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7
Chromium Sampling and Analysis
James Jacobs, William E. Motzer and David W. Abbott
Au: Pls. check this deletion
CONTENTS 7.1 Sampling Methods.....................................................................................234 7.1.1 Overview of Soil and Groundwater Sampling ........................236 7.2 Conventional Drilling Techniques ..........................................................237 7.2.1 Hollow-Stem Auger ......................................................................238 7.2.2 Cable-Tool Drilling........................................................................240 7.2.3 Rotary Drilling...............................................................................241 7.2.4 Wire Line Coring...........................................................................242 7.2.5 Monitoring Well Installation .......................................................242 7.3 Other Drilling Methods ............................................................................244 7.3.1 Horizontal Drilling........................................................................244 7.3.2 Direct Push Technology (DPT) Probe Rigs ...............................245 7.3.2.1 DPT Probe Soil Sampling ..............................................245 7.3.2.2 DPT Probe Water Sampling ..........................................246 7.3.2.3 DPT Probe Vapor Sampling ..........................................246 7.3.2.4 DPT Well Points ..............................................................247 7.3.3 Cone Penetration Testing (CPT) .................................................247 7.3.3.1 CPT Soil Sampling..........................................................247 7.3.3.2 CPT Water Sampling ......................................................248 7.3.4 Sensor Probes .................................................................................248 7.3.5 Soil Conductivity or Resistivity..................................................248 7.3.6 Pore Pressure..................................................................................248 7.3.7 Soil Texture.....................................................................................249 7.4 Direct Sensing of Contaminants..............................................................249 7.4.1 In-Situ Screening of Heavy Metals.............................................249 7.4.2 X-Ray Fluorescence .......................................................................250 7.4.3 Laser-Induced Breakdown Spectroscopy ..................................250 7.4.4 Colorimetric Indicators ............................................................... 250 7.4.5 Laser Induced Fluorescence Spectroscopy................................251 7.4.6 Membrane Interface Probe ..........................................................251
1-5667-0608-4/01/$0.00+$1.50 2004 by CRC Press LLC
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234 7.5
Chromium(VI) Handbook
Sampling Procedures and Field Data Recording .................................251 7.5.1 Equipment Decontamination ......................................................252 7.5.2 Instrument Calibration and Maintenance .................................252 7.5.3 Sample Control ..............................................................................252 7.5.3.1 Sample Labels..................................................................252 7.5.3.2 Chain-of-Custody Request for Analysis .....................253 7.5.3.3 Sample Preparation, Packaging, and Handling ........253 7.5.3.4 Sample Delivery to Laboratory ....................................253 7.5.4 Soil Sampling Protocol .................................................................254 7.5.4.1 Prior To Drilling Activities ............................................254 7.5.4.2 Manual Sampling Methods...........................................254 7.5.4.3 Pedologic and Lithologic Descriptions .......................254 7.5.4.4 Soil Sample Quality Control .........................................255 7.6 Water Sampling..........................................................................................255 7.6.1 Well Development Protocol.........................................................255 7.6.2 Groundwater Monitoring Protocol ............................................256 7.6.3 Groundwater Samples Collected from Wells ...........................256 7.6.4 Turbidity .........................................................................................257 7.6.5 Quality Control of Groundwater Samples................................258 7.6.5.1 Duplicates.........................................................................259 7.6.5.2 Field Blanks .....................................................................259 7.7 Chemical Analysis .................................................................................... 259 7.7.1 Atomic Absorption Spectroscopy (AAS)...................................259 7.7.2 Graphite Furnace Atomic Absorption (GFAA) ........................265 7.7.3 Atomic Emission Spectroscopy (AES) .......................................266 7.7.4 Inductively Coupled Plasma .......................................................267 7.7.5 Ion Chromatography ....................................................................268 7.7.6 Mass Spectrometry (MS) ..............................................................268 7.7.7 X-Ray Fluorescence (XRF) Spectroscopy...................................269 7.8 Acknowledgments .....................................................................................269 Bibliography ......................................................................................... 269
7.1
Sampling Methods
Sources of Cr(VI) contamination in soil and groundwater include, but are not limited to, steel and pulp mills, chromium plating facilities, power plants, leather tanning facilities, dye operations, discharge of chromium containing corrosion inhibitors, and erosion of natural ore deposits or mine waste. Chromium related compounds from tailings piles at mines or liquids or solid wastes from industrial processes that might leak or spill from containments, tanks, ditches, pipes, or ponds create the need to sample soil and groundwater. Typical of most sites, subsurface environmental evaluations of this type

