USGS ScienceSearch

Geology topics

William T. Foreman

Publications and source records attributed to William T. Foreman.

At least 37 records · Page 2Linked to original sources

Pesticides in Mississippi air and rain: A comparison between 1995 and 2007

A variety of current-use pesticides were determined in weekly composite air and rain samples collected during the 1995 and 2007 growing seasons in the Mississippi Delta (MS, USA) agricultural region. Similar sampling and analytical methods allowed for direct comparison of results. Decreased overall pesticide use in 2007 relative to 1995 generally resulted in decreased detection frequencies in air and rain; observed concentration ranges were similar between years, however, even though the 1995 sampling site was 500 m from active fields whereas the 2007 sampling site was within 3 m of a field. Mean concentrations of detections were sometimes greater in 2007 than in 1995, but the median values were often lower. Seven compounds in 1995 and 5 in 2007 were detected in ≥50% of both air and rain samples. Atrazine, metolachlor, and propanil were detected in ≥50% of the air and rain samples in both years. Glyphosate and its degradation product, aminomethyl-phosphonic acid (AMPA), were detected in ≥75% of air and rain samples in 2007 but were not measured in 1995. The 1995 seasonal wet depositional flux was dominated by methyl parathion (88%) and was >4.5 times the 2007 flux. Total herbicide flux in 2007 was slightly greater than in 1995 and was dominated by glyphosate. Malathion, methyl parathion, and degradation products made up most of the 2007 nonherbicide flux.

Mississippi

Concentrations of polycyclic aromatic hydrocarbons (PAHs) and azaarenes in runoff from coal-tar- and asphalt-sealcoated pavement

Coal-tar-based sealcoat, used extensively on parking lots and driveways in North America, is a potent source of PAHs. We investigated how concentrations and assemblages of PAHs and azaarenes in runoff from pavement newly sealed with coal-tar-based (CT) or asphalt-based (AS) sealcoat changed over time. Samples of simulated runoff were collected from pavement 5 h to 111 d following application of AS or CT sealcoat. Concentrations of the sum of 16 PAHs (median concentrations of 328 and 35 μg/L for CT and AS runoff, respectively) in runoff varied relatively little, but rapid decreases in concentrations of azaarenes and low molecular weight PAHs were offset by increases in high molecular weight PAHs. The results demonstrate that runoff from CT-sealcoated pavement, in particular, continues to contain elevated concentrations of PAHs long after a 24-h curing time, with implications for the fate, transport, and ecotoxicological effects of contaminants in runoff from CT-sealcoated pavement.

Environmental Pollution

Riverbank filtration potential of pharmaceuticals in a wastewater-impacted stream

Pharmaceutical contamination of shallow groundwater is a substantial concern in effluent-dominated streams, due to high aqueous mobility, designed bioactivity, and effluent-driven hydraulic gradients. In October and December 2012, effluent contributed approximately 99% and 71%, respectively, to downstream flow in Fourmile Creek, Iowa, USA. Strong hydrologic connectivity was observed between surface-water and shallow-groundwater. Carbamazepine, sulfamethoxazole, and immunologically-related compounds were detected in groundwater at greater than 0.02 μg L −1 at distances up to 6 m from the stream bank. Direct aqueous-injection HPLC-MS/MS revealed 43% and 55% of 110 total pharmaceutical analytes in surface-water samples in October and December, respectively, with 16% and 6%, respectively, detected in groundwater approximately 20 m from the stream bank. The results demonstrate the importance of effluent discharge as a driver of local hydrologic conditions in an effluent-impacted stream and thus as a fundamental control on surface-water to groundwater transport of effluent-derived pharmaceutical contaminants.

Iowa

Persistent organic contaminants in Saharan dust air masses in West Africa, Cape Verde and the eastern Caribbean

