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Analytical methods, numerical modeling, and monitoring strategies for evaluating the effects of ground-water withdrawals on unconfined aquifers in the New Jersey Coastal Plain

Analytical and numerical solutions of ground-water withdrawals in the unconfined part of the Kirkwood-Cohansey aquifer system of the Coastal Plain of New Jersey were evaluated for their usefulness in predicting the area of influence of a pumped well and in determining hydraulic characteristics of an aquifer. Additionally, simulations of ground-water withdrawal using a finite-difference model provided information on the ways in which prudent well-location strategies can disperse the local effects of withdrawal over a larger part of an aquifer system. The design of a monitoring network that is sensitive to the ground-water hydraulics of streams and wetlands of the Coastal Plain of New Jersey also was considered for its utility in providing hydrologic data necessary to establish the baseline hydrologic conditions near wetlands and streams and in signaling when ground-water levels are being adversely affected by withdrawals elsewhere in the system. The application of methods based on the Theis analytical solution to ground-water flow in unconfined aquifers can lead to erroneous estimates of the size of the area of influence generated by ground-water withdrawals. Analysis oftime-drawdown data from an unconfined aquifer system are best evaluated by means of the Neuman solution, which accounts for the effects of gravity drainage; however, the pumped well must be far enough from streams so that ground water is not drawn from nearby streams. Time-drawdown data from a test well in Winslow County, N.J., were analyzed by means of the Neuman solution. Results indicate that the aquifer has a relatively high vertical to horizontal anisotropy of 1:198, and a specific yield of 0.028, an indication that the area of influence of a pumped well at the test site would be relatively large. Results from a finite-difference ground-water-flow model of the northeastern part of the Mullica River Basin near Chesilhurst, N.J., show that the area influenced by a long-term withdrawal is best estimated from a steady state ground-water-flow analysis that includes the effects of average areal recharge. Withdrawal simulations indicate an order-of-magnitude difference between the size of the area of influence generated from a 3-day (72 hour) withdrawal and the size of the area produced under steady-state conditions. An aquifer characterized by a low specific yield will cause the area of influence to extend farther away from the pumped well. The contributing area of flow to the pumped well includes areas on the water table that would, under natural conditions, be incorporated into the contributing areas of flow to streams. Ground water that is drawn to a pumped well is diverted from nearby streams; the withdrawal decreases the size of the contributing areas of flow to streams by an amount equal to the contributing area of flow to the well. Withdrawals made from a well close to a stream divert ground water that would, under natural conditions, flow to the stream. The diverted ground water causes the area of influence of the well to be smaller than it would if the well were far from the stream. Water-table declines caused by withdrawals near streams are, to some degree, mitigated by ground-water diversion from streams. However, the withdrawals can significantly reduce ground-water seepage to nearby streams, especially along stream reaches and wetlands close to the well. Alternatively, these effects can be dispersed over a large part of the aquifer if wells are located on surface-water divides. Measurements of seasonal water-level fluctuations in the Mullica River Basin indicate that the greatest fluctuations in water levels are found in upland areas, where the average fluctuation is 3.4 feet. Fluctuations in hydraulic head in the wetland areas averages 1.3 feet. The bimodal average of ranges in water levels show that upland areas are more sensitive to recharge than lowland areas. The pattern of yearly mean water levels fluctuates irregularly about a long-term mean value. Abnormally low or high yearly average values that are brought on by periods of drought or excess recharge are short lived; over time, hydrologic conditions shift back to average levels under natural conditions. Wetland areas in the New Jersey Coastal Plain are characterized by ground-water seepage into wide, shallow depressions. Periods of inundation are longest in the deepest part of the depression, whereas inundation of areas near the fringes of wetlands due to ground-water seepage is only seasonal. The seepage face in the fringe areas expand and contract in response to seasonal variation in water-table elevation and in response to precipitation. Values of the aquifer storage coefficient and transmissivity can, in some cases, be determined by use of hydraulic head or streamflow recession analysis as an alternative to aquifer testing. The recession curves developed from hydro graphs of Middle Branch and McDonalds Branch in the New Jersey Coastal Plain indicate that the aquifer near McDonalds Branch has about 2.6 times the storage capacity of the aquifer adjacent to Middle Branch; this finding is consistent with the relatively small ranges of water-level changes measured in McDonalds Branch compared to those measured in Middle Branch.

