Acquisition of Representative Ground Water Quality Samples for Metals

R.S. Kerr Environmental Research Laboratory (RSKERL) personnel have evaluated sampling procedures for the collection of representative, accurate, and reproducible ground water quality samples for metals for the past four years. Intensive sampling research at three different field sites has shown that the method by which samples are collected has a greater impact on sample quality, accuracy, and reproducibility than whether the samples are filtered or not. In particular, sample collection practices that induce artificially high levels of turbidity have been shown to have the greatest negative impacts on sample quality. Results indicated the ineffectiveness of bailers for collection of representative metal samples. Inconsistent operator usage together with excessive purging generally resulted in excessive turbidity (>100 NTUs) and large differences in filtered and unfiltered metal samples. The use of low flow rate purging and sampling consistently produced filtered and unfiltered samples that showed no significant differences in concentrations. Turbidity levels were generally less than 5 NTUs, even in fine-textured glacial till. We recommend the use of low flow rates, during both purging and sampling, placement of the sampling intake at the desired sampling point, minimal disturbance of the stagnant water column above the screened interval, monitoring of water quality indicators during purging, minimization of atmospheric contact with samples, and collection of unfiltered samples for metal analyses to estimate total contaminant loading in the system. While additional time is spent due to use of low flow rates, this is compensated for by eliminating the need for filtration, decreased volume of contaminated purge water, and less resampling to address inconsistent data results.     

Interpretation of Gas Chromatographic Data in Subsurface Hydrocarbon Investigations

Capillary column gas chromatography (GC) is extremely useful in investigations of subsurface contamination by petroleum hydrocarbons. Fluid samples collected from observation wells are evaluated by GC methods to detect and analyze petroleum hydrocarbons in dissolved and liquid phases. The presence, types and concentrations of many petroleum-derived hydrocarbons dissolved in ground water can be determined. GC analysis can also be used to determine the composition of liquid hydrocarbon products, including gasoline, distillates and heavier oils. The degree of degradation of sampled liquid hydrocarbon product can be estimated from GC information, and this information can be helpful in estimating the length of time the product has been in the subsurface. Determination of the hydrocarbon source and migration path can be made from GC analysis of fluid samples collected at two or more locations.
This paper is intended to demonstrate interpretative techniques that can be used by hydrogeologists to facilitate the detection, identification and mitigation of subsurface hydrocarbons.     

A Gas Chromatographic/Chemical Indicator Approach to Assessing Ground Water Contamination by Petroleum Products

The water-soluble fractions of unleaded gasoline, kerosene and diesel fuel were evaluated by U.S. EPA Methods 602, 610, and 625.
Several chemical indicator compounds useful in assessing petroleum contamination of ground water, including benzene, substituted benzenes, n-alkanes, and polynuclear aromatic hydrocarbons, were identified. These were applied to the interpretation of data collected from monitoring wells at gasoline service stations that were undergoing ground water remediation. The chemical indicators are used to identify the likely type(s) of petroleum contamination. Certain hydrocarbons may be unique to specific fuel types.
Gas chromatograms of field sample extracts were compared with chromatograms of laboratory water-soluble fractions (WSFs) and neat fuels (unleaded gasoline, kerosene, and diesel). In some situations, field samples represented water-soluble fractions of the contaminating fuel. In others, a fuel-water agglomeration was indicated, with the chromatograms showing peaks that represented components of both the WSFs and the neat fuels.
The use of both gas chromatography pattern identification and chemical indicators appears to be a viable approach to assessing ground water contamination caused by petroleum products.     