Anthropogenic semivolatile organic compounds (SOCs) that persist in the environment, bioaccumulate, are toxic at low concentrations, and undergo long-range atmospheric transport (LRT) were identified and quantified in the atmosphere of a Saharan dust source region (Mali) and during Saharan dust incursions at downwind sites in the eastern Caribbean (U.S. Virgin Islands, Trinidad and Tobago) and Cape Verde. More organochlorine and organophosphate pesticides (OCPPs), polycyclic aromatic hydrocarbons (PAHs), and polychlorinated biphenyl (PCB) congeners were detected in the Saharan dust region than at downwind sites. Seven of the 13 OCPPs detected occurred at all sites: chlordanes, chlorpyrifos, dacthal, dieldrin, endosulfans, hexachlorobenzene (HCB), and trifluralin. Total SOCs ranged from 1.9–126 ng/m 3 (mean = 25 ± 34) at source and 0.05–0.71 ng/m 3 (mean = 0.24 ± 0.18) at downwind sites during dust conditions. Most SOC concentrations were 1–3 orders of magnitude higher in source than downwind sites. A Saharan source was confirmed for sampled air masses at downwind sites based on dust particle elemental composition and rare earth ratios, atmospheric back trajectory models, and field observations. SOC concentrations were considerably below existing occupational and/or regulatory limits; however, few regulatory limits exist for these persistent organic compounds. Long-term effects of chronic exposure to low concentrations of SOCs are unknown, as are possible additive or synergistic effects of mixtures of SOCs, biologically active trace metals, and mineral dust particles transported together in Saharan dust air masses.

Caribbean;Sahara

Sampling trace organic compounds in water: a comparison of a continuous active sampler to continuous passive and discrete sampling methods

A continuous active sampling method was compared to continuous passive and discrete sampling methods for the sampling of trace organic compounds (TOCs) in water. Results from each method are compared and contrasted in order to provide information for future investigators to use while selecting appropriate sampling methods for their research. The continuous low-level aquatic monitoring (CLAM) sampler (C.I.Agent® Storm-Water Solutions) is a submersible, low flow-rate sampler, that continuously draws water through solid-phase extraction media. CLAM samplers were deployed at two wastewater-dominated stream field sites in conjunction with the deployment of polar organic chemical integrative samplers (POCIS) and the collection of discrete (grab) water samples. All samples were analyzed for a suite of 69 TOCs. The CLAM and POCIS samples represent time-integrated samples that accumulate the TOCs present in the water over the deployment period (19–23 h for CLAM and 29 days for POCIS); the discrete samples represent only the TOCs present in the water at the time and place of sampling. Non-metric multi-dimensional scaling and cluster analysis were used to examine patterns in both TOC detections and relative concentrations between the three sampling methods. A greater number of TOCs were detected in the CLAM samples than in corresponding discrete and POCIS samples, but TOC concentrations in the CLAM samples were significantly lower than in the discrete and (or) POCIS samples. Thirteen TOCs of varying polarity were detected by all of the three methods. TOC detections and concentrations obtained by the three sampling methods, however, are dependent on multiple factors. This study found that stream discharge, constituent loading, and compound type all affected TOC concentrations detected by each method. In addition, TOC detections and concentrations were affected by the reporting limits, bias, recovery, and performance of each method.

Science of the Total Environment

An isotope-dilution standard GC/MS/MS method for steroid hormones in water

An isotope-dilution quantification method was developed for 20 natural and synthetic steroid hormones and additional compounds in filtered and unfiltered water. Deuterium- or carbon-13-labeled isotope-dilution standards (IDSs) are added to the water sample, which is passed through an octadecylsilyl solid-phase extraction (SPE) disk. Following extract cleanup using Florisil SPE, method compounds are converted to trimethylsilyl derivatives and analyzed by gas chromatography with tandem mass spectrometry. Validation matrices included reagent water, wastewater-affected surface water, and primary (no biological treatment) and secondary wastewater effluent. Overall method recovery for all analytes in these matrices averaged 100%; with overall relative standard deviation of 28%. Mean recoveries of the 20 individual analytes for spiked reagent-water samples prepared along with field samples analyzed in 2009–2010 ranged from 84–104%, with relative standard deviations of 6–36%. Detection levels estimated using ASTM International’s D6091–07 procedure range from 0.4 to 4 ng/L for 17 analytes. Higher censoring levels of 100 ng/L for bisphenol A and 200 ng/L for cholesterol and 3-beta-coprostanol are used to prevent bias and false positives associated with the presence of these analytes in blanks. Absolute method recoveries of the IDSs provide sample-specific performance information and guide data reporting. Careful selection of labeled compounds for use as IDSs is important because both inexact IDS-analyte matches and deuterium label loss affect an IDS’s ability to emulate analyte performance. Six IDS compounds initially tested and applied in this method exhibited deuterium loss and are not used in the final method.

