preserved to pH < 2, otherwise 7 days from sampling. Soils must be analyzed within 14 days. COMMENTS: This is the definitive test for the analysis of volatile organics. The samples can be screened via EPA 601/602 prior to EPA 624 confirmation. This method is very sensitive to erroneous sampling. PREFERRED SAMPLING CONTAINER:




• Non-Florida sites: 2 x 5 g Encores™ (or 5g aliquots in preweighed vials, plus a 2 oz. Septa jar.

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EPA Method 624/8260, cont.

Available Component Lists Component 624 8260 TTO PP TCL App.

I App.

II App.

IX 1,1,1,2-Tetrachloroethane X X X X 1,1,1-Trichloroethane X X X X X X X X 1,1,2,2-Tetrachloroethane X X X X X X X X 1,1,2-Trichloroethane X X X X X X X X 1,1-Dichloroethane X X X X X X X X 1,1-Dichloroethene X X X X X X X X 1,1-Dichloropropene X X 1,2,3-Trichlorobenzene X 1,2,3-Trichloropropane X X X X 1,2,4-Trichlorobenzene X X X 1,2,4-Trimethylbenzene X 1,2-Dibromo-3-chloropropane X X X X 1,2-Dibromoethane (EDB) X X X X 1,2-Dichlorobenzene X X X X X X X 1,2-Dichloroethane X X X X X X X X 1,2-Dichloroethene (total) X 1,2-Dichloropropane X X X X X X X X 1,3,5-Trimethylbenzene X 1,3-Dichlorobenzene X X X X X X 1,3-Dichloropropane X X 1,4-Dichlorobenzene X X X X X X X 1,4-Dioxane X 2,2-Dichloropropane X X 2-Butanone X X X X X 2-Chloroethyl vinyl ether X X X X 2-Chlorotoluene X 2-Hexanone X X X X X 2-Picoline X 4-Chlorotoluene X 4-Methyl-2-pentanone X X X X X Acetone X X X X X Acetonitrile X X Acrolein X X X X X Acrylonitrile X X X X X X Allyl Chloride X X Benzene X X X X X X X X Bromobenzene X Bromochloromethane X X X Bromodichloromethane X X X X X X X X

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Available Component Lists Component

624

8260

TTO

PP

TCL App.

I App.

II App.

IX Bromoform X X X X X X X Bromomethane X X X X X X X X Carbon Disulfide X X X X Carbon tetrachloride X X X X X X X X Chlorobenzene X X X X X X X X Chloroethane X X X X X X X X Chloroform X X X X X X X X Chloromethane X X X X X X X X Chloroprene X X cis-1,2-Dichloroethene X X X cis-1,3-Dichloropropene X X X X X X X X Dibromochloromethane X X X X X X X X Dibromomethane X X X X Dichlorodifluoromethane X X X X X Ethyl Methacrylate X X Ethylbenzene X X X X X X X X Hexachlorobutadiene X X X Iodomethane X X X Isobutyl Alcohol X X Isopropylbenzene X Methacrylonitrile X X Methyl Methacrylate X X Methylene chloride X X X X X X X X Methyl-tert-butyl ether X X X m-Xylene & p-Xylene X X X Naphthalene X X X n-Butylbenzene X n-Propylbenzene X o-Xylene X X X Pentachloroethane X p-Isopropyltoluene X Propionitrile X X sec-Butylbenzene X Styrene X X X X X X X tert-Butylbenzene X Tetrachloroethene X X X X X X X X Toluene X X X X X X X X trans-1,2-Dichloroethene X X X X X X X trans-1,3-Dichloropropene X X X X X X X

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624

8260

TTO

PP

TCL App.

I App.

II App.

IX trans-1,4-Dichloro-2-butene X X X Trichloroethene X X X X X X X X Trichlorofluoromethane X X X X X X Vinyl Acetate X X X Vinyl chloride X X X X X X X X Xylenes (total) X X X X

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EPA Method 625/ SW-846 Method 8270 BASE/NEUTRAL AND ACID EXTRACTABLE ORGANICS

METHOD SUMMARY: This is a gas chromatograph / mass spectrometer method applicable to the analysis of synthetic organic compounds (SOCs) in water and soil. A 1 liter water sample or 30-g soil sample is serially extracted with methylene chloride at a pH greater than 11 and again at a pH less than 2. The methylene chloride is dried, concentrated to 1 mL and analyzed by GC/MS. DETECTION LEVEL Varies with analyte, generally:

10-50 µg/L (parts per billion) - Water 330-1650 µg/Kg (parts per billion) - Soil

SAMPLING: Samples must be collected in glass containers. DO NOT rinse the bottle with sample prior to filling. PRESERVATIVE: Neutralize any residual chlorine present with 80 mg sodium thiosulfate per liter. Samples should be kept on ice from the time of sampling to analysis. HOLDING TIMES Aqueous samples must be extracted within 7 days, soil samples must be extracted within 14 days, and all extracts must be analyzed within 40 days of extraction. COMMENTS: This is the definitive test for the analysis of semivolatile organic compounds. For economical reasons samples may be screened using the appropriate GC method. All positive responses should then be confirmed via MS-based technique. PREFERRED SAMPLING CONTAINER: 1-L amber glass bottle for aqueous samples, 4oz glass jar for solids. ENCO La

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EPA Method 625/8270 BASE/NEUTRAL/ACID EXTRACTABLE ORGANICS, cont.


625

8270

TTO

PP

TCL

App. II App.

IX 1,2,4,5-Tetrachlorobenzene X X 1,2,4-Trichlorobenzene X X X X X X 1,2-Dichlorobenzene X X X X X X 1,3,5-Trinitrobenzene X X 1,3-Dichlorobenzene X X X X X X 1,3-Dinitrobenzene X X 1,4-Dichlorobenzene X X X X X X 1,4-Dioxane X 1,4-Naphthoquinone X X 1-Methylnaphthalene X X X 1-Naphthylamine X X 2,3,4,6-Tetrachlorophenol X X 2,3,7,8-TCDD (presence/absence) X 2,4,5-Trichlorophenol X X X X 2,4,6-Trichlorophenol X X X X X X 2,4-Dichlorophenol X X X X X X X 2,4-Dimethylphenol X X X X X X X 2,4-Dinitrophenol X X X X X X X 2,4-Dinitrotoluene X X X X X X X 2,6-Dichlorophenol X X 2,6-Dinitrotoluene X X X X X X X 2-Acetylaminofluorene X X 2-Chloronaphthalene X X X X X X 2-Chlorophenol X X X X X X X 2-Methyl-4,6-dinitrophenol X X X X X X X 2-Methylnaphthalene X X X X X X 2-Methylphenol X X X 2-Naphthylamine X X 2-Nitroaniline X X X X 2-Nitrophenol X X X X X X X 2-Picoline X 3,3’-Dimethylbenzidine X X 3,3'-Dichlorobenzidine X X X X X X 3-Methylcholanthrene X X 3-Methylphenol X X X 3-Nitroaniline X X X X

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625

8270

TTO

PP

TCL

App. II App.