Elements in Cottonwood Trees as an Indicator of Ground Water Contaminated by Landfill Leachate

Ground water at the Norman Landfill Research Site is contaminated by a leachate plume emanating from a closed, unlined landfill formerly operated by the city of Norman, Oklahoma, Ground water contaminated by the leachate plume is known to be elevated in the concentration of many, organic and inorganic constituents. Specific conductance, alkalinity, chloride, dissolved organic carbon, boron, sodium, strontium, and deuterium in ground water are considered to be indicators of the leachate plume at this site.
Leaf samples of broad-leafed cottonwood, Populus deltoides , were collected from 57 sites around the closed landfill. Cottonwood, a phreatophyte or "well plant," functions as a & surrogate well and serves as a ground water quality sampler. The leaf samples were combusted to ash and analyzed by instrumental neutron activation for 35 elements and by prompt-gamma instrumental neutron activation, for boron. A monitoring well was located within a few meters of a sampled cottonwood tree at 15 of the 57 sites, and ground water samples were collected from these monitoring wells simultaneously with a leaf sample. The chemical analyses of the ground water and leaf samples from these 15 sites indicated that boron, bromine, sodium, and strontium concentrations in leaves were significantly correlated with leachate indicator constituents in ground water. A point-plot map of selected percentiles indicated high concentrations of boron, bromine, and sodium in leaf ash from sites downgradient of the most recent landfill and from older landfills nearby.
Data from leaf analysis greatly extended the known areal extent of the leachate plume previously determined from a network of monitoring wells and geophysical surveys. This phytosgeochemical study provided a cost-effective method for assessing the extent of a leachate plume from an old landfill. Such a method may be useful as a preliminary sampling tool to guide the design of hydrogeochemical and geophysical studies.     

Use of Total Organic Carbon as an Indicator of Contamination from an Oil Refinery, South-Central Kansas

Water samples collected from 26 sites at an abandoned oil refinery in south-central Kansas were analyzed for total organic carbon (TOC) and specific volatile and semivolatile organic compounds by gas-chromatography/mass-spectrometric methods. Results from a Spearman-rho correlation analysis between TOC concentration and the number of compounds (correlation coefficient = 0.71) and TOC concentration and total concentration of compounds identified (correlation coefficient = 0.83) indicate correlations significant at the 0.01 level.
Although TOC data alone would not be sufficient to evaluate hazards posed by oil-refinery wastes, results of the correlation analysis performed using data collected from the site in Kansas indicate that TOC data can be used effectively to delineate petroleum-related ground water contamination and to help identify sources of ground water contaminants. TOC data collected from a large number of temporary sampling points during the initial phases of an investigation will provide an estimate of the extent of hydrocarbon contamination and allow placement of monitoring wells and more detailed sampling in appropriate areas.     

Nickel and Chromium in Ground Water Samples as Influenced by Well Construction and Sampling Methods

An investigation of elevated concentrations of nickel and chromium in certain ground water samples collected at Williams Air Force Base (AFB) indicated that type 304 stainless steel well materials are the source. Chloride in the ground water has apparently caused crevice corrosion of the stainless steel well screens installed during site characterization. An evaluation of site geochemistry suggested that chromium released from the well screen would precipitate, while nickel would remain dissolved. Thus, low-flow purging and sampling significantly reduces the chromium found in the ground water samples because such sampling minimizes the collection of artificially entrained particulates. In contrast to chromium, nickel concentrations did not decrease during low-flow purging and sampling, indicating that it is dissolved. Nickel and chromium concentrations are both low following high-volume purging when turbidity levels are stabilized below 10 nephelometric turbidity units prior to sampling. In the latter case, chromium concentration is low because particulate collection is minimized, and nickel concentration is low because of increased dilution. Based on these results, it is recommended that elevated levels of nickel and chromium in ground water samples collected from stainless steel monitoring wells be carefully evaluated, because well materials may be the source. In addition, although low-volume purging is increasingly becoming the sampling method of choice, high-volume purging may be a useful means of determining whether the well materials influence nickel and chromium concentrations.     