New Jersey↗

Analytical methods of the U.S. Geological Survey's New York District Water-Analysis Laboratory

The New York District of the U.S. Geological Survey (USGS) in Troy, N.Y., operates a water-analysis laboratory for USGS watershed-research projects in the Northeast that require analyses of precipitation and of dilute surface water and soil water for major ions; it also provides analyses of certain chemical constituents in soils and soil gas samples. This report presents the methods for chemical analyses of water samples, soil-water samples, and soil-gas samples collected in wateshed-research projects. The introduction describes the general materials and technicques for each method and explains the USGS quality-assurance program and data-management procedures; it also explains the use of cross reference to the three most commonly used methods manuals for analysis of dilute waters. The body of the report describes the analytical procedures for (1) solution analysis, (2) soil analysis, and (3) soil-gas analysis. The methods are presented in alphabetical order by constituent. The method for each constituent is preceded by (1) reference codes for pertinent sections of the three manuals mentioned above, (2) a list of the method's applications, and (3) a summary of the procedure. The methods section for each constitutent contains the following categories: instrumentation and equipment, sample preservation and storage, reagents and standards, analytical procedures, quality control, maintenance, interferences, safety considerations, and references. Sufficient information is presented for each method to allow the resulting data to be appropriately used in environmental investigations.

Open-File Report↗

Comparison of several analytical methods for the determination of tin in geochemical samples as a function of tin speciation

Accurate and precise determinations of tin in geological materials are needed for fundamental studies of tin geochemistry, and for tin prospecting purposes. Achieving the required accuracy is difficult because of the different matrices in which Sn can occur (i.e. sulfides, silicates and cassiterite), and because of the variability of literature values for Sn concentrations in geochemical reference materials. We have evaluated three methods for the analysis of samples for Sn concentration: graphite furnace atomic absorption spectrometry (HGA-AAS) following iodide extraction, inductively coupled plasma atomic emission spectrometry (ICP-OES), and energy-dispersive X-ray fluorescence (EDXRF) spectrometry. Two of these methods (HGA-AAS and ICP-OES) required sample decomposition either by acid digestion or fusion, while the third (EDXRF) was performed directly on the powdered sample. Analytical details of all three methods, their potential errors, and the steps necessary to correct these errors were investigated. Results showed that similar accuracy was achieved from all methods for unmineralized samples, which contain no known Sn-bearing phase. For mineralized samples, which contain Sn-bearing minerals, either cassiterite or stannous sulfides, only EDXRF and fusion ICP-OES methods provided acceptable accuracy. This summary of our study provides information which helps to assure correct interpretation of data bases for underlying geochemical processes, regardless of method of data collection and its inherent limitations. ?? 1989.

Chemical Geology↗

Appendix 1: Analytical methods and errors

Thirty eight K-Ar and eight 40Ar/39Ar high-precision age determinations were made at the US Geological Survey, Menlo Park, on a total of 22 rocks from the entire volcanic field. Duplicate or triplicate determinations were carried out on 14 samples in order to improve analytical precision. All ages were measured on whole-rock samples selected after thin-section examination. Most of the samples meet the usual criteria for whole-rock dating (Mankinen © Dal-rymple 1972), but some contain minor amounts of glass and a few samples are very glassy. The samples selected for dating were crushed to 0.5-lmm (-18 to +35 mesh). For K-Ar dating aliquots weighing c. 25 g were used for the Ar measurements. A 10 g aliquot was ground to -200 mesh and splits of the powder were used for K20 measurements, which were made in duplicate on each of two separate splits of sample powder by flame photometry after lithium metaborate fusion and dissolution (Ingamells 1970). Ar analyses were by isotope-dilution mass spectrometry using a high-purity (>99.9%) 38Ar tracer and techniques and equipment described previously (Dalrymple & Lanphere 1969). All samples for Ar extraction were baked overnight at 280°C. Mass analyses were done on a 22.68 cm radius, multiple-collector mass spectrometer with a nominal 90° sector magnet, using automated data collection (Stacey etal 1981). Errors given for the calculated K-Ar ages of individual measurements are estimates of the standard deviation of analytical precision. The errors were calculated using formulae derived by Cox & Dalrymple (1967) and Dalrymple & Lanphere (1969).