Book chapter

Chemical contaminants in water and sediment near fish nesting sites in the Potomac River basin: determining potential exposures to smallmouth bass (Micropterus dolomieu)

The Potomac River basin is an area where a high prevalence of abnormalities such as testicular oocytes (TO), skin lesions, and mortality has been observed in smallmouth bass (SMB, Micropterus dolomieu). Previous research documented a variety of chemicals in regional streams, implicating chemical exposure as one plausible explanation for these biological effects. Six stream sites in the Potomac basin (and one out-of-basin reference site) were sampled to provide an assessment of chemicals in these streams. Potential early life-stage exposure to chemicals detected was assessed by collecting samples in and around SMB nesting areas. Target chemicals included those known to be associated with important agricultural and municipal wastewater sources in the Potomac basin. The prevalence and severity of TO in SMB were also measured to determine potential relations between chemistry and biological effects. A total of 39 chemicals were detected at least once in the discrete-water samples, with atrazine, caffeine, deethylatrazine, simazine, and iso-chlorotetracycline being most frequently detected. Of the most frequently detected chemicals, only caffeine was detected in water from the reference site. No biogenic hormones/sterols were detected in the discrete-water samples. In contrast, 100 chemicals (including six biogenic hormones/sterols) were found in a least one passive-water sample, with 25 being detected at all such samples. In addition, 46 chemicals (including seven biogenic hormones/sterols) were found in the bed-sediment samples, with caffeine, cholesterol, indole, para-cresol, and sitosterol detected in all such samples. The number of herbicides detected in discrete-water samples per site had a significant positive relation to TO rank (a nonparametric indicator of TO), with significant positive relations between TO rank and atrazine concentrations in discrete-water samples and to total hormone/sterol concentration in bed-sediment samples. Such significant correlations do not necessarily imply causation, as these chemical compositions and concentrations likely do not adequately reflect total SMB exposure history, particularly during critical life stages.

Potomac River Basin

Bioassay of estrogenicity and chemical analyses of estrogens in streams across the United States associated with livestock operations

Animal manures, used as a nitrogen source for crop production, are often associated with negative impacts on nutrient levels in surface water. The concentrations of estrogens in streams from these manures also are of concern due to potential endocrine disruption in aquatic species. Streams associated with livestock operations were sampled by discrete samples (n = 38) or by time-integrated polar organic chemical integrative samplers (POCIS,n = 19). Samples were analyzed for estrogens by gas chromatography-tandem mass spectrometry (GC-MSM 2 ) and estrogenic activity was assessed by three bioassays: Yeast Estrogen Screen (YES), T47D-KBluc Assay, MCF-7 Estrogenicity Screen (E-Screen). Samples were collected from 19 streams within small (∼1-30 km 2 ) watersheds in 12 U.S. states representing a range of hydrogeologic conditions, dominated by: dairy (3), grazing beef (3), feedlot cattle (1); swine (5); poultry (3); and 4 areas where no livestock were raised or manure was applied. Water samples were consistently below the United Kingdom proposed Lowest Observable Effect Concentration for 17b-estradiol in fish (10 ng/L) in all watersheds, regardless of land use. Estrogenic activity was often higher in samples during runoff conditions following a period of manure application. Estrone was the most commonly detected estrogen (13 of 38 water samples, mean 1.9, maximum 8.3 ng/L). Because of the T47D-KBluc assay’s sensitivity towards estrone (1.4 times 17β-estradiol) it was the most sensitive method for detecting estrogens, followed by the E-Screen, GC-MS 2 , and YES. POCIS resulted in more frequent detections of estrogens than discrete water samples across all sites, even when applying the less-sensitive YES bioassay to the POCIS extracts.

Water Research

Methods, quality assurance, and data for assessing atmospheric deposition of pesticides in the Central Valley of California