The Effect of Construction, Installation, and Development on the Turbidity of Water in Monitoring Wells in Fine-Grained Glacial Till

Twenty monitoring wells were installed in fine-grained glacial till at two sites in southeastern Wisconsin to study the effects of monitoring well construction, installation, and development on the amount of fine-grained suspended material in the well. The types of well screens used were continuous slot, factory slot, factory slot with a filter wrap, and porous piezometer tips. Some of the wells were installed before the open borehole began to fill with water; others were installed after the water levels in the lower section of the borehole had begun to rise. About half of the wells were developed by surging while the others were simply bailed without surging. Installation of the wells in the initially dry holes resulted in wells that yielded samples with very low turbidity compared to wells installed in wet holes. Water samples from wells that were surged were more turbid than those that were not. The type of construction materials investigated had no effect on the turbidity of samples from the wells.     

Micro-Purge Low-Flow Sampling of Uranium-Contaminated Ground Water at the Fernald Environmental Management Project

Efforts to sample representative, undisturbed distributions of uranium in ground water beneath the Fernald Environmemal Management Project (FEMP) prompted the application of a novel technique that is less invasive in the monitoring well. Recent studies (Kearl et al. 1992; Barcelona et al. 1994) indicate that representative samples can and should be collected without prior well volume exchange purging or borehole evacuation. Field experiments conducted at the FMMP demonstrate that under specific sampling conditions in a welldefined hydrogeologic system, representative ground water samples for a monitoring program can be obtained without removing the conventional three well volumes from the well. The assumption is made that indicator parameter equilibration may not be necessary to determine when to collect representative samples at the P'liMP. Preliminary results obtained from the field experiment suggest that this may be true. The technique employs low purge rates (< 1 L/min) with dedicated bladder pumps with inlets located in the screened interval of the well, while not disturbing the stagnant water column above the screened interval. If adopted, this technique, termed micro-purge low-flow sampling, will produce representative ground water samples, significantly reduce sampling costs, and minimize; waste water over the monitoring life cycle at the FEMP. This technique is well suited for sites that have been fully characterized and are undergoing long-term monitoring.     

Field Comparison of Micropurging vs. Traditional Ground Water Sampling

Micropurge sampling of ground water wells has been suggested as a possible replacement to traditional purge and sample methods. To compare methods, duplicate ground water samples were collected at two field sites using iraditional and micropurge methods. Samples were analyzed for selected organic and inorganic constituents, and the results were compared statistically. Analysis of the data using the nonparametric sign test indicates that within a 95 percent confidence interval, there was no significant difference between the two methods for the site contaminants and the majority of analytes. These analytical results were supported by visual observations with the colloidal borescope, which demonstrated impacts on the flow system in the well when using traditional sampling methods. Under selected circumstances, the results suggest replacing traditional sampling with micropurging based on reliability, cost, and waste minimization.     

Impact of Turbidity on TCE and Degradation Products in Ground Water

Elevated particulate concentrations in ground water samples can bias contaminant concentration data. This has been particularly problematic for metal analyses where artificially increased turbidity levels can affect metals concentrations and confound interpretation of the data. However, few studies have been conducted to determine the impact of particulates on trichloroethylene (TCE), cis-dichloroethylene (c-DCE), and vinyl chloride concentrations.
Laboratory batch studies and field investigations were conducted to evaluate the effects of suspended solids on VOC concentrations in ground water samples analyzed by purge-and-trap gas chromatography. Three different solids were used to assess the effects of suspended particulates. The solids were aquifer material from a field site in North Carolina and two reference clay minerals (kaolinite and Namontimorillonite). During the laboratory portion of this study, the solids were used to determine effects on TCE concentrations under controlled laboratory conditions.
The same solids were used in a field study to compare the laboratory results with field results. Solids were added to the sample vials prior it) sample collection to intentionally increase turbidity levels in the water samples. Results of the study indicate essentially no decrease in TCE, c-DCH, or vinyl chloride concentrations due to increased turbidity levels.     