Geological Society, London, Memoirs↗

USGS42 and USGS43: Human-hair stable hydrogen and oxygen isotopic reference materials and analytical methods for forensic science and implications for published measurement results

Because there are no internationally distributed stable hydrogen and oxygen isotopic reference materials of human hair, the U.S. Geological Survey (USGS) has prepared two such materials, USGS42 and USGS43. These reference materials span values commonly encountered in human hair stable isotope analysis and are isotopically homogeneous at sample sizes larger than 0.2 mg. USGS42 and USGS43 human-hair isotopic reference materials are intended for calibration of δ(2)H and δ(18)O measurements of unknown human hair by quantifying (1) drift with time, (2) mass-dependent isotopic fractionation, and (3) isotope-ratio-scale contraction. While they are intended for measurements of the stable isotopes of hydrogen and oxygen, they also are suitable for measurements of the stable isotopes of carbon, nitrogen, and sulfur in human and mammalian hair. Preliminary isotopic compositions of the non-exchangeable fractions of these materials are USGS42(Tibetan hair)δ(2)H(VSMOW-SLAP) = -78.5 ± 2.3‰ (n = 62) and δ(18)O(VSMOW-SLAP) = +8.56 ± 0.10‰ (n = 18) USGS42(Indian hair)δ(2)H(VSMOW-SLAP) = -50.3 ± 2.8‰ (n = 64) and δ(18)O(VSMOW-SLAP) = +14.11 ± 0.10‰ (n = 18). Using recommended analytical protocols presented herein for δ(2)H(VSMOW-SLAP) and δ(18)O(VSMOW-SLAP) measurements, the least squares fit regression of 11 human hair reference materials is δ(2)H(VSMOW-SLAP) = 6.085δ(2)O(VSMOW-SLAP) - 136.0‰ with an R-square value of 0.95. The δ(2)H difference between the calibrated results of human hair in this investigation and a commonly accepted human-hair relationship is a remarkable 34‰. It is critical that readers pay attention to the δ(2)H(VSMOW-SLAP) and δ(18)O(VSMOW-SLAP) of isotopic reference materials in publications, and they need to adjust the δ(2)H(VSMOW-SLAP) and δ(18)O(VSMOW-SLAP) measurement results of human hair in previous publications, as needed, to ensure all results on are on the same scales.

Forensic Science International↗

Simultaneous speciation of arsenic, selenium, and chromium: species, stability, sample preservation, and analysis of ash and soil leachates

An analytical method using high-performance liquid chromatography separation with inductively coupled plasma mass spectrometry (ICP-MS) detection previously developed for the determination of Cr(III) and Cr(VI) has been adapted to allow the determination of As(III), As(V), Se(IV), Se(VI), Cr(III), and Cr(VI) under the same chromatographic conditions. Using this method, all six inorganic species can be determined in less than 3 min. A dynamic reaction cell (DRC)-ICP-MS system was used to detect the species eluted from the chromatographic column in order to reduce interferences. A variety of reaction cell gases and conditions may be utilized with the DRC-ICP-MS, and final selection of conditions is determined by data quality objectives. Results indicated all starting standards, reagents, and sample vials should be thoroughly tested for contamination. Tests on species stability indicated that refrigeration at 10° C was preferential to freezing for most species, particularly when all species were present, and that sample solutions and extracts should be analyzed as soon as possible to eliminate species instability and interconversion effects. A variety of environmental and geological samples, including waters and deionized water [leachates] and simulated biological leachates from soils and wildfire ashes have been analyzed using this method. Analytical spikes performed on each sample were used to evaluate data quality. Speciation analyses were conducted on deionized water leachates and simulated lung fluid leachates of ash and soils impacted by wildfires. These results show that, for leachates containing high levels of total Cr, the majority of the chromium was present in the hexavalent Cr(VI) form. In general, total and hexavalent chromium levels for samples taken from burned residential areas were higher than those obtained from non-residential forested areas. Arsenic, when found, was generally in the more oxidized As(V) form. Selenium (IV) and (VI) were present, but typically at low levels.