TABLE 7.1 Four Phases of Subsurface Investigations
Phase I II Name Preliminary site assessment Media (soil, water, air, bulk materials) investigation Corrective action plan implementation and remedial action (remediation) Verication monitoring Parameters
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III
Initial site visit/examination; generally does not include sampling Surface and subsurface investigation. Collection of appropriate media; collection of empirical chemical Implementation of site investigation to remediate surface/subsurface contamination to appropriate regulatory levels, which is a risk assessment Additional media collection
IV
generally consist of four phases of work commonly known as Phase I through Phase IV Environmental Site Assessments (ESA) (Table 7.1). The generalized four phases reect the process required to take a property potentially contaminated with Cr(VI) from assessment phase (Phase I) through the nal monitoring and site closure phase (Phase IV). The phases generally proceed in order starting with Phase I. Some sites where soil or groundwater contamination is already suspected or documented might start with Phase II in the case of known leak or conrmed Cr(VI) in a water well, or in the case of visually stained surface soils or discolored or dead vegetation in the proximity of a suspected spill or leak of Cr(VI) related substances. A Phase I ESA is a set of noninvasive techniques to acquire information from site inspection and to obtain data generated and supplied by others. A Phase I ESA involves a site inspection, the development of the history of the property, and review of data supplied by regulators, environmental lists and building permit databases, owners, tenants, and so on. Techniques include interviews of knowledgeable persons, review of historical aerial photography, and examination of published and unpublished maps. Phase I includes the collection, sorting, and tabulation of all relevant existing geologic, hydrologic, and hydrogeologic information. Noninvasive data may be collected on a property using surface geophysical methods to locate buried pits or drums that might contain Cr(VI) waste products. A Phase I ESA may coincide with the transfer of property ownership and may be part of environmental due diligence. A Phase II ESA generally involves a subsurface investigation through eld data collection that normally is invasive and is designed to evaluate the sitespecic geologic and hydrogeologic conditions by collecting soil and groundwater samples for chromium analysis. A variety of different techniques and equipment are currently available for assessing the subsurface. Environmental subsurface investigation tools range in size, cost, and operating complexity from hand augers and hand operated drive samplers to hollow-stem augers, direct push technology (DPT), and various drilling rigs. Borings are drilled for geologic, hydrogeologic, and lithologic characterization. Cr(VI) samples
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TABLE 7.2 Purpose of Groundwater Monitoring Wells
Parameter Dene Monitor Provide Explanation
Determine Estimate Develop Assist Evaluate Source:
Vertical and aerial extent of groundwater contamination Target chemical concentrations over time Measurement for detecting the contaminant plume front unexpected changes in plume size or direction of ow data base for groundwater modeling Aquifer characteristics (such as permeability, transmissivity, etc.) Extent of interaquifer movement of contaminants Effects of the remedial measures Rate of contaminant plume movement Data base for designing remedial measures In performing the remedial work (provide hydraulic control and contaminant removal) Aquifer during regular sampling events over the yearly hydrologic cycle
Modied after Sisk (1981).
may be collected using special techniques for eld screening and physical testing. Selected soil or groundwater samples are then submitted to a certied or accredited analytical laboratory for chemical analysis. As part of a Phase II ESA, groundwater monitoring wells may be installed. Several Phase II ESA subsurface investigations might be required prior to completing the Phase II process and fully characterizing vertical and horizontal extent of Cr(VI) soil and groundwater contamination. A Phase III ESA generally involves some type of corrective action; this is the remediation portion of an environmental project. This phase involves designing and implementing the corrective action plan or remediation of soil and/or groundwater. A corrective action plan, remedial option evaluations, and feasibility with remedial design are typically submitted to a regulatory agency for approval prior to commencement of the work. A Phase III ESA may be accompanied by a risk assessment, which is used to determine soil and groundwater cleanup levels. Commencement of the cleanup actions then occurs with construction of a remedial system. A Phase IV ESA occurs after remediation has been completed. In many cases, the regulatory agency in charge, requires at least one year of quarterly groundwater monitoring to verify that the major Cr(VI) contamination source has been appropriately treated or removed. This phase generally includes proper abandonment of existing groundwater monitoring wells after obtaining site closure.
7.1.1
Overview of Soil and Groundwater Sampling
Different drilling and groundwater sampling techniques have been developed and are used for evaluating the presence of Cr(VI) in soil and groundwater.
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Factors to determine the appropriate drilling technique relate to accessibility, duration and cost of project, soil, sediment and rock or sample type (undisturbed or disturbed), and sample integrity (discrete or composite). Conventional drilling methods in unconsolidated alluvial deposits for environmental investigations generally use hollow-stem auger and rotary drilling techniques, and occasionally, cable-tool drilling. For consolidated or semiconsolidated deposits, continuous wire-line, rock coring, and rotary drilling techniques are commonly used. A brief description of groundwater monitoring well installation is included in this section. More detail regarding drilling techniques is provided in Campbell and Lehr (1973), Driscoll (1986), Roscoe Moss (1990), Aller et al. (1989), Barden (1992), and U.S. Department of Interior, Bureau of Reclamation (1981). Other drilling methods used mostly for reconnaissance eldwork include horizontal drilling and DPT. DPT probe rigs and cone penetrometer testing (CPT) rigs can be used to sample soil, soil vapor, and water. In addition, sensor probes have been developed for DPT rigs, which can determine physical parameters, contaminants such as petroleum hydrocarbons, chlorinated solvents, and some trace ions, including chromium. More detailed information on DPT sampling is in Geoprobe (1997, 1998), Jacobs et al. (2000), and Jacobs (2000). Direct sensing of soils and groundwater using sensor probes can be found in Kram et al. (2000).
Au: Pls. check this ref. (year)
7.2
Conventional Drilling Techniques
There are six basic well-drilling systems with various methodologies: (1) cable tool drillingcased and open hole; (2) direct rotary drillingair, air with casing hammer or variant, air with down hole hammer, and mud; (3) reverse mud rotary drilling; (4) auger drilling, both solid- and hollow-stem; (5) core drilling, and (6) DPT/CPT methods. The water well industry (domestic, exploration, agriculture, and municipal) has typically used cable tool and direct/reverse rotary systems, while the environmental industry has used either DPT/CPT methods for reconnaissance level investigations or hollow-stem auger methods for installation of permanent monitoring wells. The distinct difference in drilling methods dramatically impacts the construction, design, and development of the well. For example, the size of the environmental monitoring wells usually range from 2- to 4-inch diameter; in contrast, the water well industry uses anywhere from 4- to 20-inch diameter casing, typically greater than 6-inch diameter. These diameter differences restrict the use of some development tools and impact the effectiveness of well development. Experience has shown that when most 2-inch diameter monitoring wells are sampled, water quality is characterized as very turbid and muddy because monitoring wells generally are not properly or fully developed after installation. Water quality
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measurements (especially for Cr(VI)) from monitoring wells that are not developed do not represent the aquifers actual water quality. Another notable difference between the water well and environmental industry is the use of steel casing, in the former, and polyvinyl chloride (PVC) casing and screen materials in the latter. Because of the superior strength of steel versus weaker PVC casing and screen, more rigorous and harsh development methods can be utilized. With steel casing effective removal of mud slurries, wall cakes, drilling additives, uids, and ne-grained material near the well screen/lter pack/borehole interface can be accomplished. The effectiveness of well development is directly proportional to the amount of energy applied to the interface. PVC casing and screens will break at lower applied energies than steel casing, resulting in poorly developed monitoring wells. Not only is the applied development energy important but also how that energy is effectively transferred to the screen/lter pack/ borehole interface. The percent open area of the intake (well screen) is directly related to efcient transfer of the development energy to the interface. For example, a PVC slotted pipe may have an 8% open area, whereas a PVC or steel wirewrap screen has a 50% open area. Most of the applied energy in slotted pipe interacts with the inside surface of the casing rather than the well screen/ lter pack/borehole interface. Typically, PVC wirewrap screens are not used because of the signicantly lower strength in comparison to either PVC slotted pipe or steel screens. The larger open area provides for a more interactive area in the well with the aquifer. 7.2.1 Hollow-Stem Auger
Hollow-stem continuous ight auger drilling is commonly used for soil sampling to depths of tens of feet, depending on drilling conditions. Hollow-stem auger rigs work well with a variety of unconsolidated soil and alluvial lithologies, including clays, silts, sands, and small-size gravels. However, this technology is not designed to penetrate or sample bedrock or geologic materials greater than small-sized gravel or hardpan (dene hardpan). Hollow-stem augers consist of a series of continuous, interconnected hollow auger ights, usually 5- to 10-feet in length. Hollow-stem auger operates on the principle of a cork (Archemedes) screw. Typical hollow-stem-augers for use in environmental investigation have inside diameters (ID) of 4.25 to 10.25 inches to construct 2- and 4-inch diameter monitoring wells. Hollow-stem ight augers are hydraulically pressed downward and rotated to start drilling. Soil cuttings are rotated up the outside of the continuous ight in the borehole annulus, which results in smearing of silts and clays and drilled materials along the borehole wall. A center rod with plug and pilot bit are mounted at the bottom. The plug is designed to keep soil from entering the mouth of the lead auger while drilling. Upon reaching the sampling depth, the center rod string with plug and pilot bit attached is removed from the mouth of the auger and replaced by a soil sampler.
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FIGURE 7.1 Hollow stem auger drilling rig, richmond, california. (Source: Todd Engineers, 1979.)
Soil sampling is achieved by passing a smaller diameter drill rod into the hollow-stem auger with a soil sampler attached at the bottom. The soil sampler is lowered into the borehole through the hollow-stem of the auger and sampling or coring is started. The sampler is typically either a thin-wall or modied split-barrel sampler with thin walled sample liners. For chromium sampling, polyethylene terephthalate glycol (PETG), PVC, or teon liners are recommended. For nonmetal analysis, including petroleum or chlorinated solvents, brass or stainless steel liners can be used. Samples can be continuously retrieved, although for environmental investigations, soil samples are typically collected at 5.0-foot intervals, or at signicant changes in soil pedology or alluvium lithology. In addition, soil samples are usually collected at intervals of obvious contamination in order to develop a complete soil contamination prole.
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For environmental investigations, the most popular split-barrel samplers are 2.5- or 3-inch outside diameter (OD) samplers. The standard split-barrel sampler has its interior honed or otherwise machined to accept brass or stainless steel liners or rings. Three sample tubes each 6-inches in length, which can be removed from the sampler for capping and shipment to the laboratory, line the split-barrel sampler. Reloading the sampler with liners allows continued sampler use. Typically, the upper 6-inch sample tube is used for lithologic description and physical testing (i.e., permeability and sieve analysis). The middle sample tube is used for eld-screening for constituents of concern, and the bottom sample tube is used to send to a chemical laboratory for analysis. If Cr(VI) waste had been mixed or associated with a petroleum hydrocarbon or chlorinated solvent, the middle tube might be screened with an organic vapor meter to detect volatile organic compounds. The sampler is driven into the soil at the desired sampling interval ahead of the auger bit by using a 140-pound hammer falling freely for 30 inches. Boreholes are either grouted using a tremie (dene tremie) pipe or converted into a monitoring well. Soil or drill cuttings are not used to backll borings due to the potential for cross contamination.
7.2.2
Cable-Tool Drilling
Cable tool drilling techniques can be used for Cr(VI) investigations. Cable tool drilling is the oldest drilling technique available and is not often used in environmental investigations. Cable tool rigs, called percussion rigs, operate by repeatedly lifting and dropping into the borehole a heavy string of drilling tools attached to a cable, crushing larger cobbles and rocks into smaller fragments creating a mud slurry. During cable tool drilling, the hole is continuously cased with steel. A drive shoe is attached to the bottom of the casing to prevent damage to the casing and to cut the borehole sides. A drive collar is used to protect the casing at the surface during driving operations. Cable tool drilling can also be accomplished without casing, which is known as open-hole drilling. The tool string is attached to the cable by means of a rope socket, which is suspended through a pulley from the mast of the drill rig, through the pitman or spudder arm, to the cable storage drum. Drive clamps are attached to the drill string to advance the casing. The process of driving the casing downward about 2 to 5 feet, is followed by periodically bailing slurry and broken rocks from the bottom of the borehole. During cable tool drilling, in permeable and loose materials, the casing may fall on its own weight. Water generally is required to create a slurry at the bottom of the borehole in the unsaturated zone. Because the casing is advanced, soil or unconsolidated alluvium and groundwater samples can be collected during drilling. To open the casing to the water-bearing zone, the cable tool drilled well can be completed with telescope wirewrap screens; a pull-back method or downhole pipe perforators may also be used.
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FIGURE 7.2 Cable tool drilling rig, riverside county, california. (Source: Todd Engineers, 2002.)
7.2.3
Rotary Drilling
Rotary drilling techniques can be used for Cr(VI) investigations, especially appropriate in chromium mining areas where the bedrock is near or at the surface or landlls located in semi-consolidated to consolidated sedimentary rock. Rotary drilling techniques include direct mud rotary, direct air rotary, direct air rotary with a casing driver, direct air rotary with downhole hammer, and reverse dual tube rotary circulation. Direct mud rotary drilling uses prepared water-based drilling uids (usually bentonite), which is pumped down the drill stem through the bit at the end of the drill rods. Drilling uids
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and cuttings are circulated up the outside annular space back to the surface. Fluid at the surface is routed via a pipe or ditch to a sedimentation tank or pit, then to a suction pit where it is recirculated back through the drill rods. Air rotary drilling is similar to that of direct mud rotary, except that air is used as a circulation medium instead of water and the air is not recirculated. Although air lifts the cuttings from the hole, small quantities of water or foaming surfactants (not recommended) are sometimes used to facilitate cutting removal. In unconsolidated deposits, air rotary can be used with or without a casing. Simultaneous drilling and drive casing is needed when large quantities of groundwater are encountered. In reverse circulation, the circulating medium (mud) is pumped downward between the outer bore hole and inner drill pipe, out through the drill bit, then up the inside of the drill pipe. Air can be used in reverse rotary only in the unsaturated zone. Rotary drilling techniques are typically not used in subsurface environmental investigations due to poor sampling capabilities. However, site characterization can be signicantly enhanced using downhole geophysical instruments providing a better understanding of the hydrogeologic framework. Sample integrity may be questionable because added water or mud may chemically react with the formation water and cuttings. With mud rotary, the mud lter cake that develops along the borehole wall may adversely affect adjacent formation permeabilities, similar to the smearing of clays during hollow-stem auger drilling. With air rotary, dispersion of potentially hazardous and toxic particulates in the air during drilling may be a concern, especially with Cr(VI). 7.2.4 Wire Line Coring
Wire line coring produces cylindrically shaped cores. A modied rotary rig is used in conjunction with water, drilling mud, or air. This method has been used in mining areas containing chromium, where bedrock is at or near the surface. The core diameter varies depending on bit size, manufacturer specications, or standards supplied by the Diamond Core Drill Manufacturers Association. Core sizes generally range from about 0.75-inches to greater than 6-inches. Cutting occurs by drill bits located at the end of a rotating barrel or tube. The barrel gradually slides down into the annular opening. The core is then separated from the rest of the formation mass and the barrel containing the core is retrieved. 7.2.5 Monitoring Well Installation
The purpose of monitoring well network in a Cr(VI) contaminant investigation is to evaluate the hydrogeologic framework, which indicates groundwater movement, degradation of groundwater quality from Cr(VI), and to accomplish specic study objects. A work plan and drilling permit application are frequently submitted to and approved by the lead regulatory agency prior to well installation. The borehole for a monitoring or extraction well
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FIGURE 7.3 Reverse mud rotary drilling rig, livermore, california. (Source: Todd Engineers, 1999.)
is frequently drilled using a truck-mounted, continuous ight, hollow-stem auger drill rig. According to many regulatory agency guidelines, boreholes for monitoring wells are usually a minimum of 2.0 to 4.0 inches larger than the outside diameter of the well casing (DWR, 1981, 1990). Hollow-stem augers provide minimal interruption of drilling while permitting soil sampling at the desired intervals. Licensed drillers should install all wells. Well materials for monitoring and extraction wells must be chemically compatible with the potential contaminants (Barcelona et al., 1983). Casing, both blank and screen sections, can be constructed of berglass-reinforced plastic, mild steel, galvanized iron, stainless steel, concrete, or thermoplastic which include PVC, acrylonitrile butadiene styrene (ABS), and styrene rubber (SR). Based on cost, availability, and chemical compatibility, the most common casings and screens used for shallow drilling projects in environmental
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investigations are made of PVC. Deeper wells are typically constructed of either thicker gauge PVC or mild steel. For hollow-stem auger drilling, the auger will remain in the borehole while the well casing is set, to prevent caving. The well is cased with blank and factory-slotted, threaded schedule 40 PVC pipe. The slotted PVC casing is placed from the bottom of the borehole to the top of the aquifer. The blank casing extends from the top of the slotted casing to approximately ground surface. The slots can range from 0.01 or 0.25 inches wide to 1.5 inches long (10 to 250 slot), with approximately 42 slots per linear foot. Slot sizes are determined by a grain size sieve analysis. A threaded PVC cap is fastened to the bottom of the casing. Centering devices may be fastened to the casing to assure even distribution of lter pack and grout within the borehole annulus. Well screens and casings are typically steam cleaned regardless of composition prior to installation to insure that no machine oils or other chemicals are on the casing surfaces. After setting the casing within the auger, lter pack is poured into the annulus to ll from the bottom of the boring to above the exposed interval. The auger is withdrawn as lter pack is poured into the annulus between the auger and casing, being careful to ensure that 2 or 3 feet of lter material is always in the auger. One to two feet of bentonite pellets are then placed above the lter pack, and then hydrated with deionized water. Bentonite pellets are placed to prevent the grout and surface contaminants from reaching the lter material. Neat Portland cement, a common grout for sealing environmental wells, contains approximately 5% bentonite powder. The grout is tremied into the annular space from the top of the bentonite plug to the surface. Approved grout mixtures and grouting techniques may vary depending on local conditions and regulations. A lockable PVC cap is typically placed on the wellhead. A trafc-rated ush-mounted steel cover is installed around a wellhead located in trafc areas. A steel pipe monument is usually set over a wellhead in landscaped areas. The ush-mounted cover box or pipe monument contacts the grout. Grout lls the space between the monument and the sides of the borehole. The monument and grout surface seal is set at or above grade so that drainage is away from the monument. The monument lid is clearly marked Monitoring Well, with the well number.
7.3
7.3.1
Other Drilling Methods