The U.S. Geological Survey monitored atmospheric deposition of pesticides in the Central Valley of California during two studies in 2001 and 2002–04. The 2001 study sampled wet deposition (rain) and storm-drain runoff in the Modesto, California, area during the orchard dormant-spray season to examine the contribution of pesticide concentrations to storm runoff from rainfall. In the 2002–04 study, the number and extent of collection sites in the Central Valley were increased to determine the areal distribution of organophosphate insecticides and other pesticides, and also five more sample types were collected. These were dry deposition, bulk deposition, and three sample types collected from a soil box: aqueous phase in runoff, suspended sediment in runoff, and surficial-soil samples. This report provides concentration data and describes methods and quality assurance of sample collection and laboratory analysis for pesticide compounds in all samples collected from 16 sites. Each sample was analyzed for 41 currently used pesticides and 23 pesticide degradates, including oxygen analogs (oxons) of 9 organophosphate insecticides. Analytical results are presented by sample type and study period. The median concentrations of both chloryprifos and diazinon sampled at four urban (0.067 micrograms per liter [μg/L] and 0.515 μg/L, respectively) and four agricultural sites (0.079 μg/L and 0.583 μg/L, respectively) during a January 2001 storm event in and around Modesto, Calif., were nearly identical, indicating that the overall atmospheric burden in the region appeared to be fairly similar during the sampling event. Comparisons of median concentrations in the rainfall to those in the McHenry storm-drain runoff showed that, for some compounds, rainfall contributed a substantial percentage of the concentration in the runoff; for other compounds, the concentrations in rainfall were much greater than in the runoff. For example, diazinon concentrations in rainfall were about 70 percent of the diazinon concentration in the runoff, whereas the chlorpyrifos concentration in the rain was 1.8 times greater than in the runoff. The more water-soluble pesticides—carbaryl, metolachlor, napropamide, and simazine—followed the same pattern as diazinon and had lower concentrations in rain compared to runoff. Similar to chlorpyrifos,compounds with low water solubilities and higher soil-organic carbon partition coefficients, including dacthal, pendimethalin, and trifluralin, were found to have higher concentrations in rain than in runoff water and were presumed to partition to the suspended sediments and organic matter on the ground. During the 2002–04 study period, the herbicide dacthal had the highest detection frequencies for all sample types collected from the Central Valley sites (67–100 percent). The most frequently detected compounds in the wet-deposition samples were dacthal, diazinon, chlorpyrifos, and simazine (greater than 90 percent). The median wet-deposition amounts for these compounds were 0.044 micrograms per square meter per day (μg/m 2 /day), 0.209 μg/m 2 /day, 0.079 μg/m 2 /day, and 0.172 μg/m 2 /day, respectively. For the dry-deposition samples, detection frequencies were greater than 73 percent for the compounds dacthal, metolachor, and chlorpyrifos, and median deposition amounts were an order of magnitude less than for wet deposition. The differences between wet deposition and dry deposition appeared to be closely related to the Henry’s Law (H) constant of each compound, although the mass deposited by dry deposition takes place over a much longer time frame. Pesticides detected in rainfall usually were detected in the aqueous phase of the soil-box runoff water, and the runoff concentrations were generally similar to those in the rainfall. For compounds detected in the aqueous phase and suspended-sediment samples of soil-box runoff, concentrations of pesticides in the aqueous phase generally were detected in low concentrations and had few corresponding detections in the suspended- sediment samples. Dacthal, diazinon, chlorpyrifos, and simazine were the most frequently detected pesticides (greater than 83 percent) in the aqueous-phase samples, with median concentrations of 0.010 μg/L, 0.045 μg/L, 0.016 μg/L, and 0.077 μg/L, respectively. Simazine was the most frequently detected compound in the suspended-sediment samples (69 percent), with a median concentration of 0.232 μg/L. Results for compounds detected in the surficial-soil samples collected throughout the study period showed that there was an increase in concentration for some compounds, indicating atmospheric deposition of these compounds onto the soil-box surface. In the San Joaquin Valley, the compounds chlorpyrifos, dacthal, and iprodione were detected at higher concentrations (between 1.4 and 2 times greater) than were found in the background samples collected from the San Joaquin Valley soil-box sites. In the Sacramento Valley, the compounds chlorpyrifos, dacthal, iprodione, parathionmethyl, and its oxygen analog, paraoxon-methyl, were detected in samples collected during the study period in low concentrations, but were not detected in the background concentration of the Sacramento Valley soil mix.

California

Effects of surface applications of biosolids on groundwater quality and trace-element concentrations in crops near Deer Trail, Colorado, 2004-2010