Analytical and Bioanalytical Chemistry↗

UPb ages of zircon rims: A new analytical method using the air-abrasion technique

We present a new technique for directly dating, by conventional techniques, the rims of zircons. Several circumstances, such as a xenocrystic or inherited component in igneous zircon and metamorphic overgrowths on igneous cores, can result in grains with physically distinct age components. Pneumatic abrasion has been previously shown by Krogh to remove overgrowths and damaged areas of zircon, leaving more resistant and isotopically less disturbed parts available for analysis. A new abrader design, which is capable of very gently grinding only tips and interfacial edges of even needle-like grains, permits easy collection of abraded material for dating. Five examples demonstrate the utility of the “dust-collecting” technique, including two studies that compare conventional, ion microprobe and abrader data. Common Pb may be strongly concentrated in the outermost zones of many zircons and this Pb is not easily removed by leaching (even in weak HF). Thus, the benefit of removing only the outermost zones (and avoiding mixing of age components) is somewhat compromised by the much higher common Pb contents which result in less precise age determinations. A very brief abrasion to remove the high common Pb zones prior to collection of material for dating is selected.

Chemical Geology: Isotope Geoscience Section↗

An analytical method for hydrogeochemical surveys: Inductively coupled plasma-atomic emission spectrometry after using enrichment coprecipitation with cobalt and ammonium pyrrolidine dithiocarbamate

Trace metals that are commonly associated with mineralization were concentrated and separated from natural water by coprecipitation with ammonium pyrollidine dithiocarbamate (APDC) and cobalt and determined by inductively coupled plasma-atomic emission spectroscopy (ICP-AES). The method is useful in hydrogeochemical surveys because it permits preconcentration near the sample sites, and selected metals are preserved shortly after the samples are collected. The procedure is relatively simple: (1) a liter of water is filtered; (2) the pH is adjusted; (3) Co chloride and APDC are added to coprecipitate the trace metals; and (4) later, the precipitate is filtered, dissolved, and diluted to 10 ml for a 100-fold concentration enrichment of the separated metals. Sb(III), As(III), Cd, Cr, Cu, Fe, Pb, Mo, Ni, Ag, V, and Zn can then be determined simultaneously by ICP-AES. In an experiment designed to measure the coprecipitation efficiency, Sb(III), Cd and Ag were recovered at 70 to 75% of their original concentration. The remaining metals were recovered at 85 to 100% of their original concentrations, however. The range for the lower limits of determination for the metals after preconcentration is 0.1 to 3.0 μg/l.

Journal of Geochemical Exploration↗

Biological effects of hydrocarbon degradation intermediates: Is the total petroleum hydrocarbon analytical method adequate for risk assessment?

In crude oil contaminant plumes, the dissolved organic carbon (DOC) is mainly hydrocarbon degradation intermediates only partly quantified by the diesel range total petroleum hydrocarbon (TPHd) method. To understand potential biological effects of degradation intermediates, we tested three fractions of DOC: (1) solid-phase extract (HLB); (2) dichloromethane (DCM-total) extract used in TPHd; and (3) DCM extract with hydrocarbons isolated by silica gel cleanup (DCM-SGC). Bioactivity of extracts from five wells spanning a range of DOC was tested using an in vitro multiplex reporter system that evaluates modulation of the activity of 46 transcription factors; extracts were evaluated at concentrations equivalent to the well water samples. The aryl hydrocarbon receptor (AhR) and pregnane X receptor (PXR) transcription factors showed the greatest upregulation, with HLB exceeding DCM-total, and no upregulation in the hydrocarbon fraction (DCM-SGC). The HLB extracts were further studied with HepG2 chemically activated luciferase expression (CALUX) in vitro assays at nine concentrations ranging from 40 to 0.01 times the well water concentrations. Responses decreased with distance from the source but were still present at two wells without detectable hydrocarbons. Thus, our in vitro assay results indicate that risks associated with degradation intermediates of hydrocarbons in groundwater will be underestimated when protocols that remove these chemicals are employed.