Oxygen-Containing Compounds Identified in Groundwater from Fuel Release Sites Using GCxGC-TOF-MS

This research continues a 7-year study of oxygen-containing organic compounds present in groundwater at gasoline and diesel fuel release sites that are quantified as diesel-range “total petroleum hydrocarbons” when measured by methods utilizing solvent extraction and gas chromatography. Two-dimensional gas chromatography with time-of-flight mass spectrometry was used to tentatively identify 1162 compounds (TICs) in 113 groundwater samples from 22 sites. Samples were collected from wells either upgradient of the release, within the source zone, or downgradient of the source but still within the plume of dissolved organics associated with release. The names and formulas of all TICs found in samples from each well type are presented and the results from upgradient and downgradient locations are compared in detail. About 60% of the most frequently detected TICs in downgradient wells were also detected in upgradient wells. A majority of these were saturated straight chain alkyl acids, commonly called fatty acids, or fatty acid esters. Of TICs frequently detected in downgradient wells but not upgradient wells, over half were branched alkyl alcohols. Hierarchical cluster analysis results suggest about 80% of the chemical composition of downgradient samples is more similar to upgradient samples than to source area samples. This similarity is due to the presence of the same types of fatty acids and esters. Principal component analysis indicates a continuum of biodegradation between the source area and downgradient samples with the latter becoming more consistent with upgradient samples. Results suggest some TICs may not be petroleum degradation intermediates but compounds synthesized by microorganisms through secondary production and carbon cycling.     

Polar Compounds from the Dissolution of Weathered Diesel

Hydrocarbon and nonhydrocarbon components dissolving in water from fresh diesel and field samples of highly weathered diesel (spilled up to 50 years ago) from two sites were investigated. The fresh and weathered diesels were equilibrated with water using a slow-stirring method, and the product and equilibrated aqueous water samples analyzed by a range of analytical procedures. The water phase equilibrated with weathered diesels had higher total dissolved organics concentrations (96 and 8.6 mg/L at the two sites) compared to the water phase equilibrated with fresh diesel (average of 3.4 mg/L). Compound class characterization of dissolved organics in water from the weathered diesel showed that polar components were a significant compound class (98% and 42% at the two sites) and appeared largely as an unresolved complex mixture (UCM) in the total ion chromatograms (TICs). Identification of 1-adamantanol in the polar fraction of both weathered diesel samples (3.6 and 0.3 μg/L at the two sites) suggested that at least some of the associated polar components are from a petroleum source. The analysis of total petroleum hydrocarbons (TPH) is aimed at measuring only dissolved carbon and hydrogen-containing compounds, and dissolved polar compounds present as a UCM are often assumed to be from natural organic matter (NOM) and removed. This may result in a gross underestimation of the total soluble organic material in water associated with weathered diesels. In addition, the risk posed by these fuel-derived polar compounds is unknown.     

太湖蓝藻水样中藻蓝蛋白提取方法比较

以2011年8月20日采集的太湖梅梁湾的夏季蓝藻水华为研究对象,通过12个样点平行样的藻蓝蛋白实验提取,基于光谱吸收特征和浓度值,对反复冻融法、超声波法、溶胀法、丙酮法的提取效果进行比较评价.结果表明:4种方法获取的藻蓝蛋白提取液在620 nm附近出现吸收峰,其中,反复冻融法的峰高最强,超声波法最弱,说明反复冻融法的提取效果优于其他方法;反复冻融法、超声波法、溶胀法获取的部分蓝蛋白提取液在670 nm附近具有次吸收峰,与藻蓝蛋白标样的吸收曲线存在差异;反复冻融法、超声波法提取的藻蓝蛋白浓度值变异系数小于0.6,表明这两种方法较其他方法稳定;反复冻融法提取的藻蓝蛋白浓度值高于其他3种方法,可推荐作为太湖蓝藻水样中藻蓝蛋白的提取方法.     

The Application of a Statistical Trend Analysis Model to Ground Water Monitoring Data from Solid Waste Landfills

A statistical trend methodology is used to compare ground water quality between eight landfill sites in western Michigan as a case study. Monitoring data were collected over a 15-year period on 36 parameters at an upgradient and downgradient well selected at each of the eight sites. This yielded a total of 576 monitoring data sets available for analysis. New trend and contamination indices are introduced that are used to compare ground water contamination between these eight sites. These indices are used to assess each landfill's relative potential for environmental harm.
Many questions remain unanswered, but what is demonstrated here is that this type of methodology has the potential to be used to assess trends of ground water chemistry concentrations at landfill sues in a region. A specific purpose of such an assessment could be to provide a quantified basis for the prioritization of funds allocated for cleanup of contaminated landfill sites. Having a technical capability to reduce large amounts of ground water monitoring data to appropriate summaries, which then can be used to assess environmental contamination between several sites, could also have important economic and health implications in other settings. Hopefully this paper will encourage further development of such technologies for these purposes.     