Horizontal Drilling
Horizontal or lateral radial wells have been used by the water supply well and oil industry for decades. In map view, horizontal water wells emanate from a center hub well, which is generally 8 to 12 feet in diameter. Most applications are where the area of concern, such as a contaminant plume, is
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inaccessible due to above-ground structures. Horizontal wells are also used where thin water-bearing zones prevent traditional vertical extraction wells from efciently pumping groundwater. Horizontal wells can have a larger area of impact compared to vertical wells. These advantages make horizontal wells attractive as groundwater aeration (sparging), vapor recovery, pumpand-treat, and injection wells. Horizontal wells can also be used for pressureor jet-grouting a permanent barrier under and around an affected area, bioremediation by use for delivery of microbes, nutrients, and oxygen into the affected area, or as a French drain and landll leachate collection system. Cleaning and rehabilitation of clogged or inefcient horizontal wells is expensive and limits their use to one-time construction. 7.3.2 Direct Push Technology (DPT) Probe Rigs
DPT probe rigs, also called drive point sampling rigs, collect soil, vapor, or water by driving samplers into the subsurface without the rotary action associated with the more conventional hollow-stem auger rigs. DPT works well with a variety of unconsolidated sediments, including clays, silts, and sands; however, this technology is not designed to penetrate or sample coarse-grained formations or bedrock. Small DPT probes were rst developed in the late 1980s and placed on pickup trucks and vans. DPT rigs generally push the rods from the back of the truck. A percussion hammer may be added to such probe units to enhance the depth penetration. Truck-mounted DPT probe rigs, are typically hydraulically powered. The percussion/probing equipment pushes rods connected to smalldiameter (0.8 to 3.0 inch) samplers. DPT sampling relies on dry impact methods to push or hammer boring and sampling tools into the subsurface for preliminary or reconnaissance environmental assessments. This technology does not require drilling uids or water during operation. DPT equipment produces soil samples but generally does not produce large volumes of soil cuttings or other drilling derived wastes, associated with the hollow-stem auger drilling. 7.3.2.1 DPT Probe Soil Sampling Coring starts at the ground surface with an open-tube soil sampler. Soil samples are commonly collected in 2- to 5-foot long clear plastic (PETG, PVC, or butyrate) liners contained within an outer sampler. Plastic liners are easily cut with a knife and are transparent for easy soil and sediment identication and logging. After removal from the sampler, the soil liner container is immediately capped on both ends with teon and/or plastic end caps. Samples are labeled, placed in individual transparent plastic sampling bags, appropriately cooled, and shipped to a federal or state accredited or certied analytical laboratory. Various DPT soil samplers have been designed and manufactured by numerous companies. The main sampler types used in DPT projects include
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FIGURE 7.4 Direct air rotary drilling rig, minden, nevada. (Source: Todd Engineers, 2000.)
split-spoon samplers, open-tube samplers, piston samplers, and dual tube samplers. Split-spoon sampler consists of the sample barrel, which can be split in two along the length of the sampler to expose soil liners. The splitspoon sampler without sample liners is useful for lithologic logging where soil samples will not be collected for chemical analysis. 7.3.2.2 DPT Probe Water Sampling Various types of sealed samplers are available for DPT groundwater sampling. Many DPT probe water samplers use a retractable or expendable drive point. After driving to the zone of interest, the outer casing is raised from the borehole, exposing the underlying well screen. For a nondiscrete groundwater sample, the outer casing contains open-slots. The open-slotted tool is driven from ground surface into the water table. Groundwater is collected using an inner tubing or smaller diameter bailer inserted into the center of the openslotted water sampler. Water samples collected from this method cannot be compared to samples collected at a later date without drilling a new DPT. 7.3.2.3 DPT Probe Vapor Sampling Only if Cr(VI) is associated with a volatile organic compound, such as a chlorinated solvent or petroleum hydrocarbons, will soil vapor sampling be
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a method that might add value to the Cr(VI) subsurface investigation. As the soil vapor probe is being driven into the subsurface, vapor samples can be continuously pumped to the surface in vapor compatible tubing for analysis through conventional eld analyzers, such as a photoionization detector/ame ionization detector (PID/FID) and gas chromatographs. Vapor samples may also be collected in Tedlar bags or steel canisters for transport to an analytical laboratory. What about steel canisters?? 7.3.2.4 DPT Well Points Groundwater and vapor monitoring probes, implants, mini-wells, sparge points, well points or piezometers can be installed with DPT rigs. Well points ranging from approximately 0.5- to 4-inches in diameter can be installed using DPT methods. Generally, DPT installed well points are constructed without a lter pack. A sand pack enhances screened intervals, and probes can be designed and installed with a premade lter pack. The annulus of the well point is generally sealed with bentonite and cement. 7.3.3 Cone Penetration Testing (CPT)
Au: Pls. verify this sentence.
CPT equipment, a form of DPT, has been used manually since the 1920s in Europe. This early CPT equipment did perform direct sensing of soil properties for engineering studies; however, manual methods and tedious calculations made widespread use impractical. In the 1970s, companies like Fugro Geosciences, Inc. (1999) developed automated and computerized CPT rigs for geotechnical uses. Truck-mounted CPT rigs were designed for sampling and performing direct sensing to depths of 200 to 250 ft. These probes have been used extensively in the construction industry to obtain geotechnical data. Within the past ten years, CPT rigs have been used more frequently for environmental applications. 7.3.3.1 CPT Soil Sampling Many soil sample collection options exist for CPT rigs, each depending on the specic medium to be sampled. Many of the CPT soil samplers resemble hollow-stem split-spoon cutting tools. Typically, a push rod with a closed tip (piston sampler) is advanced to a depth just above the desired sampling depth. The cutting tip of a CPT soil sampler is generally opened using a spring-loaded hinge system inside the sampling string. Once the hinge is triggered, the open cutting tube is advanced to the desired depth, lling the cylindrical sample chamber with soil. The former tip is retracted during soil sampling collection. This technique tends to work best in dry soil with low gravel percentages. In some over-pressured sandy environments beneath the water table, sample collection can be difcult. If relatively ner-grained material is located below the sand of interest, it is sometimes useful to space the sampling interval so that the ner material forms a plug at the bottom of the push stroke.
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7.3.3.2 CPT Water Sampling Groundwater samplers typically work by either pumping or mass displacement. The ConeSipper(r) water sampler consists of a screened lower chamber and an upper collection chamber. Two small-diameter teon tubes connect the upper collection chamber to a control panel in the truck. The truck ballast and hydraulic rams are used to push the sampler to a predetermined depth. While the probe is being advanced, nitrogen under relatively high pressure, is supplied to the collection chamber via the pressure/vacuum teon tube to purge the collection chamber and prevent groundwater from entering the chamber before the probe reaches the desired depth. Once the desired depth is reached, the pressurized nitrogen is shut off, excess nitrogen pressure is removed from the 100 ml upper collection chamber, and the chamber lls with groundwater. Finally, nitrogen under relatively low pressure is supplied to the collection chamber to gently displace the water and slowly push the water to the surface through the small-diameter teon sampling tube. Sample collection times range from 20 min to 2 h, depending on the soil type adjacent to the sampling port. The groundwater samples are placed directly into 40 ml volatile organic analysis (VOA) containers.
7.3.4
Sensor Probes
Typical CPT rigs hydraulically push a small diameter instrumented probe and steel support rods into soils. Conventional probes used with the hydraulic ram systems are equipped with transducers for measuring point penetration resistance and sleeve friction. An empirical relationship between these physical strength measurements and soil types is used to derive soil classication logs for the layers penetrated. The most common sensors consist of load cells on the cone tip and sleeve (Robertson and Campanella, 1983a, 1983b; Robertson, 1990).
7.3.5
Soil Conductivity or Resistivity
Conductivity tools can be used to determine soil type. These systems are based on the observation that ne-grained materials will conduct electricity better than coarse-grained materials. Soil conductivity or resistivity logging produces a real time display of conductivity or resistivity. The probe is useful in detecting changes in subsurface lithology. Conductivity or resistivity logging can have vertical resolution of 1- to 4-inch clay layers that may inuence plume migration.
7.3.6
Pore Pressure
Piezocone pore pressure probes are equipped with transducers for determining pore pressure. Piezocones tend to yield better soil type data and
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resolution than the probes that rely only on tip resistance and sleeve friction, since they yield point measurements and do not rely as much on averaging based on properties within the vicinity of the sensors. Piezocone soil classication data are only valid in saturated soils, since a positive pore pressure is required to obtain a reading on the pressure transducer. Many of the newer probes consist of both systems, allowing for continuous proling throughout the unsaturated zone and saturated regions including perched zones.
7.3.7
Soil Texture
New sensors based on real time video imaging have been developed for determining soil texture. While the video resolution is exceptional, the images can sometimes be difcult to use for determining soil classication in the saturated zone, since pore uids can yield complex images. Research is underway to rene the images to determine pore uid saturation levels, relative permeability, moisture content, and hydraulic conductivity.
7.4
Direct Sensing Of Contaminants
For contaminant investigations, sensor probes have been developed to detect and delineate zones containing heavy metals (chromium, arsenic, copper, lead, mercury, silver, and lead), light nonaqueous phase liquids (LNAPLs), polycyclic aromatic hydrocarbons (PAHs), petroleum oils and lubricants (POLs), dense nonaqueous phase liquids (DNAPLs), light and heavy metals, explosives, and radionuclides.
7.4.1
In-Situ Screening of Heavy Metals
The Tri-Services (U.S. Army, Navy, and Air Force) provided research, development, and a technology demonstration program to perform in-situ screening of heavy metals, including chromium. As part of the Site Characterization and Analysis Penetrometer System (SCAPS), sensors have been developed to detect, delineate, and monitor sites with a variety of contaminants. Two in-situ detection techniques for evaluating chromium and other metals have been developed. The X-ray uorescence (XRF) based sensor systems originally developed for in-situ measurement of petroleum hydrocarbons in soils have now been adapted for metals (USEPA, 1999). Another technology is the Laser-Induced Breakdown Spectroscopy (LIBS) technique, a sensor probe method to evaluate in-situ concentrations of Cr(VI) and other metals. More detailed information is available in Lieberman (1998), Lieberman and Knowles (1998), and Lieberman et al. (1990, 1991, and 1997).
250 7.4.2 X-Ray Fluorescence
Field portable X-ray uorescence (XRF) analyzers are nondestructive and are used to monitor concentrations of chromium, as well as other metals. The XRF analyzers are available in two forms: a portable above ground tool and down-hole sensor probe. The above-ground analyzer is used for screening soil cores and is generally less expensive to own and operate. A sophisticated down-hole XRF spectroscopy sensor probe is used to screen in-situ concentrations of metals while boring. The down-hole probe is pushed into the subsurface by CPT rigs. Wires transfer the data to the surface to be analyzed by the above-ground spectrometer. The XRF analyzer can detect metals below 100 parts per million (ppm). The depth constraint on the XRF sensor probe is the depth limitation of the CPT rig. A special operators permit or license is required to operate portable XRF devices. In addition to other heavy metals, XRF also provides rapid, real-time concentrations of nonmetallic toxic elements, and radioactive metals. XRF works by providing a source of X-rays to bombard a soil sample, exciting the elements (atomic number > 0), such as chromium or other element in the soil sample. The bombardment by the X-rays excites the atoms present to emit X-rays that are characteristic of that particular element. The eld portable XRF analyzers can be operated in-situ using a sensor probe, or on the surface. The X-ray source may vary, depending on the analysis that is required. For more information, see Kram et al. (2000) and Elam et al. (1998a and 1998b). 7.4.3 Laser-Induced Breakdown Spectroscopy
Laser-Induced Breakdown Spectroscopy (LIBS) provides for rapid, in the eld analysis of heavy metals, including chromium, in soils. In the ber optic LIBS method, sample atomization and excitation of the metallic elements in the soil is provided directly by a laser spark on the sensor probe. Focusing pulses of laser light on the soil produce the spark. The plasma spark is emitted briey, and the wavelength of the emitted light (the constituent colors), are indicative of the elements present in the soil. The brightness or intensity of the emitted light at a specic wavelength, which is associated with a particular elemental metal, indicates the concentration of the specic metal, such as chromium. The spectrometer splits this emitted light into its constituent colors. A computer then analyzes the colors. Little or no sample preparation time is required using the LIBS technology. The complete spectrum can be obtained during one single laser shot, allowing for rapid analysis. The downhole lasers for LIBS weigh less than 2 pounds. Theriault et al. (1998), and Kram and Lory (1998), Kram et al. (2000) describe the LIBS technology in more detail. 7.4.4 Colorimetric Indicators
Au: Pls. check this ref. citation.
Field portable analysis is available for a variety of organic and inorganic contaminants, including chromium. Colorimetric indicators use a chemical
251
buffer that produces various colors, which quantitatively or qualitatively identify chemical contaminants. For example, Cr(VI) can be analyzed at concentrations in parts per billion (ppb) to ppm using well established colorimetric laboratory methods. Field determinations of colorimetric results are cumbersome, having signicant analytical error and therefore should only be used on a reconnaissance level. The concentration of the chromium is related to the intensity and hue of the color of the reaction products. Calibration of these types of instruments is important to accurate results. 7.4.5 Laser Induced Fluorescence Spectroscopy
Laser Induced Fluorescence (LIF) was developed by the U.S. Army Engineers Waterways Experiment Station CPT development program to identify various chemicals in the subsurface using a CPT probe. Although LIF does not identify chromium, it does identify wavelengths of petroleum hydrocarbons and other organic chemicals that might be associated with chromium in the subsurface. Kram and Lory (1998) describe details of other LIF systems and similar sensing technologies. 7.4.6 Membrane Interface Probe
Although the membrane interface probe (MIP) detects only volatile organic compounds (VOCs) and not metals, chromium is sometimes associated with waste products containing VOCs. The MIP uses a thin lm uorocarbon polymer membrane in direct contact with the soil. This membrane is typically heated to a temperature of 100 to 120C. This thin lm membrane is attached to a stainless steel screen, which serves as a rigid support for the uorocarbon polymer. A clean carrier gas, such as nitrogen, helium, or clean air is used to carry the VOCs in the soil to the surface and into the gas detector, such as the PID/FID. As the probe is pushed into the soil, VOCs in the subsurface contact the heated surface of the MIP polymer membrane. Upon contact, a certain quantity of the VOCs will absorb into the polymer membrane. Once absorbed into the membrane, VOC molecules move by diffusion across the membrane to regions where their concentration is lowest. (Geoprobe, 1997).
7.5
Sampling Procedures and Field Data Recording
All information pertinent to eld investigations is typically kept on daily eld logs and other eld documents. Boring logs, water sampling data sheets and chain-of-custody forms comprise the eld documents in which all pertinent information about borehole samples and groundwater samples are recorded.
252 7.5.1 Equipment Decontamination
Prior to arriving at a sampling site, all sampling equipment should be cleaned with phosphate-free detergent, and double rinsed with deionized water. This procedure should also be carried out on-site prior to, between, and after sampling. Hollow-stem auger drilling equipment should be steam cleaned prior to arriving on site, and between uses. The decontamination water is contained and disposed off in an approved manner.
7.5.2
Instrument Calibration and Maintenance
The following eld equipment is frequently used during the environmental site during sample collection. Calibration procedures and frequency are listed in the manufacturers guidebooks. Organic vapor meter (OVM) to measure soil vapors Photoionization detector (PID) to measure soil vapors Water level sounder to measure water depth and total depth of well Oil-water interface probe to measure water depth, free-product thickness and depth of well pH/temperature/conductivity meter for water samples