The U.S. Geological Survey (USGS), in cooperation with Metro Wastewater Reclamation District (Metro District), studied biosolids composition and the effects of biosolids applications on groundwater quality and trace-element concentrations in crops of the Metro District properties near Deer Trail, Colorado, during 2004 through 2010. Priority parameters for each monitoring component included the nine trace elements regulated by Colorado for biosolids (arsenic, cadmium, copper, lead, mercury, molybdenum, nickel, selenium, and zinc); other constituents also were analyzed. All concentrations for the priority parameters in monthly biosolids samples were less than Colorado regulatory limits, and the concentrations were relatively consistent. Biosolids likely were the largest source of nitrogen and phosphorus on the Metro District properties. Plutonium isotopes were not detected in the biosolids, but many organic wastewater compounds (organic wastewater compounds: wastewater indicators, pharmaceuticals, and hormones) were detected in substantial concentrations relative to minimum reporting levels and various surface-water concentrations. Bismuth, copper, mercury, nitrogen, phosphorus, silver, biogenic sterols, detergent degradates, disinfectants, fire retardants, fragrances, pharmaceuticals, and plasticizers would be the most likely biosolids signature to indicate the presence of Metro District biosolids in soil or streambed sediment from the study area. Antimony, cadmium, cobalt, copper, molybdenum, nickel, nitrogen, phosphorus, selenium, tungsten, vanadium, zinc, detergent degradates, disinfectants, fire retardants, fragrances, pharmaceuticals or their degradates, and plasticizers would be the most likely biosolids signature for groundwater and surface water in the study area. More biosolids-signature components detected and larger concentration differences from untreated materials, baseline, and blank samples indicate more evidence of biosolids presence or effects. Although the inorganic constituent concentrations were relatively large in samples from one monitoring well, the concentrations of organic wastewater compounds in groundwater samples were not correspondingly large. Concentrations of organic wastewater compounds in the groundwater samples from all five monitoring wells were less than the minimum reporting levels with only a few detections. Some of the organic wastewater compounds detected could have anthropogenic sources that are not biosolids. Concentrations of priority parameters in groundwater varied spatially and temporally but generally were less than Colorado regulatory limits. Concentrations of dissolved nitrate, arsenic, and selenium, in addition to chloride, sulfate, total dissolved solids, boron, iron, manganese, and uranium, in samples from some wells exceeded the Colorado standards. Concentrations of dissolved nitrate (three wells), molybdenum (one well), selenium (two wells), and uranium (one well) in shallow groundwater had significant (alpha = 0.05) upward trends in some parts of the study area. The biosolids-signature results indicate that the aquifers intercepted by the five routinely sampled wells likely have received some recharge through treated (biosolids-applied) fields or biosolids-affected ponds. Adverse effects from this biosolids-related recharge range from few (if any) at one well to large and significantly (alpha = 0.05) increasing nitrate concentrations at another well. A statistical evaluation of five paired wheat-grain samples from treated (biosolids-applied) fields and untreated (control) fields did not indicate any evidence that biosolids applications significantly (alpha = 0.05 or 0.10) increased concentration of any of these constituents in wheat grain. The wheat-grain concentrations from this study were similar to those from other studies for fields in North America where no biosolids were applied. The data for the limited crop samples indicate that biosolids applications are not increasing the concentrations of arsenic, cadmium, copper, lead, mercury, molybdenum, nickel, selenium, sulfur, and zinc in mature wheat grain from the study area.

Colorado

Chiral pesticides: Identification, description, and environmental implications

Anthropogenic chemicals, including pesticides, are a major source of contamination and pollution in the environment. Pesticides have many positive uses: increased food production, decreased damage to crops and structures, reduced disease vector populations, and more. Nevertheless, pesticide exposure can pose risks to humans and the environment, so various mitigation strategies are exercised to make them safer, minimize their use, and reduce their unintended environment effects. One strategy that may help achieve these goals relies on the unique properties of chirality or molecular asymmetry. Some common terms related to chirality are defined in Table 1.

Archives of Environmental Contamination and Toxico

PAH volatilization following application of coal-tar-based pavement sealant

Coal-tar-based pavement sealants, a major source of PAHs to urban water bodies, have recently been identified as a source of volatile PAHs to the atmosphere. We tracked the volatilization of PAHs for 1 year after application of a coal-tar-based pavement sealant by measuring gas-phase PAH concentrations above the pavement surface and solid-phase PAH concentrations in sealant scraped from the surface. Gas-phase concentrations at two heights (0.03 and 1.28 m) and wind speed were used to estimate volatilization flux. The sum of the concentrations of eight frequently detected PAHs (ΣPAH 8 ) in the 0.03-m sample 1.6 h after application (297,000 ng m -3 ) was about 5000 times greater than that previously reported for the same height above unsealed parking lots (66 ng m -3 ). Flux at 1.6 h after application was estimated at 45,000 μg m -2 h -1 and decreased rapidly during the 45 days after application to 160 μg m -2 h -1 . Loss of PAHs from the adhered sealant also was rapid, with about a 50% decrease in solid-phase ΣPAH 8 concentration over the 45 days after application. There was general agreement, given the uncertainties, in the estimated mass of ΣPAH 8 lost to the atmosphere on the basis of air sampling (2–3 g m -2 ) and adhered sealant sampling (6 g m -2 ) during the first 16 days after application, translating to a loss to the atmosphere of one-quarter to one-half of the PAHs in the sealcoat product. Combining the estimated mass of ΣPAH 8 released to the atmosphere with a national-use estimate of coal-tar-based sealant suggests that PAH emissions from new coal-tar-based sealcoat applications each year (~1000 Mg) are larger than annual vehicle emissions of PAHs for the United States.