IX 4-Aminobiphenyl X X 4-Bromophenyl phenyl ether X X X X X X 4-Chloro-3-methyl phenol X X X X X X X 4-Chloroaniline X X X X 4-Chlorophenylphenyl ether X X X X X X 4-Methylphenol X X X X 4-Nitroaniline X X X X 4-Nitrophenol X X X X X X X 4-Nitroquinoline 1-oxide X 5-Nitro-o-toluidine X X 7,12-Dimethyl benz[a]anthracene X X a,a-Dimethylphenethylamine X Acenaphthene X X X X X X X Acenaphthylene X X X X X X X Acetophenone X X Aniline X Anthracene X X X X X X X Aramite X Benzidine X X X X Benzo(a)anthracene X X X X X X X Benzo(a)pyrene X X X X X X X Benzo(b)fluoranthene X X X X X X X Benzo(g,h,i)perylene X X X X X X X Benzo(k)fluoranthene X X X X X X X Benzoic acid X Benzyl alcohol X X X Benzyl-butylphthalate X X X X X X X Bis(2-chloroethoxy) methane X X X X X X X Bis(2-chloroethyl) ether X X X X X X X Bis(2-chloro-isopropyl) ether X X X X X X X Bis(2-ethylhexyl) phthalate X X X X X X X Carbazole X Chrysene X X X X X X X Diallate X Dibenzo(a,h) anthracene X X X X X X X

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625

8270

TTO

PP

TCL

App. II App.

IX Dibenzofuran X X X X Diethyl phthalate X X X X X X X Dimethyl phthalate X X X X X X X Di-n-butyl phthalate X X X X X X X Di-n-octyl phthalate X X X X X X X Dinoseb X Diphenylamine X X Ethyl Methanesulfonate X X p-(dimethylamino) azobenzene X X X X X Fluoranthene X X X X X X X Fluorene X X X X X X X Hexachlorobenzene X X X X X X X Hexachlorobutadiene X X X X X X X Hexachlorocyclopentadiene X X X X X X X Hexachloroethane X X X X X X X Hexachlorophene X Hexachloropropene X X Indeno (1,2,3-c,d)pyrene X X X X X X X Isophorone X X X X X X X Isosafrole X X Methapyrilene X X Methyl Methanesulfonate X X Naphthalene X X X X X X Nitrobenzene X X X X X X X N-Nitrosodiethylamine X X N-Nitrosodimethylamine X X X X X X N-Nitrosodi-n-butyl amine X X N-Nitrosodi-n-propyl amine X X X X X X X N-Nitrosodiphenylamine X X X X X X X N-Nitrosomethylethylamine X X N-Nitrosomorpholine X N-Nitrosopiperidine X X N-Nitrosopyrrolidine X X O,O,O-Triethyl phosphorothioate X X o-Toluidine X X

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625

8270

TTO

PP

TCL

App. II App.

IX Pentachlorobenzene X X Pentachloronitrobenzene X X Pentachlorophenol X X X X X X X Phenacetin X X Phenanthrene X X X X X X X Phenol X X X X X X X p-Phenylenediamine X X Pronamide X X Pyrene X X X X X X X Pyridine X X Safrole X X

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SW-846 Method 8270 SIM PAH’s POLYAROMATIC HYDROCARBONS via Selected Ion Monitoring (SIM)


METHOD SUMMARY: This is a gas chromatograph / mass spectrometer method applicable to the analysis of synthetic organic compounds (SOCs) in water and soil. A 1 liter water sample or 30-g soil sample is serially extracted with methylene chloride at a pH less than 2. The methylene chloride is dried, concentrated to 1 mL and analyzed by GC/MS. DETECTION LEVEL Varies with analyte, generally:

0.1 µg/L (parts per billion) - Water 3.3 µg/Kg (parts per billion) - Soil

SAMPLING: Samples must be collected in glass containers. DO NOT rinse the bottle with sample prior to filling. PRESERVATIVE: Neutralize any residual chlorine present with 80 mg sodium thiosulfate per liter. Samples should be kept on ice from the time of sampling to analysis. HOLDING TIMES Aqueous samples must be extracted within 7 days, soil samples must be extracted within 14 days, and all extracts must be analyzed within 40 days of extraction. COMMENTS: 8270-SIM offers the user lower detection limits than that of the standard “scan mode” product, but with certain limitations. Refer to section IV.C.4 for additional information regarding this technique. PREFERRED SAMPLING CONTAINER: 1-L amber glass bottle for aqueous samples, 4oz glass jar for solids.

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EPA Method 613/ SW-846 Method 8280 2,3,7,8-TETRACHLORODIBENZO-p-DIOXIN

(Dioxin or TCDD) METHOD SUMMARY: A 1 liter water sample or a 30 g soil sample is spiked with radio-isotope labeled 2,3,7,8-TCDD and extracted with methylene chloride and concentrated to a final volume of 1 mL or less. The sample is then analyzed using a gas chromatograph/mass spectrometer. DETECTION LEVEL: <100 ng/L (100 parts per trillion) -Water< 3.3 µg/Kg ( 3.3 parts per billion) - Soil SAMPLING: Samples must be collected in glass container. DO NOT rinse the bottle with sample prior to filling. PRESERVATIVE: Neutralize any residual chlorine present with 80 mg of sodium thiosulfate per liter. Samples should be kept on ice from time of sampling to extraction. HOLDING TIMES: Aqueous samples must be extracted within 7 days, soil samples must be extracted within 14 days, and all extracts must be analyzed within 40 days of extraction. COMMENTS: This is the definitive test for the analysis of dioxin. The analysis is very extensive and hence somewhat costly. Approximate costs run at $500 per sample. Generally, the samples are screened using EPA 625 or 8270 and if positive results are found, then EPA 613 or 8280 is used as a confirmation. PREFERRED SAMPLING CONTAINER: 1-L amber glass bottle for aqueous samples, 4 oz glass jar for solids.