7.5.3
Sample Control
Proper identication, preparation, packaging, handling, shipping and storage of samples obtained in the eld is the responsibility of eld personnel. Samples must be readily identiable and should be as representative as possible of in-situ conditions.
7.5.3.1 Sample Labels Each sample container is labeled at the time of collection. The label is attached to the individual sample containers. The labels should contain the following minimum information: Project name and number Date and time of collection Name of collector Sample number
Location of sample collection (i.e., boring and depth, or well number) Preservation or special handling employed
253
7.5.3.2 Chain-of-Custody Request for Analysis A chain-of-custody form for each sample and container is used to track possession of the samples from the time they were collected in the eld until the time they are submitted to and analyzed in the laboratory. The chain-of-custody form will contain the following minimum information: Project name and number Name and signature of collector Date and time of sample collection Number of containers in a sample set Description of sample and container(s) Name and signatures of persons who are involved in the chain-ofcustody Inclusive dates and times of possession Type of analysis requested If a sample is known to have a high chemical concentration, eld personnel should make a note on the chain-of-custody so that appropriate dilutions may be made in the laboratory.
7.5.3.3 Sample Preparation, Packaging, and Handling For chromium sampling, PETG, PVC or teon sample liners are recommended. Brass or stainless steel liners are not suggested for chromium sampling due to the potential for chromium alloys in the metal sample liners. For nonmetal analysis, including petroleum or chlorinated solvents, brass or stainless steel liners can be used. The tube ends are covered with teon tape and plastic end caps, labeled, and sealed in plastic bags. Groundwater samples are placed in laboratory supplied containers, which are compatible with the requested analysis. For chromium and other metal analysis, plastic bottles rather than glass are recommended because metals may be sorbed to glass. Samples are placed into a cooler, generally with bagged ice. For nonmetals analyses, glass bottles are wrapped in padding (i.e., bubble wrap or foam) to prevent breakage.
7.5.3.4 Sample Delivery to Laboratory Environmental samples are delivered to a state certied laboratory under chain-of-custody procedures, usually within 48 h of sampling. Samples are generally maintained, in a cooler, at 4C for transport/shipping to the laboratory. Containers are sealed with security tape to assure the sample integrity during transport and/or shipping. A chain-of-custody should always accompany transported and delivered samples.
254 7.5.4 Soil Sampling Protocol
Soil samples should be collected in accordance with local, state, and federal regulations and/or guidelines. Standard U.S. Environmental Protection Agency (USEPA) methodologies for sampling and analysis are routinely used for environmental projects. Soil cuttings and excess sampling materials should be properly stored and labeled on site in approved United Nations (UN)-designated containers pending off site disposal. 7.5.4.1 Prior to Drilling Activities An underground utility locating service should be contacted between 2 days and 2 weeks prior to drilling. In northern California and Nevada, the public service utility provider is known as Underground Service Alert (USA); in southern California it is known as Dig-Alert. Other areas of the U.S. have similar public service providers. Generally, an 800 telephone number may be found via the Internet or in the local Yellow Pages phone book. These public service providers will contact local utilities (gas and electric, water, sewer, and telecommunications), which will identify and mark buried utilities around and on the property if free access to the property is available. The exact boring locations must be marked, generally with white paint, by the Project Scientist, Geologist, or Engineer based on a prepared and approved work plan. The locating service also provides a unique number that will be used by individual utility companies to identify the property. This identication number is generally active for 28 to 30 days. Private locating services may be required for properties where there is no free access. 7.5.4.2 Manual Sampling Methods Undisturbed samples are obtained using a slide hammer and core sampler with a single sampling cup at the end. Hand-held slide hammers, typically weighing 12 to 30 pounds, are dropped approximately 12 to 24 in. onto the steel extension rods. The soil sampler with retaining sample liner is connected to the leading edge of the extension rods. Some soil sampling systems have foot pedals attached to the rods allowing the operator to step down to push the manual sampler into the ground. Sampling depth can be increased using small hand-held augers to drill down to the target depth. Specialized augers have been developed for sand, mud, and boggy soils. Benets for the manual sampling method are minimal set-up time, low costs and minimum disturbance of the site. The depth of sampling is the limiting factor for the manual sampling method and the level of physical effort is large inches to four feet in length. 7.5.4.3 Pedologic and Lithologic Descriptions Soils and unconsolidated deposits are commonly described according to American Society for Testing Materials (ASTM) Method D 2488-84 and the
Au: Pls. complete the sentence
255
Unied Soil Classication System (USCS) for physical description and identication of soils. Other soils identication systems include the Burmister Soil Identication System (BSIS) for unconsolidated deposits, which are commonly used, with the USCS. Other soil description systems include the Comprehensive Soil Classication System (CSCS) developed by the U.S. Department of Agriculture. The CSCS describes soils as to agricultural productivity potential and best agricultural land use. A complete geologic description rather than engineering soil descriptions (ASTM and USCS) of the subsurface materials can provide information on the depositional geologic environment and yield to a better understanding of the sites geologic framework. The ASTM Soil Classication Flow Chart and the USCS are generally accepted soil description methods used in the engineering and environmental elds. Descriptions for moisture, density, strength, and plasticity are made using ASTM guidelines. However, these descriptions are all geotechnical properties related to the structural aspects and load bearing capacity of the soil and not to the hydrogeologic properties of the soil. For consolidated deposits (including igneous, metamorphic, and sedimentary rocks) the samples should be described using standard rock classications. Color is described by comparing the soil sample with a Munsell Rock Color Chart (Munsell, 1988) The soil is described when moist or wet. Each soil stratum is identied in the order given by: color, soil type, classication symbol, Munsell color designation, consistency or relative density, moisture, structure, and modifying information such as grain size, particle shape, cementation, and stratication. 7.5.4.4 Soil Sample Quality Control Soil sample quality control may involve collection of duplicate samples. These are collected because small variations in soil pedology and alluvial lithology occurring in unconsolidated deposits within several inches may lead to signicant differences in analytical concentrations. Duplicate soil samples should be collected as close as possible to the original sample, in the same soil horizon, lithologic zone, or sampling interval. The recommended minimum for duplicate soil samples is 5% (1 in 20) of total collected samples.
7.6
7.6.1
Water Sampling
Well Development Protocol
Wells are developed to remove residual drilling mud and uids from the well bore, and to improve well performance by removing any ne material in the lter pack that can pass from the native soil or sediment into the well. Well development techniques include pumping, bailing, swabbing, surging,
256
jetting, airlifting, and adding chemical agents. In most cases, surging and pumping is satisfactory. Development water is inspected for product sheen, odors, or sediments. Approximately 3 to 5 wetted casing volumes are removed during development. The well is considered fully developed when consistent pH, temperature, and conductivity readings (within 10%) indicate characteristic groundwater for the aquifer. If the aquifer is slow to recharge, development will continue until the well is pumped dry. Slow recharge to the well likely means that the well is not fully developed and the development process should continue with more rigorous methods and possibly chemicals (i.e., dispersants and occulants); alternatively, the well may not have been properly designed or the permeability of the water-bearing zone is too small. Effective development procedures and activities are key to acquiring a representative groundwater sample especially for Cr(VI). Wells should be developed until the water is sand- and turbid-free. Turbidity has a signicant impact on the reliability and interpretation of minor ion results. Cross contamination of wells from pumps is avoided by using proper decontamination procedures. All development water is stored in UN rated or approved 55-gallon drums, covered with lids, and labeled with the well number(s) and date of rst accumulation. The development water is stored on site pending laboratory analysis, after which the water is disposed off properly.
7.6.2
Groundwater Monitoring Protocol
Monitoring of depth to water and free product thickness within wells at the site is conducted using a water level sounding device or an interface probe. For consistency, all measurements are taken from a reference point on the wellhead at the survey mark. Total depth of well is also measured. To reduce the potential for cross contamination between wells, the monitoring is performed in the order from the least to the most contaminated, if known. Wells containing free product are monitored last. The water level sounders are decontaminated between wells. Water level data collected from the wells are used to develop a water table contour map for the site.
7.6.3
Groundwater Samples Collected from Wells
Au: Pls. dene this term
If free product is detected, a product sample is sometimes collected for source identication. Where several chemical analyses are to be performed for a given well, individual samples are collected in order of decreasing volatility. Purging will proceed from the least to the most contaminated well, if known or indicated by eld evidence. Samples are collected using a disposable polyethylene bailer with a bottom siphon and nylon cord. The
257
groundwater in the bailer is inspected for free product. Samples are transferred to clean laboratory supplied containers.
7.6.4
Turbidity
Turbidity is the state, condition, or quality of opaqueness or reduced clarity of a uid, due to the presence of suspended matter (Bates and Jackson, 1987) and is the measure of the ability of suspended material to disturb or diminish the penetration of light through a uid. Turbidity refers to the presence of suspended solids and organic matter in water that results in reduced clarity and is measured in nephelometric turbidity units (NTU). Unlike surface water, which often contains suspended solids and colloidal or soluble organic matter, groundwater is rarely turbid (Driscoll, 1986). Turbidity is not to be confused with color, which usually results from leaching of organic debris (Hem, 1989). A water sample can have color and no turbidity. Turbidity represents not only an aesthetic problem (graphically depicted in the block buster movie Back to the Future 3 by Marty McFly), but is associated with apparent excessive concentrations of metals such as iron, manganese, and, in particular, trace ions (aluminum, antimony, arsenic, barium, beryllium, cadmium, chromium, copper, lead, mercury, nickel, selenium, silver, thallium, and zinc). Excessive metal concentrations can be caused by the combined and indistinguishable analytical measurements of un-dissolved and dissolved trace ion fractions in the liquid. Accordingly, elevated turbidity levels may be accompanied with elevated trace ion concentrations, even if samples are ltered prior to laboratory analysis. Adding a turbid water sample to acid-charged container to preserve metal ion concentrations will dissolve a portion of the suspended sediment or colloidal metals resulting in overestimation of the true metal concentration in groundwater. Therefore, sample acidization should not be performed for turbid water samples. Rather the sample should be eld ltered or immediately transported to the analytical laboratory. Recommended primary federal and state drinking water goals for turbidity concentrations are less than 1 NTU. A secondary standard of 0.5 NTU is based on the level at which the human eye can detect turbidity (Roscoe Moss, 1990). Turbidity in monitoring, observation, or production well water can result from many causes relating to the installation, drilling, construction, development, completion, operation, sampling methods, and maintenance of the well and may include, among others: 1. Incomplete well development is probably the most common reason for elevated turbidity. 2. Inappropriate well screen and aperture size design specically because of low-open area intake devices such as PVC horizontal or vertical slot screens.
Au: Pls. check the correction
258
Chromium(VI) Handbook 3. Incorrect lter pack design and screen location caused by inadequate characterization of the aquifer grain size and poor formation sample collection. 4. Nonlaminar or turbulent near-well groundwater ow due to over pumping. 5. Excessive pumping water levels causing cascading water. 6. Improper pump design causing excessive well pumpage. 7. Ineffective foot valves on pumps resulting in inconsequential well development.
However, elevated turbidity levels can also be related to ineffective subsurface ltration of induced surface water to the well, or an inadequate sanitary seal with subsequent vertical leakage of water along the side of the casing. Effective surface water inltration to a well is related to the lineal distance between the surface water body and the well intake plus the aquifer grain size and sorting. For example, the closer the well intake is to surface water, the more likely it is that natural subsurface ltration of groundwater will be minimal. Furthermore, clean gravels (gravels with unlled voids) do not have the ltering capacity of bimodal medium- to coarse-grained sands and gravels. However, it is relatively rare to nd such clean gravels in the geologic environment. In most cases, elevated turbidity levels can be attributed to the design, operation, and maintenance of the well. Wells with machine-made or mills knife perforations usually do not produce turbid-free or sand-free groundwater, in contrast to properly designed and placed wirewrap well screens. Perforations or screens placed opposite or directly underlying negrained aquifer or nonaquifer materials may result in persistent and elevated turbidity as the ne-grained materials are removed from around the well. Such mining can result in the collapse of overlying ne-grained materials. Excessive well yields or over-pumping not only increase well inefciencies and shorten well life expectancies, but increase near-well entrance velocities so that ne-grained material can be continuously mobilized and pumped out of the well. This can result in collapse of the framework of the aquifer and increased turbidity levels. Finally, if well development has been incomplete, elevated turbidity may result from the displacement of ne-grained material adjacent to the well screen or perforations. 7.6.5 Quality Control of Groundwater Samples
A quality control program, which is independent from the laboratorys program, is maintained. This program includes the submittal of duplicates, eld blanks, and travel blanks to the laboratory. Spiked samples are not supplied from the eld; the analytical laboratory provides these. Quality
259
control samples are packaged and sealed in the same manner as the other samples. 7.6.5.1 Duplicates A duplicate sample is collected for either 5% (1 in 20) of the samples or one per sampling round, whichever is greater. A duplicate sample is submitted to the laboratory for the same analyses as the original sample; it is acquired by lling separate containers from the same well bailer as the actual sample. The bailers contents are evenly divided between the actual and duplicate samples, to insure duplication. The duplicate sample is labeled so as it is not identied as a duplicate either on the sample container or on the chain-of-custody. 7.6.5.2 Field Blanks Field blanks are prepared for either 5% (1 in 20) of the samples or one per sampling set, whichever is greater. The eld blank is submitted to the laboratory for the same analyses as the rest of the sampling set. The eld blank is acquired by dispensing deionized water into the sampling bailer and then to sample containers in the same manner as groundwater samples. Field blanks are assigned an independent sample number.
7.7
Chemical Analysis
Chemical analysis for Cr is dependent on different analytical instruments, which have different instrumental detection limits. Some of these are briey described below; more detailed descriptions are in Kebbekus and Mitra (1998), Harris (2000), and PerkinElmer (2000). Commonly used analytical methods are summarized in Table 7.3. 7.7.1 Atomic Absorption Spectroscopy (AAS)
AAS requires that a sample be atomized or broken into individual atoms; it uses light absorption to measure gas-phase atom concentrations. In AAS, a ground state atom absorbs energy in the form of light with a specic wave length. As the number of atoms of the element is increased, the amount of light energy also increases. This relationship can be used to determine the amount of light present in an unknown substance versus a standard in which the quantity of the element is known. In AAS, the unknown is introduced into the instrument in aerosol form. It is vaporized by applying energy from an air-acetylene or nitrous oxide-acetylene ame. The ame burner head is aligned so that a light beam from an element-specic lamp passes through the ame where it is absorbed. A detector measures the resultant wave length intensity.
260
TABLE 7.3
Summary of Chromium Analytical Methods