Atmospheric Environment

Volatilization of polycyclic aromatic hydrocarbons from coal-tar-sealed pavement

Coal-tar-based pavement sealants, a major source of PAHs to urban water bodies, are a potential source of volatile PAHs to the atmosphere. An initial assessment of volatilization of PAHs from coal-tar-sealed pavement is presented here in which we measured summertime gas-phase PAH concentrations 0.03 m and 1.28 m above the pavement surface of seven sealed (six with coal-tar-based sealant and one with asphalt-based sealant) and three unsealed (two asphalt and one concrete) parking lots in central Texas. PAHs also were measured in parking lot dust. The geometric mean concentration of the sum of eight frequently detected PAHs (ΣPAH 8 ) in the 0.03-m samples above sealed lots (1320 ng m -3 ) during the hottest part of the day was 20 times greater than that above unsealed lots (66.5 ng m -3 ). The geometric mean concentration in the 1.28-m samples above sealed lots (138 ng m -3 ) was five times greater than above unsealed lots (26.0 ng m -3 ). Estimated PAH flux from the sealed lots was 60 times greater than that from unsealed lots (geometric means of 88 and 1.4 μg m -2 h -1 , respectively). Although the data set presented here is small, the much higher estimated fluxes from sealed pavement than from unsealed pavement indicate that coal-tar-based sealants are emitting PAHs to urban air at high rates compared to other paved surfaces.

Chemosphere

Determination of steroid hormones and related compounds in filtered and unfiltered water by solid-phase extraction, derivatization, and gas chromatography with tandem mass spectrometry

A new analytical method has been developed and implemented at the U.S. Geological Survey National Water Quality Laboratory that determines a suite of 20 steroid hormones and related compounds in filtered water (using laboratory schedule 2434) and in unfiltered water (using laboratory schedule 4434). This report documents the procedures and initial performance data for the method and provides guidance on application of the method and considerations of data quality in relation to data interpretation. The analytical method determines 6 natural and 3 synthetic estrogen compounds, 6 natural androgens, 1 natural and 1 synthetic progestin compound, and 2 sterols: cholesterol and 3--coprostanol. These two sterols have limited biological activity but typically are abundant in wastewater effluents and serve as useful tracers. Bisphenol A, an industrial chemical used primarily to produce polycarbonate plastic and epoxy resins and that has been shown to have estrogenic activity, also is determined by the method. A technique referred to as isotope-dilution quantification is used to improve quantitative accuracy by accounting for sample-specific procedural losses in the determined analyte concentration. Briefly, deuterium- or carbon-13-labeled isotope-dilution standards (IDSs), all of which are direct or chemically similar isotopic analogs of the method analytes, are added to all environmental and quality-control and quality-assurance samples before extraction. Method analytes and IDS compounds are isolated from filtered or unfiltered water by solid-phase extraction onto an octadecylsilyl disk, overlain with a graded glass-fiber filter to facilitate extraction of unfiltered sample matrices. The disks are eluted with methanol, and the extract is evaporated to dryness, reconstituted in solvent, passed through a Florisil solid-phase extraction column to remove polar organic interferences, and again evaporated to dryness in a reaction vial. The method compounds are reacted with activated -methyl--trimethylsilyl trifluoroacetamide at 65 degrees Celsius for 1 hour to form trimethylsilyl or trimethylsilyl-enol ether derivatives that are more amenable to gas chromatographic separation than the underivatized compounds. Analysis is carried out by gas chromatography with tandem mass spectrometry using calibration standards that are derivatized concurrently with the sample extracts. Analyte concentrations are quantified relative to specific IDS compounds in the sample, which directly compensate for procedural losses (incomplete recovery) in the determined and reported analyte concentrations. Thus, reported analyte concentrations (or analyte recoveries for spiked samples) are corrected based on recovery of the corresponding IDS compound during the quantification process. Recovery for each IDS compound is reported for each sample and represents an absolute recovery in a manner comparable to surrogate recoveries for other organic methods used by the National Water Quality Laboratory. Thus, IDS recoveries provide a useful tool for evaluating sample-specific analytical performance from an absolute mass recovery standpoint. IDS absolute recovery will differ and typically be lower than the corresponding analyte’s method recovery in spiked samples. However, additional correction of reported analyte concentrations is unnecessary and inappropriate because the analyte concentration (or recovery) already is compensated for by the isotope-dilution quantification procedure. Method analytes were spiked at 10 and 100 nanograms per liter (ng/L) for most analytes (10 times greater spike levels were used for bisphenol A and 100 times greater spike levels were used for 3--coprostanol and cholesterol) into the following validation-sample matrices: reagent water, wastewater-affected surface water, a secondary-treated wastewater effluent, and a primary (no biological treatment) wastewater effluent. Overall method recovery for all analytes in these matrices averaged 100 percent, with overall relative standard deviation of 28 percent. Mean recoveries of the 20 individual analytes for spiked reagent-water samples prepared along with field samples and analyzed in 2009–2010 ranged from 84–104 percent, with relative standard deviations of 6–36 percent. Concentrations for two analytes, equilin and progesterone, are reported as estimated because these analytes had excessive bias or variability, or both. Additional database coding is applied to other reported analyte data as needed, based on sample-specific IDS recovery performance. Detection levels were derived statistically by fortifying reagent water at six different levels (0.1 to 4 ng/L) and range from about 0.4 to 4 ng/L for 16 analytes. Interim reporting levels applied to analytes in this report range from 0.8 to 8 ng/L. Bisphenol A and the sterols (cholesterol and 3-beta-coprostanol) were consistently detected in laboratory and field blanks. The minimum reporting levels were set at 100 ng/L for bisphenol A and at 200 ng/L for the two sterols to prevent any bias associated with the presence of these compounds in the blanks. A minimum reporting level of 2 ng/L was set for 11-ketotestosterone to minimize false positive risk from an interfering siloxane compound emanating as chromatographic-column bleed, from vial septum material, or from other sources at no more than 1 ng/L.