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SW-846 Method 8310 POLYNUCLEAR AROMATIC HYDROCARBONS (HPLC)


METHOD SUMMARY: A 1 liter water sample or 30 g soil sample is extracted with methylene chloride, dried and concentrated to 10 mL or less. The sample is then solvent exchanged into acetonitrile and analyzed using a high performance liquid chromatograph (HPLC) equipped with either an ultraviolet (UV) detector, or ultraviolet and fluorescence detectors in series. DETECTION LEVEL: <1 µg/L (aqueous) or 10 µg/Kg (Solids) for most analytes. SAMPLING: Samples must be collected in glass container. DO NOT rinse the bottle with sample prior to filling. PRESERVATIVE: Neutralize any residual chlorine present with 80 mg of sodium thiosulfate per liter. Samples should be kept on ice from time of sampling to extraction. HOLDING TIMES: Aqueous samples must be extracted within 7 days, soil samples must be extracted within 14 days, and all extracts must be analyzed within 40 days of extraction. COMMENTS: Although more selective than the FID detection used in method 8100, positive detector responses should be confirmed via GC/MS. Naphthalene is also an EPA 8021 listed compound, which can be used as an economical confirmation technique (for relatively clean water matrices only). Note that the typical 8310 analysis from ENCO will contain all of the components above. Depending upon the regulatory program, several of the components may not be required (example: 1-methylnaphthalene in North Carolina). Please specify the particular component list required when submitting samples for analysis. PREFERRED SAMPLING CONTAINER: 1-L amber glass bottle for aqueous samples, 4 oz glass jar for solids.

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SW-846 Method 8330 EXPLOSIVES (HPLC)

Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) 1,3,5-Trinitrobenzene (1,3,5-TNB) 1,3-Dinitrobenzene (1,3-DNB) Methyl-2,4,6-trinitrophenylnitramine (Tetryl) Nitrobenzene (NB) 2,4,6-Trinitrotoluene (2,4,6-TNT) 4-Amino-2,6-dinitrotoluene (4-Am-DNT) 2-Amino-4, 6-dinitrotoluene (2-Am-DNT) 2,4-Dinitrotoluene (2,4-DNT) 2,6-Dinitrotoluene (2,6-DNT) 2-Nitrotoluene (2-NT) 3-Nitrotoluene (3-NT) 4-Nitrotoluene (4-NT)

METHOD SUMMARY: Method 8330 provides a salting-out extraction procedure for low concentration (parts per trillion, or nanograms per liter) of explosives residues in surface or ground water. Direct injection of diluted and filtered water samples can be used for water samples of higher concentration. Solid samples can also be analyzed following an extensive ultrasonic extraction. Following extraction, both water and soil samples are analyzed using an HPLC equipped with an ultraviolet detector. DETECTION LEVEL: ranges from 0.02 to 15 µg/L (aqueous) or 250 to 2200 µg/Kg (Solids) for most analytes. SAMPLING: Samples must be collected in glass containers. PRESERVATIVE: Samples should be kept on ice from time of sampling to extraction. HOLDING TIMES: Aqueous samples must be extracted within 7 days, soil samples must be extracted within 14 days, and all extracts must be analyzed within 40 days of extraction. COMMENTS: Confirm available constituents and required detection limits prior to sample submission. The 8330 procedure requires all positive results be confirmed on a secondary column. PREFERRED SAMPLING CONTAINER: 1-L amber glass bottle for aqueous samples, 4-8 oz glass jar for solids.

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Florida Method FL-PRO Petroleum Range Organics

Total Petroleum Hydrocarbons within the alkane range of C8–C40. METHOD SUMMARY: A 1 liter water sample or 30 g soil sample is extracted with methylene chloride, dried and concentrated to 10 mL or less. The extract is subjected to a silica gel cleanup to remove any aliphatic hydrocarbons present, then analyzed using a gas chromatograph equipped with a flame ionization detector (FID). DETECTION LEVEL: 0.2 mg/L (aqueous) or 6.0 mg/Kg (Solids) SAMPLING: Samples must be collected in glass container. DO NOT rinse the bottle with sample prior to filling. PRESERVATIVE: Neutralize any residual chlorine present with 80 mg of sodium thiosulfate per liter. Aqueous samples are preserved to a pH of less than 2 with sulfuric acid. Samples should be kept on ice from time of sampling to extraction. HOLDING TIMES: Aqueous samples must be extracted within 7 days, soil samples must be extracted within 14 days, and all extracts must be analyzed within 40 days of extraction. COMMENTS: This method was developed by the Florida Department of Protection to replace the freon-based procedures 418.1 and 9073 for all petroleum-related work (procedures required by FL Administrative Codes 62-770 and 62-775). The method was developed to quantify total response from C8 (midpoint of most gasolines) through C40 (heavier than most motor oils). Results cannot be compared between the freon-based procedures and the FL-PRO due to differences in the solvents’ solubility characteristics and the temperature limitations associated with GC analyses. PREFERRED SAMPLING CONTAINER: 2 x 1-L amber glass bottle for aqueous samples, 1x4 oz glass jar for solids.

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SW-846 Method 8015 (NHVO) NON-HALOGENATED VOLATILE ORGANICS

Methanol Ethanol n-Propanol Isopropanol n-Butanol Isobutanol 2-Methyl-1-butanol 3-Methyl-1-butanol 2-Butanone 2-Hexanone

METHOD SUMMARY: This method can be performed by standard purge an trap, or by direct aqueous injection (DAI), depending upon the required components and quantitation levels. To perform by purge and trap, an inert gas is bubbled through a 5-25 mL water sample or 1-5 g soil sample contained in a specially designed purging chamber. Aqueous samples are purged at ambient temperature, while soils must be heated to approximately 55°C. The volatile constituents are efficiently transferred from the aqueous phase to the vapor phase. The vapor is swept through a sorbent trap where the components are trapped. After purging is completed, the trap is backflushed with the inert gas to desorb the components onto a gas chromatographic column. The gas chromatograph is temperature programmed to separate the compounds that are then detected with a Flame Ionization Detector (FID). In the Direct Aqueous Injection technique, a small (1-5 µL) sample is directly injected on the GC column for separation and analysis. DETECTION LEVEL: 0.01-1 mg/L or 0.05-5 mg/Kg (component specific) SAMPLING: Aqueous samples must be collected in 40-mL VOC vials. Aqueous samples, once in the vial, should contain no air bubbles. All samples must be iced or refrigerated from the time of collection until analysis. Soil samples should be collected in 2-4 oz glass jars with Teflon lined septum tops with minimal headspace. PRESERVATIVE: Aqueous: None required to 7 days, HCl to pH < 2 will allow for 14 days. Solids: None COMMENTS Samples are very sensitive to improper sampling and storage. Aqueous samples must be taken in duplicate or triplicate 40 mL VOC vials with no air bubbles (headspace) present. PREFERRED SAMPLING CONTAINER:


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SW-846 Method 8015 (GRO) Gasoline Range Organics

(C6-C10 Alkane Range) METHOD SUMMARY: This is a purge and trap gas chromatographic method. An inert gas is bubbled through a 5-25 mL water sample or 1-5 g soil sample contained in a specially designed purging chamber. Aqueous samples are purged at ambient temperature, while soils must be heated to approximately 55°C. The volatile constituents are efficiently transferred from the aqueous phase to the vapor phase. The vapor is swept through a sorbent trap where the components are trapped. After purging is completed, the trap is backflushed with the inert gas to desorb the components onto a gas chromatographic column. The gas chromatograph is temperature programmed to separate the compounds that are then detected with a Flame Ionization Detector (FID). DETECTION LEVEL: 0.08 mg/L or 0.4 mg/Kg SAMPLING: Aqueous samples must be collected in 40-mL VOC vials. Aqueous samples, once in the vial, should contain no air bubbles. All samples must be iced or refrigerated from the time of collection until analysis. Soil samples should be collected in 2-4 oz glass jars with Teflon lined septum tops with minimal headspace. PRESERVATIVE: Aqueous: None required to 7 days, HCl to pH < 2 will allow for 14 days. Solids: None (see comment below) COMMENTS: Samples are very sensitive to improper sampling and storage. Aqueous samples must be taken in duplicate or triplicate 40 mL VOC vials with no air bubbles (headspace) present. This procedure is most commonly requested to determine the total concentrations present of Gasoline Range Organics (C6-C10 alkane range). Please specify the state of origin or regulatory agency when submitting samples, since the method requirements vary by state program. Similar to the purgeable GC and GC/MS analyses, some areas now require the use of the 5035 procedure for volatile analyses. Please refer to method 8260 for container and sampling requirements. It is frequently referred to as “5030” – although the 5030 reference only addresses the method of sample preparation (purge and trap) PREFERRED SAMPLING CONTAINER:


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SW-846 Method 8015 (DRO) Diesel Range Organics

(C10-C24 Alkane Range) METHOD SUMMARY: This is an extractable gas chromatographic method. The gas chromatograph is temperature programmed to separate the compounds that are then detected with a Flame Ionization Detector (FID). DETECTION LEVEL: 0.1 mg/L or 3.3 mg/Kg SAMPLING: Aqueous samples must be collected in 1 liter glass jars. DO NOT rinse the bottle with sample prior to filling. All samples must be iced or refrigerated from the time of collection until analysis. Soil samples should be collected in a 2 to 4 oz glass jar with Teflon lined septum tops with minimal headspace. PRESERVATIVE: Aqueous: H2SO4 to pH < 2 ; Solids: None COMMENTS This procedure is most commonly requested to determine the total concentrations present of Diesel Range Organics (C10-C24 alkane range). Depending upon the state of origin, quantitation may be required to include an extended range – to C28. Please specify the state of origin or regulatory agency when submitting samples, since the method requirements vary by state program. It is frequently referred to as “3550” – although the 3550 reference only addresses the method of sample preparation (sonication). Aqueous samples are commonly prepared using SW-846 Method 3510 – Separatory Funnel Extraction. PREFERRED SAMPLING CONTAINER:

Aqueous: 1 L amber glass Soils: 2-4 oz widemouth jars

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Volatile Petroleum Hydrocarbons (Massachusetts) MA VPH

METHOD SUMMARY: A 5 mL water sample or a methanol-extracted 15-25 g soil sample is analyzed using a gas chromatograph equipped with PID and FID detectors in series. From the analyses, determinations of various ranges are made including: C5 - C8 Aliphatics, C9 - C12 Aliphatics, and C9 - C10 Aromatics. In Florida, the fractionated results are then used to determine appropriate cleanup strategies by comparing to Table C4 of the Technical Report “Development of Soil Cleanup Target Levels (SCTLs) for Chapter 62-777, F.A.C. DETECTION LEVEL: 100 ug/L (aqueous) or 10 mg/Kg (solids) SAMPLING: Aqueous : samples must be collected with minimal agitation to avoid loss of the analytes of

interest. Containers must be filled completely (no headspace permitted). DO NOT rinse bottle with sample prior to filling.

Soil : Samples may be collected and methanol-preserved in the field, or collected using sealed tube devices such as the EnCore™ sampler. If collected using the EnCore™ device, samples must be methanol preserved in the laboratory within 48 hours of collection. As such, samples should be shipped or delivered to the laboratory as soon as possible to avoid holding time excursions.

PRESERVATIVE: Aqueous : pH < 2 (HCl or H2SO4Soil : Either method (methanol or EnCore) ship and store at 4C. (Field Preservation with

methanol: use methanol in a 1:1 ratio with soil, e.g. add 5 mL to 5 g soil)

), ship and store at 4C.

HOLDING TIMES: Aqueous: Analyze within 14 days of collection. Soil: Analyze within 28 days of collection (Note: samples submitted in EnCores™ must

be prepared within 48 hours of collection!) PREFERRED SAMPLING CONTAINERS: Aqueous: 2 or 3 x 40-mL glass vials Soil: Either one 60 mL glass vial containing soil preserved on a 1:1 basis with methanol,

or one EnCore ™. COMMENTS: This method was first released in Massachusetts in 1997. Since then, many states (including NC and FL) have adopted this procedure. This procedure is much more involved both from a preparatory and analytical standpoint than previous 8015 or "Gasoline Range" methods. VPH is an appropriate analytical technique for the evaluation of the following petroleum products: gasoline, mineral spirits, and some petroleum naphthas. It is inappropriate for the evaluation of kerosene, fuel oil #2, fuel oil #4, fuel oil #6, diesel, jet fuel, and most lubricating oils.