Name Used for Instrument Type Units Detect. Limit Holding Timesa Method Preservativesa Documentation
Oxidation Analytical State Method No.
Air:
Cr(total)
EPA 29 Metals with Mercury
2.5
6 months
mg/m3
None
EPA 40CFR Part 60 Appendix A None EPA 40CFR, Part 60 Appendix A
Cr(total)
EPA 29 NonMercury Metals
2.5
mg/m3
6 months
Cr(VI)
EPA 0061/ 7199
ICP using EPA method 6010B or ICP-MS by method 6020 ICP using EPA method 6010B or ICP-MS by method 6020 IC-PCR, similar to methods 306 and 306A
8.0
ng/dscm
EPA SW-846
Cr(total) ICP-PCR
EPA 306
ICP or GFAA
5.0
mg/l
60 days 14 days
Cr(VI)
Metals To determine particulate emissions emissions from from stationary stationary sources sources. Metals To determine particulate emissions emissions from stationary from stationary sources sources. Hexavalent Determine Cr(VI) chromium emissions from emissions from hazardous waste stationary incinerators,municipal sources waste incinerators, municipal waste combustors, and sludge incinerators. May also be used for Cr (total) Chromium Emissions from and/or decorative and hard hexavalent chrome electroplating chromium facilities, chromium from anodizing operations, stationary and continuous sources chromium plating operations at iron and steel facilities
Refrigeration not EPA 40CFR, required Part 63 4C
Cr(total) ICP or GFAA ICP-PCR 14 days
EPA 306A
5.0
60 days Refrigeration not EPA 40CFR, required Part 63 4C
mg/l
Cr(VI)
Cr(total)
EPA IO-3.3
XRF spectroscopy
0.0039 mg/cm3
EPA 625/R-96/ 010A
0.0027 0.002 0.0014 0.0011 0.0006