Reducing the impacts of flood-induced reservoir turbidity on a regional water supply system

This paper proposed an integrated simulation model to incorporate the impact of flood-induced reservoir turbidity into water supply. The integrated model includes a regional water allocation model and a one-dimensional settling model of cohesive particles based on Kynch’s theory. It simulates the settling of sediment flocculation in a turbid reservoir. The restrictions of water supply during floods is mimicked by simulating turbidity profiles for control points and then quantifying the associated treatment capability of raw water in the regional water allocation model for each time step. This framework can simulate shortages caused by flood-induced high turbidity as well as extended droughts, thus provide a basis for comprehensive evaluations of emergent and regular water supply facilities. A case study of evaluating different measures to mitigate the impact of turbid reservoir on water supply in northern Taiwan is presented to demonstrate the efficacy of the proposed approach.     

Screened Auger Sampling: The Technique and Two Case Studies

The screened auger is a laser-slotted, hollow-stem auger through which a representative sample of ground water is pumped from an aquifer and tested for water-quality parameters by appropriate field-screening methods. Screened auger sampling can be applied to ground water quality remedial investigations, providing:(1) a mechanism for determining a monitoring well's optimal screen placement in a contaminant plume; and (2) data to define the three-dimensional configuration of the contaminant plume.
Screened auger sampling has provided an efficient method for investigating hexavalent chromium and volatile organic compound contamination in two sandy aquifers in Cadillac, Michigan. The aquifers approach 200 feet in thickness and more than 1 square mile in area. A series of screened auger borings and monitoring wells was installed, and ground water was collected at 10-foot intervals as the boreholes were advanced to define the horizontal and vertical distribution of the contaminant plumes. The ability of the screened auger to obtain representative ground water samples was supported by the statistical comparison of field screening results and subsequent laboratory analysis of ground water from installed monitoring wells.     

Comparison of Two Integrated Methods for the Collection and Analysis of Volatile Organic Compounds in Ground Water

The principal difficulties with determinations of volatile organic compounds (VOCs) in ground water are the reliability of sampling procedures and analytical methods. Two integrated methods have been developed for routine sampling, processing, and analysis of VOCs in ground water. These methods involve in situ collection of ground water using a modified syringe sampler from PVC piezometers or using dedicated glass syringes from stainless steel multilevel bores. The samples are processed in the syringe using purge and trap or microsolvent extraction and analyzed by GC/MSD.
The modified purge-and-trap method is time-consuming and limited to volatile organic compounds. However, it is extremely sensitive and flexible: the volume of sample used can be varied by the use of different-size glass syringes (sample volumes from 1 to 100 mL).
In cases where extremely low sensitivity (<10 mg 1⁻¹) is not critical, the microextraction technique is a more cost-effective method, allowing twice as many samples to be analyzed in the same time as the purge-and-trap method. It enables less volatile compounds such as polynuclear aromatic hydrocarbons, phenol, and cresols to be analyzed in the same GC run. Also, the microextraction method can be used in the field to avoid delays associated with transportation of ground water samples to the laboratory.     