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Extractable Petroleum Hydrocarbons (Massachusetts) MA EPH

METHOD SUMMARY: A 1 liter water sample or a 10 g soil sample is extracted with methylene chloride, dried using sodium sulfate, solvent exchanged into hexane and concentrated to 1 mL. The hexane extract is then fractionated into aliphatic and aromatic fractions using a silica gel cleanup. Each extract is then analyzed separately using a gas chromatograph equipped with a flame ionization detector (FID). From the separate extracts, concentrations of various ranges are determined. The target ranges are C9 - C18 Aliphatics, C19 - C36 Aliphatics, and C11-C22 Aromatics. In Florida, the fractionated results are then used to determine appropriate cleanup strategies by comparing to Table C4 of the Technical Report “Development of Soil Cleanup Target Levels (SCTLs) for Chapter 62-777, F.A.C. DETECTION LEVEL: 100 ug/L (aqueous) or 10 mg/Kg (solids) SAMPLING: Grab samples must be collected in glass containers. DO NOT rinse the bottle with sample prior to filling. PRESERVATIVE: Samples should be kept on ice from sampling to analysis. Aqueous samples are preserved with either sulfuric or hydrochloric acid to a pH <2. HOLDING TIMES: Aqueous samples must be extracted within 14 days, soil samples must be extracted within 7 days, and all extracts must be analyzed within 40 days of extraction. PREFERRED SAMPLING CONTAINERS: Aqueous: Two 1-L amber glass bottles for aqueous samples Solids: One 4 oz glass jar for solids. COMMENTS: This method was first released in Massachusetts in 1997. Since then, many states (including NC and FL) have adopted this procedure. This procedure is much more involved both from a preparatory and analytical standpoint than previous 8015 or "Diesel Range" methods. EPH is an appropriate analytical technique for the evaluation of the following petroleum products: kerosene, fuel oil #2, fuel oil #4, fuel oil #6, diesel, jet fuel, and certain lubricating oils. It is inappropriate for the evaluation of gasoline, mineral spirits, petroleum naphthas, or other petroleum products containing significant percentages of hydrocarbons lighter than C9.

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Total Petroleum Hydrocarbons (TPHWG) TPH Working Group

METHOD SUMMARY: This FDEP-approved gas chromatographic method is designed to determine the concentrations in soil and water of petroleum hydrocarbons from n-hexane (C6) to n-pentatriacontane (C35); an approximate boiling point range from 70 °C to 500 °C. This includes the gasoline, diesel range, and some portions of heavier fuels and lubricating oils. This method also describes the separation of the petroleum hydrocarbons into aliphatic and aromatic fractions for further delineation and identification. In Florida, the fractionated results are then used to determine appropriate cleanup strategies by comparing to Table C4 of the Technical Report “Development of Soil Cleanup Target Levels (SCTLs) for Chapter 62-777, F.A.C.

C5-C7 Aromatic C5-C6 Aliphatic >C8-C10 Aromatic >C6-C8 Aliphatic >C10-C12 Aromatic >C8-C10 Aliphatic >C12-C16 Aromatic >C10-C12 Aliphatic >C16 -C21 Aromatic >C12-C16 Aliphatic >C21 -C35 Aromatic >C16-C35 Aliphatic

DETECTION LEVEL: estimated: 5 mg/L (aqueous) or 50 mg/Kg (solids) depending upon ranges being measured. SAMPLING: Grab samples must be collected in glass containers. DO NOT rinse the bottle with sample prior to filling. PRESERVATIVE: Samples should be kept on ice from sampling to analysis. Aqueous samples are preserved with hydrochloric acid to a pH <2. HOLDING TIMES: Aqueous samples must be extracted and analyzed within 7 days, soil samples must be extracted and analyzed within 14 days. PREFERRED SAMPLING CONTAINERS: Aqueous: 2 or 3 x 40-mL glass vials Solids: One 4 oz glass jar COMMENTS: This method is typically employed following the characterization of a site with hydrocarbon contamination. Cleanup levels vary for the ranges and fractions based on relative toxicity data. This procedure was developed primarily by the Shell Development Company, and has been adopted for use (either wholly or in part) in several state petroleum programs.

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EPA Method 504.1 (Drinking Water) Microextractables – EDB and DBCP

1,2-Dibromoethane (EDB) 1,2-Dibromo-3-chloropropane (DBCP) 1,2,3-Trichloropropane

METHOD SUMMARY: 35 mL of water is extracted with hexane and analyzed on a gas chromatograph equipped with an electron capture detector (ECD). DETECTION LEVEL: 0.02 µg/L (20 parts per trillion) - water SAMPLING Because of the components’ volatile nature, sampling should be performed with the same consideration as other volatile parameters (ex: 8021/8260). PRESERVATIVE Neutralize any residual chlorine present with 3 mg sodium thiosulfate. Samples should be kept at 4o

C from the time of sampling to analysis.

HOLDING TIME: Samples must be extracted and analyzed within 14 days, and analyzed within 24 hours of extraction.. COMMENTS Care should be taken in the sampling to avoid excessive aeration. This method is also sensitive to interferences from trihalomethanes (bromodichloromethane, bromoform, chloroform, and dibromochloromethane), commonly associated with chlorinated water supplies. PREFERRED SAMPLING CONTAINER: 40-mL vial, 3 per site

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EPA Method 551.1 (Drinking Water) Microextractables – Chloral Hydrate

Chloral Hydrate This method may also be applied to a wide range of Disinfection Byproducts (DBPs), Chlorinated Solvents, and Pesticides/Herbicides

METHOD SUMMARY: A 50 mL sample aliquot is extracted with 3 mL of MTBE or 5 mL of pentane. Two µL of the extract is then injected into a GC equipped with a fused silica capillary column and electron capture detector for separation and analysis. Procedural standard calibration is used to quantitate method analytes. DETECTION LEVEL: 0.011 µg/L (11 parts per trillion) - water SAMPLING Do not rinse the preservative out of the bottles. Sampling should be performed with the same consideration as other volatile parameters (ex: 524). PRESERVATIVE Neutralize any residual chlorine present with 1 g sodium sulfite/phosphate buffer. Samples should be kept at 4o


HOLDING TIME: Samples must be extracted within 14 days of sampling and the extracts analyzed within 14 days of extractions. COMMENTS Care should be taken in the sampling to avoid excessive aeration. This method is also sensitive to interferences from trihalomethanes (bromodichloromethane, bromoform, chloroform, and dibromochloromethane), commonly associated with chlorinated water supplies. Avoid contact with plastic items during sampling, as Phthalate contamination may be introduced which could interfere with the analysis. PREFERRED SAMPLING CONTAINER: 60-mL Amber VOA vial, 3 per site

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EPA Method 552.2 (Drinking Water) Haloacetic Acids