AAS
Cr(total)
NIOSH 7200
0.06
mg
NIOSH issue 2, August 15, 1994
Cr(total) ICP-AES
NIOSH 7024
AAS
0.06 1.0
mg mg
Cr(total)
NIOSH 7300
Chromium and/ Less expensive method than or hexavalent EPA 306 Emissions from chromium decorative and hard chrome from stationary electroplating facilities, sources (Mason chromium anodizing Jar Method) operations, and continuous chromium plating operations at iron and steel facilities Metals in heavy Method applies to ambient urban/ aerosols for ne particle (<2.5 mm) samplers, dichotomous industrial samplers, versatile air pollution samplers (VAPS) and PM10 samplers Metals in heavy urban/ industrial Metals in suburban areas Metals in suburban areas Metals in pristine area Metals in clean room manufacturing Chromium and For particulates with compounds concentrations in the (as Cr) by AAb range of 0.05 to 2.5 mg/m3 Compounds For particles ranging from 0.05 (as Cr) by AA to 2.5 mg/m3 Elements by ICP 500 L air sample with digestion by HNO3/HClO4
NIOSH issue 2, August 15, 1994 NIOSH issue 2, August 15, 1994
(Continued )
261
262
TABLE 7.3 (Continued)

Name
Metals and metalloid particulates by AA
Oxidation Analytical State Method No. Used for 0.04