The Suction Side Sample Catcher in Ground Water Quality Sampling

A suction side sample collector (SSSC) is a contrivance installed hydraulically ahead of the intake port of a pumping device. This paper describes construction and operational details of SSSCs fitted to a submersible pump with packer for use in a 6-inch cased borehole, an air lift pump with packer for use in a 1-inch or 2.5-inch cased borehole, a bladder pump for use in a casing of 2-inch or greater diameter, and a jet pump with packer for use in a 2-inch cased borehole.
Each form of SSSC has been thoroughly tested in ground water quality sampling for volatile organic chemicals. Comparative data for samples collected with the SSSCs and conventional sample collecting gear are presented. The SSSC is demonstrated to be superior to other methods of collecting volatile organic chemical samples owing to its freedom from contamination by the pump delivery line and to its mode of collecting the sample from a position in the well remote from disturbance by the pumping technique.
SSSCs are conveniently decontaminated, easily transported, and can be used to deliver samples to the laboratory while still at formation pressure. The air-lift pumps, described in this paper for use with SSSCs in 1- and 2.5-inch casings, have pumping capacities greater than obtained by other methods that can operate in these small casings. Discharge rates of up to 2 gpm are routinely achieved with the 1-inch model and higher rates are common With the 2.5-inch model. The use of packers with these pumps reduces the time needed to replace the water in the casing with fresh water from the formation.     

Assessing herbicide concentrations in the saturated and unsaturated zone of a Chalk aquifer in southern England

The behavior of the herbicides isoproturon (IPU) and chlortoluron (CTU) in ground water and shallow unsaturated zone sediments were evaluated at a site situated on the Chalk in southern England. Concentrations of IPU in ground water samples varied from < 0.05 to 0.23 microgram/L over a five-year period of monitoring, and were found to correlate with application of the pesticide. Concentrations of pesticides in ground water samples collected during periods of rising water table were significantly higher than pumped samples and suggest that rapidly infiltrating recharge water contains higher herbicide concentrations than the native ground water. Significant variations in herbicide concentrations were observed over a three-month period in ground water samples collected by an automated system, with concentrations of IPU ranging from 0.1 to 0.5 microgram/L, and concentrations of a recent application of CTU ranging from 0.2 to 0.8 microgram/L. Different extraction methods were used to assess pore water concentrations of herbicides in the unsaturated zone, and samples were analyzed by standard HPLC analysis and immunoassay (ELISA) methods. These data indicated highly variable concentrations of herbicide ranging from 4 to 200 g/ha for HPLC and 0.01 to 0.04 g/ha for ELISA, but indicate a general pattern of decreasing concentrations with depth. The results of this study indicate that transport of IPU and CTU through the unsaturated zone to shallow ground water occurs and that this transport increases immediately following herbicide application. Measured concentrations of herbicides are generally lower than specified by the European Union Drinking Water Directive, but are observed to spike above this limit. These results imply that, while delivery of pesticides to ground water can occur as a result of normal agricultural practices, the impact on potable supplies is likely to be negligible due to the potential for degradation during the relatively long travel time through the unsaturated zone and high degree of dilution that occurs within the aquifer. As a result of the wide variation in concentrations detected by different techniques, it is suggested that for future site investigations more than one sampling strategy be employed to characterize the occurrence of pesticide residues and elucidate the transport mechanisms.     

The Ground Water Recharge and Pollution Potential of Dry Wells in Pima County, Arizona

This paper summarizes a study to estimate the potential for dry-well drainage of urban runoff to recharge and pollute ground water in Tucson, Arizona. We selected three candidate dry wells for study. At each site we collected samples of runoff, dry-well sediment, vadose-zone sediment, perched ground water, and ground water. Water content data from vadose-zone samples suggest that dry-well drainage has created a transmission zone for water movement at each site. Volatile organic compounds, while undetected in runoff samples, were present in dry-well sediment, perched ground water at one site, and ground water at two sites. The concentrations of volatile organics (toluene and ethylbenzene) in the water samples were less than the corresponding EPA human health criteria. Pesticides were detected only in runoff and dry-well sediment. Lead and chromium occurred in runoff samples at concentrations above drinking water standards. Nickel, chromium, and zinc concentrations were elevated in vadose-zone samples at the commercial site. Of the metals, only manganese, detected at the residential site, exceeded Secondary Drinking Water Standards in ground water. It is concluded that the three dry wells examined during this study are currently not a major source of ground water pollution.