Bromochloroacetic Acid (BCAA) Monobromoacetic Acid (MBAA) Bromodichloroacetic Acid (BDCAA) Trichloroacetic Acid (TCAA) Chlorodibromoacetic Acid (CDBAA) Tribromoacetic Acid (TBAA) Dalapon Monochloroacetic Acid (MCAA) Dibromoacetic Acid (DBAA) Dichloroacetic Acid (DCAA) METHOD SUMMARY: A 40-mL volume of sample is adjusted to pH <0.5 and extracted with 4-mL of methyltert- butyl-ether (MTBE). The haloacetic acids that have been partitioned into the organic phase are then converted to their methyl esters by the addition of acidic methanol followed by slight heating. The acidic extract is neutralized by a backextraction with a saturated solution of sodium bicarbonate and the target analytes are identified and measured by capillary column gas chromatography using an electron capture detector (GC/ECD). Analytes are quantitated using procedural standard calibration. DETECTION LEVEL: 1 µg/L (1 part per billion) - water SAMPLING Fill sample bottles to just overflowing but do not rinse the preservative out of the bottles. PRESERVATIVE Convert any free residual chlorine present to combined chlorine with 6 mg of ammonium chloride. Samples should be kept at 4o


HOLDING TIME: Samples must be extracted within 14 days of sampling and the extracts analyzed within 7 days of extractions. COMMENTS After collecting the sample in the bottled containing the ammonium chloride, seal the bottle and agitate by hand for 1 minute. Avoid contact with plastic items during sampling, as Phthalate contamination may be introduced which could interfere with the analysis. PREFERRED SAMPLING CONTAINER: 60-mL Amber VOA vial, 3 per site ENCO La

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EPA Method 505 (Drinking Water) Chlorinated Pesticides and PCBs

Alachlor Aldrin Atrazine Chlordane 57-74-9 alpha-Chlorodane gamma-Chlorodane Dieldrin Endrin Heptachlor Heptachlor Epoxide Hexachlorobenzene Hexachlorocyclopentadiene Lindane Methoxychlor cis-Nonachlor trans-Nonachlor Simazine Toxaphene Aroclor 1016 Aroclor 1221 Aroclor 1232 Aroclor 1242 Aroclor 1248 Aroclor 1254 Aroclor 1260 METHOD SUMMARY: A 35-mL sample is extracted with 2-mL of hexane. The concentrations of pesticides and PCBs in the extract are measured using a gas chromatography (GC) system equipped with an electron capture detector (ECD). DETECTION LEVEL: 0.02 ug/L to 0.2 ug/L (20 to 200 parts per trillion) - water SAMPLING Fill sample bottles to just overflowing but do not rinse the preservative out of the bottles. PRESERVATIVE Neutralize any residual chlorine present with 3 mg of sodium thiosulfate. Samples should be kept at 4o


HOLDING TIME: Samples must be extracted within 14 days of sampling except for heptachlor (7 days) and the extracts analyzed within 24 hours of extractions. COMMENTS Avoid contact with plastic items during sampling, as Phthalate contamination may be introduced which could interfere with the analysis. PREFERRED SAMPLING CONTAINER: 40-mL VOA vial, 3 per site

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EPA Method 515.4 (Drinking Water) Chlorophenoxy Herbicides

Acifluorfen 3,5-Dichlorobenzoic acid Bentazon Dichlorprop Chloramben Dinoseb 2,4-D Pentachlorophenol Dalapon Picloram 2,4-DB 2,4,5-T Dacthal acid metabolites 2,4,5-TP (Silvex) Dicamba Quinclorac

METHOD SUMMARY: A 40-mL volume of sample is adjusted to pH >12 with 4 N sodium hydroxide and allowed to sit for one hour at room temperature to hydrolyze derivatives. Following hydrolysis, a wash step using a hexane:MtBE mixture is performed as a sample cleanup and to remove Dacthal. The aqueous sample is then acidified with sulfuric acid to a pH of less than 1 and extracted with 4-mL of methyl tert-butyl ether (MtBE). The chlorinated acids that have been partitioned into the MtBE are then converted to methyl esters by derivatization with diazomethane. The target esters are separated and identified by fast capillary column gas chromatography using an electron capture detector (GC/ECD). Analytes are quantified using a procedural standard calibration technique with an internal standard. DETECTION LEVEL: 0.04 ug/L to 1 ug/L (40 to 1000 parts per trillion) - water SAMPLING Fill sample bottles to just overflowing but do not rinse the preservative out of the bottles. Take care not to aerate the sample. After collecting the sample, seal the bottle and agitate by hand for 15 seconds. PRESERVATIVE Neutralize any residual chlorine present with 2 mg of sodium sulfite. Samples should be kept at 4o


HOLDING TIME: Samples must be extracted within 14 days of sampling except for heptachlor (7 days) and the extracts analyzed within 21 days of extractions. COMMENTS Avoid contact with plastic items during sampling, as Phthalate contamination may be introduced which could interfere with the analysis. PREFERRED SAMPLING CONTAINER: 40-mL Amber VOA vial, 3 per site

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EPA Method 525.2 (Drinking Water) SOCs - Semivolatiles

Acenaphthylene Alachlor Aldrin Ametryn Anthracene Atraton Atrazine Benz[a]anthracene Benzo[b]fluoranthene Benzo[k]fluoranthene Benzo[a]pyrene Benzo[g,h,i]perylene Bromacil Butachlor Butylate Butylbenzylphthalate Carboxin Chlordane components alpha-Chlordane gamma-Chlordane trans-Nonachlor Chlorneb Chlorobenzilate Chlorpropham Chlorothalonil Chlorpyrifos 2-Chlorobiphenyl Chrysene Cyanazine Cycloate Dacthal (DCPA) 4,4'-DDD 4,4'-DDE 4,4'-DDT Diazinon Dibenz[a,h]anthracene Di-n-Butylphthalate 2,3-Dichlorobiphenyl Dichlorvos Dieldrin Diethylphthalate Di(2-ethylhexyl)adipate Di(2-ethylhexyl)phthalate Dimethylphthalate 2,4-Dinitrotoluene 2,6-Dinitrotoluene Diphenamid Disulfoton Disulfoton Sulfoxide Disulfoton Sulfone Endosulfan I Endosulfan II Endosulfan Sulfate Endrin Endrin Aldehyde EPTC Ethoprop Etridiazole Fenamiphos Fenarimol Fluorene Fluridone Heptachlor Heptachlor Epoxide 2,2', 3,3', 4,4', 6-Heptachlorobiphenyl Hexachlorobenzene 2,2', 4,4', 5,6'-Hexachlorobiphenyl Hexachlorocyclohexane, alpha Hexachlorocyclohexane, beta Hexachlorocyclohexane, delta Hexachlorocyclopentadiene Hexazinone Indeno[1,2,3,c,d]pyrene Isophorone Lindane Merphos Methoxychlor Methyl Paraoxon Metolachlor Metribuzin Mevinphos MGK Molinate Napropamide Norflurazon 2,2', 3,3', 4,5', 6,6'-Octachlorobiphenyl Pebulate 2,2', 3', 4,6'-Pentachlorobiphenyl Pentachlorophenol Phenanthrene cis-Permethrin trans-Permethrin Prometon Prometryn Pronamide Propachlor Propazine Pyrene Simazine Simetryn Stirofos Tebuthiuron Terbacil Terbufos Terbutryn 2,2', 4,4'-Tetrachlorobiphenyl Toxaphene Triademefon 2,4,5-Trichlorobiphenyl Tricyclazole Trifluralin Vernolate Aroclor 1016 Aroclor 1221 Aroclor 1232 Aroclor 1242 Aroclor 1248 Aroclor 1254 Aroclor 1260