Techniques and Methods

Concentrations of Semivolatile Organic Compounds Associated with African Dust Air Masses in Mali, Cape Verde, Trinidad and Tobago, and the U.S. Virgin Islands, 2001-2008

Every year, billions of tons of fine particles are eroded from the surface of the Sahara Desert and the Sahel of West Africa, lifted into the atmosphere by convective storms, and transported thousands of kilometers downwind. Most of the dust is carried west to the Americas and the Caribbean in the Saharan Air Layer (SAL). Dust air masses predominately impact northern South America during the Northern Hemisphere winter and the Caribbean and Southeastern United States in summer. Dust concentrations vary considerably temporally and spatially. In a dust source region (Mali), concentrations range from background levels of 575 micrograms per cubic meter (mu/u g per m3) to 13,000 mu/u g per m3 when visibility degrades to a few meters (Gillies and others, 1996). In the Caribbean, concentrations of 200 to 600 mu/u g per m3 in the mid-Atlantic and Barbados (Prospero and others, 1981; Talbot and others, 1986), 3 to 20 mu/u g per m3 in the Caribbean (Prospero and Nees, 1986; Perry and others, 1997); and >100 mu/u g per m3 in the Virgin Islands (this dataset) have been reported during African dust conditions. Mean dust particle size decreases as the SAL traverses from West Africa to the Caribbean and Americas as a result of gravitational settling. Mean particle size reaching the Caribbean is <1 micrometer (mu/u m) (Perry and others, 1997), and even finer particles are carried into Central America, the Southeastern United States, and maritime Canada. Particles less than 2.5 mu/u m diameter (termed PM2.5) can be inhaled deeply into human lungs. A large body of literature has shown that increased PM2.5 concentrations are linked to increased cardiovascular/respiratory morbidity and mortality (for example, Dockery and others, 1993; Penn and others, 2005).