Instrument Type Units

mg/ml
Detect. Limit
Holding Timesa
Method Preservativesa Documentation

OSHA ID-121
Cr(total)
OSHA ID-121
Cr(total)
OSHA ID125G
AAS or ES Determine the amount of specic metals and metallaoid particles in workplace atmosphere using wipe methods for 100 cm2 Metals and Collection and subsequent ICAP-AES metalloid analysis of airborne metal particulates by and metalloid particles ICAP-AES
1.3
mg
OSHA-125G
Water: ICP-AES
Cr(total)
EPA 200.7
4.0
mg/l
Preserve within HNO3 to 2 weeks pH < 2 of collection; 6 months holding time for analysis
EPA/600/ R-94-111
Cr(total) ICP-MS
EPA 200.8
0.9
mg/l
Preserve within HNO3 to 2 weeks of pH < 2 collection; 6 months holding time for analysis
EPA/600/ R-94-111
Cr(VI)
EPA 218.6
IC-PDC
0.2 4.7
mg/l
24 hours; cool to none 4C
Cr(total)
EPA 6010B
Metals and trace Determination of dissolved elements by elements in ground water, ICP-AES surface water, and drinking water. Also used for determination of total recoverable element concentrations in wastewater, sludges, and soil samples Trace elements Analysis of dissolved trace by ICP-MS elements in groundwater, surface water, and drinking water. Also used for total recoverable elements in wastewaters, sludges and soil samples Hexavalent Determines Cr(VI) in drinking chromium in water using IC-PDC drinking water Elements by Analysis of trace elements in ICP-AES aqueous matrices ICP-AES
mg/l
6 months
HNO3 to pH < 2
SW-846
Au: Pls. check this deletion ICP-MS Spectrophot ometer
Cr(total)
EPA 6020
0.02
6 months 24 hours prior to analysis or extracts. SW-846 SW-846,
mg/l mg/l
HNO3 to pH < 2 4C
Cr(VI)
EPA 7196A water
Elements by ICP Analysis of elements in an aqueous matrix Hexavalent Determine concentration chromium by of dissolvent Cr(VI) in colorimetry EP/TCLP characteristic extracts and ground water. Can be used to determine domestic and industrial wastes providing no interfering substances are present
50
Solids: ICP or GFAA 200 methods for metals
Cr(total
TCLP water
5.0
mg/l 6 months for metals from TCLP to extraction
Cr(total) ICP-AES
EPA 6010B
0.5
mg/kg
None prior to SW-846 extraction; refrigeration unless this causes irreversible change to waste SW-846
Cr(total) ICP-MS
EPA 6020
mg/kg
6 months
SW-846
Cr(VI)
EPA 7196A solids
Toxicity Determine the mobility of Characteristics organic and inorganic Leaching analytes in liquid, solid, Procedure andmultiphasic wastes. (TCLP) Technique is followed by standard analytical methods ICP-MS Determination of trace elements in solid matrices including soil, organic material, and industrial wastes ICP-MS Analysis of elements in different matrices including soil, others solids, and industrial waste Hexavalent Determine concentration of chromium by dissolvent Cr(VI) in EP/TCLP colorimetry characteristic extracts and groundwater. Can be used to determine domestic and industrial wastes providing no interfering substances are present Spectrophotometer
50
mg/l
24 hours prior to 4C analysis or extracts
SW-846
(Continued )
263
264
TABLE 7.3
(Continued)
Name 0.5
mg/kg
Oxidation Analytical State Method No. Used for Units
Instrument Type
Detect. Limit
Holding Timesa
Method Preservativesa Documentation
Cr(VI)
EPA 7199
Cr(total) mg/l 6 months for metals from TCLP to extraction
TCLP solids
Determines Determines Cr(VI) in drinking IC-PDC Cr(VI) in soil water using IC-PDC using IC-PDC Toxicity ICP or GFAA 200 Determine the mobility of Characteristics organic and inorganic methods for Leaching metals analytes in liquid, solid, and Procedure multiphasic wastes. Technique is followed by (TCLP) standard analytical methods
5.0
None prior to extraction; refrigeration unless this causes irreversible change to waste
SW-846
Au: Pls provide notes
Notes:
a Holding times and sample preservations are for total and hexavalent chromium only. For methods where multi-elements are analyzed, different metals may have different holding times and sample preservation requirements. Check method documentation. b Elemental analysis for total chromium; not compound specic. However, hexavalent chromium can be sampled on a PVC lter and may be determined by a colorimetric analysis using NIOSH Methods 7600/7604.
Source: NIOSH (1994), USEPA (1999), Zymax (2001) AAS = Atomic Absorption Spectrophotometry AES = Atomic Emission Spectroscopy GFAA = Graphite Furnace Atomic Absorption ICP = Inductively Coupled Plasma IC-PCR = Ion Chromatography Post-Column Reactor ICAP = Inductively Coupled Argon Plasma MS = Mass Spectroscopy XRF = X-ray Fluorescence Spectroscopy
265
ABSORPTION
+ n=1 n=2 n=3
EMISSION
+ n=1 n=2 n=3
FIGURE 7.5 Emission spectroscopy (ES). Principle of Emission Spectroscopy (ES). Atoms in sample are energized (Flame, discharge, plasma). An electron in an atom absorbs the energy by moving from a lower energy shell or orbit (e.g., n = 1) to a higher energy shell (e.g., n = 3)the absorption process. This energized (excited) state is not stable and the electron quickly releases its gained energy by moving from n = 3 to n = 2 (as shown) or to n = 1 (not shown)the emission process. This released energy is a specic amount (a specic wavelength) characteristic of the type of atom (of the element).
7.7.2
Graphite Furnace Atomic Absorption (GFAA)
Graphite furnace atomic absorption is an improvement on AAS because in AAS only a small fraction of the sample reaches the ame, causing the atomized sample to rapidly pass through the light path. To improve on the AAS analytical method, electrothermal vaporization using a graphite furnace is required. With GFAA, an electrically heated graphite tube replaces the ame used in AAS and the sample is introduced directly into the tube. The tube is then heated to remove solvents and major matrix components; the remaining sample is then atomized. Because all of the analyte is atomized and the atoms are retained in the tube sensitivity and detection limits are improved.
266
anode cathode prism hollow-cathode slit slit wavelength burner/flame FIGURE 7.6 Flame Atomic Absorption (FAA) Spectroscopy Principle of Atomic Absorption Spectroscopy (AAS). Light of specic wavelengths from an element-specic hollow-cathode lamp passes through the ame of the gaseous atomized sample. In the sample ame, the element that is the same as in the hollow-cathode lamp absorbs the light from the lamp. The transmitted light is separated into its wavelengths by a prism or grating and the measured intensity is inversely related to the concentration of the element.
7.7.3
Atomic Emission Spectroscopy (AES)
AES uses quantitative measurements of optical emissions of excited atoms to determine an analytes concentration. Atoms in a solution are aspirated and excited into an unstable energy state by vaporization and subsequent atomizing by a ame, a discharge, or a plasma. This excitation provides enough energy so that the unstable atoms emit light as they ultimately decay back to lower levels. An AES instrument is very similar to that used for AAS except that no primary light source is used in AES.
inert anode sample
cathode graphite hollow-cathode slit slit wavelength FIGURE 7.7 Graphite Furnace Atomic Absorption (GFAA) Graphite Furnace (noname) Atomic Absorption (GFAA) Spectroscopy. Same as for Figure 7.6 except that the sample is not burned in a ame. Instead, a graphite furnace heats the sample, converting it to an atomized gas. Typically, an inert gas such as argon, ows across the sample and through the furnace. The residence time of atoms in the furnace (0.1 s) is about 500 times longer than in the ame of FAA, allowing improved atomization of compounds. Also, GFAA usually has a detection limit at least 10 times lower than that of FAA. prism