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EPA Method 525.2 - continued METHOD SUMMARY: Organic compound analytes, internal standards, and surrogates are extracted from a water sample by passing 1 L of sample water through a cartridge or disk containing a solid matrix with a chemically bonded C organic phase (liquid-solid extraction, LSE). 18 The organic compounds are eluted from the LSE cartridge or disk with small quantities of ethyl acetate followed by methylene chloride, and this extract is concentrated further by evaporation of some of the solvent. The sample components are separated, identified, and measured by injecting an aliquot of the concentrated extract into a high resolution fused silica capillary column of a gas chromatography/mass spectrometry (GC/MS) system. Compounds eluting from the GC column are identified by comparing their measured mass spectra and retention times to reference spectra and retention times in a data base. Reference spectra and retention times for analytes are obtained by the measurement of calibration standards under the same conditions used for samples. The concentration of each identified component is measured by relating the MS response of the quantitation ion produced by that compound to the MS response of the quantitation ion produced by a compound that is used as an internal standard. Surrogate analytes, whose concentrations are known in every sample, are measured with the same internal standard calibration procedure. DETECTION LEVEL: 0.02 ug/L to 6 ug/L (20 to 6000 parts per trillion) - water SAMPLING Fill sample bottles to just overflowing but do not rinse the sodium sulfite preservative out of the bottles. Take care not to aerate the sample. After filling the bottle, the sample pH is adjusted to <2 with 6 N hydrochloric acid. PRESERVATIVE Neutralize any residual chlorine present with 50 mg of sodium sulfite. After collection the pH is adjusted to <2 with 6N HCl. Samples should be kept at 4o


HOLDING TIME: Samples must be extracted within 14 days of sampling and the extracts analyzed within 30 days of extractions. COMMENTS Avoid contact with plastic items during sampling, as Phthalate contamination may be introduced which could interfere with the analysis. PREFERRED SAMPLING CONTAINER: 1-Liter Amber Glass, minimum of 1 per site

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EPA Method 531.1 (Drinking Water) SOC’s - Carbamates

Aldicarb Aldicarb sulfone Aldicarb sulfoxide Baygon Carbaryl Carbofuran 3-Hydroxycarbofuran Methiocarb Methomyl Oxamyl METHOD SUMMARY: The water sample is filtered and a 400-uL aliquot is in jected into a reverse phase HPLC column. Separation of the analytes is achieved using gradient elution chromatography. After elution from the HPLC column, the analytes are hydrolyzed with 0.05 N sodium hyrdroxide. The methyl amine formed during hydrolysis is reacted with 0-phthalaldehyde (OPA) and 2-mercaptoethanol to form a highly fluorescent derivative which is detected by a fluorescence detector. DETECTION LEVEL: 0.5 ug/L to 4 ug/L (500 to 4000 parts per trillion) - water SAMPLING Fill sample bottles to just overflowing but do not rinse the preservative out of the bottles. After the sample is collected, seal and shake vigorously for 1 minute. PRESERVATIVE 1.8 mL of monochloroacetic acid buffer and 4.8 mg sodium thiosulfate is added to each sample bottle prior to sample collection. Samples should be kept at 4o


HOLDING TIME: Samples must be analyzed within 28 days of collection. COMMENTS PREFERRED SAMPLING CONTAINER: 60-mL VOA vial, 3 per site ENCO La

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EPA Method 547 (Drinking Water) SOC’s - Glyphosate

Glyphosate METHOD SUMMARY: A water sample is filtered and a 200 µL aliquot injected into a cation exchange HPLC column. Separation is achieved by using an isocratic elution. After elution from the analytical column at 65°C, the analyte is oxidized with calcium hypochlorite. The product (glycine) is then coupled with o-phthalaldehyde-2-mercaptoethanol complex at 38°C to give a fluorophor, which is detected by a fluorometer with excitation at 340 nm and detection of emission measured at >455 nm DETECTION LEVEL: 0.7 mg/L (700 parts per billion) - water SAMPLING Fill sample bottles to just overflowing but do not rinse the preservative out of the bottles. PRESERVATIVE 10 mg of sodium thiosulfate is added to each sample bottle prior to sample collection to remove residual chlorine. Samples should be kept at 4o


HOLDING TIME: Samples must be analyzed within 14 days of preparation. COMMENTS PREFERRED SAMPLING CONTAINER: 40-mL VOA vial, 3 per site

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EPA Method 548.1 (Drinking Water) SOC’s - Endothall

Endothall METHOD SUMMARY: Liquid-solid extraction (LSE) cartridges containing an intermediate strength, primarily tertiary amine anion exchanger are mounted on a vacuum manifold and conditioned with appropriate solvents. LSE disks may be used instead of cartridges of all quality control criteria specified in Section 9.0 are met. A 100 mL sample is extracted and the analyte is eluted with 8 mL of acidic methanol. After addition of a small volume of methylene chloride as a co-solvent, the dimethyl ester of endothall is formed within 30 minutes with modest heating (50°C). After addition of salted reagent water, the ester is partitioned into 8-10 mL of methylene chloride. The extract volume is reduced to 1 mL with nitrogen purge for a concentration factor of 100. The extract is analyzed by GC/MS with a megabore capillary column. DETECTION LEVEL: 0.1mg/L (100 parts per billion) - water SAMPLING Fill sample bottles to just overflowing but do not rinse the preservative out of the bottles. After the sample is collected, adjust the pH to <2 with 1:1 HCl. PRESERVATIVE 80 mg of sodium thiosulfate is added to each sample bottle prior to sample collection to remove residual chlorine. Samples should be kept at 4o


HOLDING TIME: Samples must be prepared within 7 days of collection and analyzed within 14 days of preparation. COMMENTS PREFERRED SAMPLING CONTAINER: 1-L Amber glass, minimum 1 per site ENCO La

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EPA Method 549.2 (Drinking Water) SOC’s – Diquat/Paraquat