Data Series

Endocrine active chemicals, pharmaceuticals, and other chemicals of concern in surface water, wastewater-treatment plant effluent, and bed sediment, and biological characteristics in selected streams, Minnesota: Design, methods, and data, 2009

This report presents the study design, environmental data, and quality-assurance data for an integrated chemical and biological study of selected streams or lakes that receive wastewater-treatment plant effluent in Minnesota. This study was a cooperative effort of the U.S. Geological Survey, the Minnesota Pollution Control Agency, St. Cloud State University, the University of St. Thomas, and the University of Colorado. The objective of the study was to identify distribution patterns of endocrine active chemicals, pharmaceuticals, and other organic and inorganic chemicals of concern indicative of wastewater effluent, and to identify biological characteristics of estrogenicity and fish responses in the same streams. The U.S. Geological Survey collected and analyzed water, bed-sediment, and quality-assurance samples, and measured or recorded streamflow once at each sampling location from September through November 2009. Sampling locations included surface water and wastewater-treatment plant effluent. Twenty-five wastewater-treatment plants were selected to include continuous flow and periodic release facilities with differing processing steps (activated sludge or trickling filters) and plant design flows ranging from 0.002 to 10.9 cubic meters per second (0.04 to 251 million gallons per day) throughout Minnesota in varying land-use settings. Water samples were collected from the treated effluent of the 25 wastewater-treatment plants and at one point upstream from and one point downstream from wastewater-treatment plant effluent discharges. Bed-sediment samples also were collected at each of the stream or lake locations. Water samples were analyzed for major ions, nutrients, trace elements, pharmaceuticals, phytoestrogens and pharmaceuticals, alkylphenols and other neutral organic chemicals, carboxylic acids, and steroidal hormones. A subset (25 samples) of the bed-sediment samples were analyzed for carbon, wastewater-indicator chemicals, and steroidal hormones; the remaining samples were archived. Biological characteristics were determined by using an in-vitro bioassay to determine total estrogenicity in water samples and a caged fish study to determine characteristics of fish from experiments that exposed fish to wastewater effluent in 2009. St. Cloud State University deployed and processed caged fathead minnows at 13 stream sites during September 2009 for the caged fish study. Measured fish data included length, weight, body condition factor, and vitellogenin concentrations.

Minnesota

Water- and air-quality monitoring of Sweetwater Reservoir watershed, San Diego County, California — Phase one results continued, 2001-2003

In 1998, the U.S. Geological Survey, in cooperation with the Sweetwater Authority, began a study to monitor water, air, and sediment at the Sweetwater and Loveland Reservoirs in San Diego County, California. The study includes regular sampling of water and air at Sweetwater Reservoir for chemical constituents, including volatile organic compounds (VOC), polynuclear aromatic hydrocarbons (PAH), pesticides, and major and trace elements. The purpose of this study is to monitor changes in contaminant composition and concentration during the construction and operation of State Route 125. To accomplish this, the study was divided into two phases. Phase One sampling (water years 1998–2004) determined baseline conditions for the detection frequency and the concentrations of target compounds in air and water. Phase Two sampling (starting water year 2005) continues at selected monitoring sites during and after construction of State Route 125 to assess the chemical impact this roadway alignment may have on water quality in the reservoir. Water samples were collected for VOCs and pesticides at Loveland Reservoir during Phase One and will be collected during Phase Two for comparison purposes. Air samples collected to monitor changes in VOCs, PAHs, and pesticides were analyzed by adapting methods used to analyze water samples. Bed-sediment samples have been and will be collected three times during the study; at the beginning of Phase One, at the start of Phase Two, and near the end of the study. In addition to the ongoing data collection, several special studies were initiated to assess the occurrence of specific chemicals of concern, such as trace metals, anthropogenic indicator compounds, and pharmaceuticals. This report describes the study design, and the sampling and analytical methods, and presents data from water and air samples collected during the fourth and fifth years of Phase One of the study (October 2001 to September 2003). Data collected during the first three years has been previously published. Three types of quality-control samples were used in this study: blanks, spikes, and replicates. Blanks and spikes are used to estimate result bias, and replicates are used to estimate result variability. Additionally, surrogate compounds were added at the laboratory to samples of VOCs, PAHs, pesticides, anthropogenic indicator compounds, and pharmaceuticals to monitor sample-specific performance of the analytical method.

California

Pesticides in air and rainwater in the midcontinental United States, 1995: Methods and data

Weekly composite high-volume air and wet-only deposition samples were collected from April through September 1995 at paired urban and agricultural areas in Mississippi, Iowa, and Minnesota, and at a background site in Michigan's Upper Peninsula. This report describes the methods used to collect, analyze, and quality assure the samples, and presents the results of all chemical analyses and quality control procedures. Each sample was analyzed for 49 compounds, including several pesticides not examined in previous atmospheric studies. Eighty-five percent of the herbicides, 70 percent of the insecticides, and 100 percent of the transformation products that were targeted for analysis were detected in one or more samples at each paired site.

Open-File Report