argon plasma emitted argon + sample emitted
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plasma
induction
argon argon + sample FIGURE 7.8 Inductively-coupled plasma (ICP) spectroscopy. Plasma torch for Inductively-Coupled Plasma (ICP) Spectroscopy. A high-frequency alternating current in a copper coil strongly heats argon, producing thermal electrons that ionizes the gas forming a plasma. An aerosol consisting of argon gas and sample particle mixture is introduced into the plasma torch where the sample is atomized and energized. This results in the emission of element-specic energies or wavelengths.
7.7.4
Inductively Coupled Plasma
ICP commonly uses an argon plasma that can reach temperatures as high as 10,000 K but generally ranges between 5500 and 8000 K. At these temperatures, complete element atomization occurs, reducing interference effects commonly seen in ame AAS. The plasma is formed by a stream of argon gas passing between two quartz tubes with a radio frequency power at 27 MHz applied to a coil and an oscillating magnetic eld. The sample
column
stationary phase
mobile phase mixture separated ions
FIGURE 7.9 Ion Chromatography (IC). Conceptual diagram showing the principle of Ion Chromatography (IC). A mixture of ions in a mobile phase (solvent) ows into a column (tube) containing a stationary phase (e.g., a resin). The difference in afnity of different ions toward the station phase compared to the afnity toward the mobile phase results in a different rate of movement for different ions through the column. Thus, the different eluted ions are separated.
268
is introduced with an ultrasonic nebulizer in which it is directed onto a piezoelectric crystal.
7.7.5
Ion Chromatography
IC requires the separation of ions in a sample. For small ions masses less than 500 atomic mass units (amu), an ion exchange resin is used in which the ionic species is retained. The exchange of ions can be for both cations and anions. A conductivity detector measures the electrical conductivity of the eluting mobile phase. IC has the ability to distinguish not only between anions and cations but it can also be used to determine species having different oxidation states.
7.7.6
Mass Spectrometry (MS)
A mass spectrometer is similar to the monochromator in an AAS or ICP emission system where the atoms or molecules of a substance are ionized, accelerated by an electric eld, and then separated according to their mass. Rather than separating light according to its wavelength, the MS separates ions according to their mass-to-charge ratio. This instrument is often coupled with an ICP allowing for multi element capabilities at much lower detection limits than ICP alone or GFAA. MS can also be used in measuring elemental isotope concentrations and ratios.
sample
sample changed to
ionization
acceleration
mass analyzer and detector
vacuum system FIGURE 7.10 Mass spectrometry (MS). Principle of Mass Spectrometry (MS). MS requires that samples be in the gas phase and all operations are in vacuum (pressure less than 106 mmHg). Solid or liquid samples are converted to gas, and the gas is ionized. Charged plates (or rods) accelerate the ions in a specic direction (e.g., in a tube), the less massive ions moving more rapidly and arriving at a detector before the more massive ions do. Thus, components of the sample are separated my mass (more accurately, by mass/charge, m/e). The ion current is a measure of quantity of ions and relates to the concentration of the components in the sample.
Chromium Sampling and Analysis 7.7.7 X-Ray Fluorescence (XRF) Spectroscopy
269
Fluorescence is the generation of secondary radiation from an atom. The principle of X-ray uorescence (XRF) is similar to that shown in Figure 7.5, whereby the atoms of an energized sample give off specic X-rays that are characteristic of the element. Although the method is able to rapidly analyze nearly all elements simultaneously and is nondestructive, XRF is not commonly used for trace element analysis because it is at least 100 times less sensitive than ES, FAA, GFAA, ICP, or MS.
7.8
Acknowledgments
Geoprobe (R) is a Registered Trademark of Kejr Engineering, Inc. and ConeSipper(R) is a Registered Trademark of Vertek Division of Applied Research Associates.
Bibliography
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fm Page 233 Friday, July 23, 2004 5:46 PM

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1-5667-0608-4/01/$0.00+$1.50 2004 by CRC Press LLC

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Chromium Sampling and Analysis

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Determine Estimate Develop Assist Evaluate Source:

Modied after Sisk (1981).

Overview of Soil and Groundwater Sampling

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Chromium Sampling and Analysis

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Conventional Drilling Techniques

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Chromium Sampling and Analysis

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Chromium Sampling and Analysis

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Chromium Sampling and Analysis

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Other Drilling Methods

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Chromium Sampling and Analysis

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Chromium Sampling and Analysis

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Soil Conductivity or Resistivity

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Chromium Sampling and Analysis

Direct Sensing Of Contaminants

In-Situ Screening of Heavy Metals

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250 7.4.2 X-Ray Fluorescence

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Chromium Sampling and Analysis

Sampling Procedures and Field Data Recording

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252 7.5.1 Equipment Decontamination

Instrument Calibration and Maintenance

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254 7.5.4 Soil Sampling Protocol

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Chromium Sampling and Analysis

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Groundwater Monitoring Protocol

Groundwater Samples Collected from Wells

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Chromium Sampling and Analysis

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