Diquat Paraquat METHOD SUMMARY: A measured volume of liquid sample, approximately 250 mL, is extracted using a C8 solid sorbent cartridge or a C8 disk which has been specially prepared for the reversed-phase, ion-pair mode. The disk or cartridge is eluted with 4.5 mL of an acidic aqueous solvent. After the ion-pair reagent is added to the eluate, the final volume is adjusted to 5.0 mL. Liquid chromatographic conditions are described which permit the separation and measurement of diquat and paraquat in the extract by absorbance detection at 308 nm and 257 nm, respectively. A photodiode array detector is utilized to provide simultaneous detection and confirmation of the method analytes DETECTION LEVEL: 0.02 mg/L (20 parts per billion) - water SAMPLING Fill sample bottles to just overflowing but do not rinse the preservative out of the bottles. After the sample is collected, adjust the pH to <2. PRESERVATIVE 80 mg of sodium thiosulfate is added to each sample bottle prior to sample collection to remove residual chlorine. After the sample is collected, adjust the pH <2 with 1:1 sulfuric acid. Samples should be kept at 4o


HOLDING TIME: Samples must be prepared within 7 days of collection and analyzed within 14 days of preparation. COMMENTS The analytes are light-sensitive, particularly Diquat. PREFERRED SAMPLING CONTAINER: 500-mL Amber Plastic, minimum 1 per site

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EPA Method 524.2 (Drinking Water) VOCs - Purgeable Organic Contaminants, including Trihalomethanes (THMs)

Acetone Acrylonitrile Allyl chloride Benzene Bromobenzene Bromochloromethane Bromodichloromethane Bromoform Bromomethane 2-Butanone n-Butylbenzene sec-Butylbenzene tert-Butylbenzene Carbon disulfide Carbon tetrachloride Chloroacetonitrile Chlorobenzene 1-Chlorobutane Chloroethane Chloroform Chloromethane 2-Chlorotoluene 4-Chlorotoluene Dibromochloromethane 1,2-Dibromo-3-chloropropane 1,2-Dibromoethane Dibromomethane 1,2-Dichlorobenzene 1,3-Dichlorobenzene 1,4-Dichlorobenzene trans-1,4-Dichloro-2-butene Dichlorodifluoromethane 1,1-Dichloroethane 1,2-Dichloroethane 1,1-Dichloroethene cis-1,2-Dichloroethene trans-1,2-Dichloroethene 1,2-Dichloropropane 1,3-Dichloropropane 2,2-Dichloropropane 1,1-Dichloropropene 1,1-Dichloropropanone cis-1,3-Dichloropropene trans-1,3-Dichloropropene Diethyl ether Ethylbenzene Ethyl methacrylate Hexachlorobutadiene Hexachloroethane 2-Hexanone Isopropylbenzene 4-Isopropyltoluene Methacrylonitrile Methylacrylate Methylene chloride Methyl iodide Methylmethacrylate 4-Methyl-2-pentanone Methyl-t-butyl ether Naphthalene Nitrobenzene 2-Nitropropane Pentachloroethane Propionitrile n-Propylbenzene Styrene 1,1,1,2-Tetrachloroethane 1,1,2,2-Tetrachloroethane Tetrachloroethene Tetrahydrofuran Toluene 1,2,3-Trichlorobenzene 1,2,4-Trichlorobenzene 1,1,1-Trichloroethane 1,1,2-Trichloroethane Trichloroethene Trichlorofluoromethane 1,2,3-Trichloropropane 1,2,4-Trimethylbenzene 1,3,5-Trimethylbenzene Vinyl chloride o-Xylene m-Xylene p-Xylene METHOD SUMMARY: Volatile organic compounds and surrogates with low water solubility are extracted (purged) from the sample matrix by bubbling an inert gas through the aqueous sample. Purged sample components are trapped in a tube containing suitable sorbent materials. When purging is complete, the sorbent tube is heated and backflushed with helium to desorb the trapped sample components into a capillary gas chromatography (GC) column interfaced to a mass spectrometer (MS). The GC separates the components and the MS detects the analytes. Reference spectra and retention times for analytes are obtained by the measurement of calibration standards under the same conditions used for samples.

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EPA Method 524.2 - continued DETECTION LEVEL: 0.020 to 200 ug/L (20 to 200 parts per trillion) - water SAMPLING Because of the components’ volatile nature, aeration of the sample should be avoided. Fill the vials to just overflowing taking care not to flush out the preservative. PRESERVATIVE 25 mg sodium thiosulfate is added to each vial to neutralize any chlorine presernt. After filling the sample vial, acidify to ph < 2 with 0.10 mL 1:1 HCl. Samples should be kept at 4o

C from the time of sampling to analysis. Note – it is not necessary to acidify the sample if ONLY the Trihalomethanes are being analyzed. Current EPA guidance recommends that acide not be added to a sample when MtBE is a target compound.

HOLDING TIME: Samples must be analyzed within 14 days of collection. COMMENTS If a sample foams vigorously when HCl is added, discard that sample. Collect another sample and do not acidify it. Flag the sample as “not acidified”. The sample must be analyzed within 24 hours of collection if the target analyte list contains more than just THMs. PREFERRED SAMPLING CONTAINER: 40-mL vial, 3 per site

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EPA Method 1613 (Drinking Water) SOC’s – Dioxins and Furans by Isotop Dilution HRGC/HRMS

Dioxin (2,3,7,8-TCDD) METHOD SUMMARY: Samples are extracted, cleaned, and concentrated. Extracts are analyzed using high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS). An individual analyte is identified by comparing the GC retention time and ion abundance ratio of two exact ions with the corresponding retention time of an authentic standard and the theoretical or acquired ion-abundance ratios. Quantitative analysis is performed using selected ion current profile (SICP) areas. DETECTION LEVEL: 0.03 ng/L (0.03 parts per trillion) - water SAMPLING Fill sample bottles to just overflowing following conventional sampling practices. Fill the bottles to just overflowing, but do not rinse out the preservative. PRESERVATIVE 80 mg of sodium thiosulfate is added to each sample bottle prior to sample collection to remove residual chlorine. Samples should be kept at 4o


HOLDING TIME: Samples must be prepared and analyzed within 12 months of collection. COMMENTS Dioxins and Furans are very stable compounds, allowing for a long holding time. The sample preparation and cleanup steps for this method along with the high-resolution instrumentation allow for an extremely low detection levels. PREFERRED SAMPLING CONTAINER: 1-L Amber glass, 2 per site

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Inc. Laboratories, 2009 Copyright · C. Gas Chromatography/Mass Spectrometry . Gas...

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Transcript of Inc. Laboratories, 2009 Copyright · C. Gas Chromatography/Mass Spectrometry . Gas...