Minnesota↗

Comparison of traditional and molecular analytical methods for detecting biological agents in raw and drinking water following ultrafiltration

Aims: To compare the performance of traditional methods to quantitative polymerase chain reaction (qPCR) for detecting five biological agents in large-volume drinking-water samples concentrated by ultrafiltration (UF). Methods and Results: Drinking-water samples (100 l) were seeded with Bacillus anthracis, Cryptospordium parvum, Francisella tularensis, Salmonella Typhi, and Vibrio cholerae and concentrated by UF. Recoveries by traditional methods were variable between samples and between some replicates; recoveries were not determined by qPCR. Francisella tularensis and V. cholerae were detected in all 14 samples after UF, B. anthracis was detected in 13, and C. parvum was detected in 9 out of 14 samples. Numbers found by qPCR after UF were significantly or nearly related to those found by traditional methods for all organisms except for C. parvum. A qPCR assay for S. Typhi was not available. Conclusions: qPCR can be used to rapidly detect biological agents after UF as well as traditional methods, but additional work is needed to improve qPCR assays for several biological agents, determine recoveries by qPCR, and expand the study to other areas. Significance and Impact of the Study: To our knowledge, this is the first study to compare the use of traditional and qPCR methods to detect biological agents in large-volume drinking-water samples. ?? 2009 The Society for Applied Microbiology.

Journal of Applied Microbiology↗

A study of porewater in water saturated sediments of levee banks and marshes in the lower Coeur d'Alene River valley, Idaho: Sampling, analytical methods, and results

This report contains information about the composition of interstitial porewater and solids from water saturated, metal contaminated levee banks at the river's edge and marshes in the lower Coeur d'Alene River valley. Data include pH, alkalinity, and concentrations of sulfate and metals (arsenic [As], cadmium [Cd], copper [Cu], iron [Fe], mercury [Hg], manganese [Mn], lead [Pb], antimony [Sb], and zinc [Zn]) in porewater and sulfur (S), carbon (C), and metal contents of associated solids. The results indicate that the pH of the porewater in all of the sediments is less than the pH of the Coeur d'Alene River. Dissolved concentrations of Mn and Fe are elevated in all of the porewater and levels of sulfate in porewater are below detection limits in almost all marsh sediments and in levee banks at the 2 sites furthest downstream. These observations suggest that levee bank and marsh sediments are suboxic or anoxic below the surface. Concentrations of dissolved Cd are greater in the Coeur d'Alene River than in porewater, while concentrations of As are greater in the porewater relative to the Coeur d'Alene River. Some concentrations of Cu, Pb, Sb, and Zn in porewater are lower, while others are higher, than dissolved concentrations in the Coeur d'Alene River. In addition, leaching experiments (i.e., Standard Elutriate Tests [SET]) were done in the laboratory to evaluate potential water quality impacts resulting from the addition of oxygen and water to these sediments. The intent of the experiments was to simulate how metal concentrations in water may be affected during dredging of contaminated sediments in the lower Coeur d'Alene River valley. The results indicate that there are releases of protons, sulfate, As, Mn, Pb, Sb, and Zn from the majority of levee bank and marsh sediments during leaching by Coeur d'Alene River water. At a water to sediment ratio of 4 to 1, most values of pH and dissolved concentrations of Cd, Fe, Pb, and Zn in the leaching solutions exceed the freshwater aquatic life standards for water of a hardness of 100 mg CaCOa/L. This work was funded by the U.S. EPA and was done to support their Remedial Investigation/Feasibility Study of the Coeur d'Alene and Spokane River basins.

Idaho↗