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Selenium contamination of the Grasslands, a major California waterfowl area

In a recent study at Kesterson Reservoir in California, selenium was shown to cause mortality and deformities in embryos of aquatic birds. The present study was conducted to determine if selenium or other contaminants in agricultural drainwater used for marsh management were likely to cause similar adverse effects in the nearby Grasslands area. Selenium concentrations were elevated (greater than 15 ppm, dry-weight) in livers of some birds of all species collected from the Grasslands. Mean selenium concentrations in all species sampled in the South Grasslands were significantly higher (P less than 0.05) than those from the 'control site', the Volta Wildlife Area. Mean selenium levels in black-necked stilts (Himantopus mexicanus) from the South Grasslands (35.6 ppm) were similar (P greater than 0.05) to levels in stilts from Kesterson (46.4 ppm), but means for American avocets (Recurvirostra americana) from the South Grasslands (67.3 ppm) were higher (P less than 0.05) than those from Kesterson (28.4 ppm). Bird eggs and fish from the Grasslands also contained elevated levels of selenium. Concentrations of eight heavy metals in fish generally reflected those patterns previously found in water entering the study areas. Of the organochlorines detected in fish, only DDE occurred at concentrations potentially harmful to birds (6.1 and 3.0 ppm, wet weight, at two South Grassland sites). The effect on avian health or reproduction of the other contaminants, singly or in combination, could not be determined. However, selenium levels were apparently sufficiently elevated in 1984 to have caused adverse effects on avian reproduction in the South Grasslands.

California

Trace element residues in bluegills and common carp from the lower San Joaquin River, California, and its tributaries

Whole-body samples of bluegills (Lepomis macrochirus) and common carp (Cyprinus carpio) from the San Joaquin River and two tributaries (Merced River and Salt Slough) were analyzed to determine if the concentrations of any of nine elements were elevated as a result of exposure of the fish to agricultural subsurface (tile) drainage water. Highest concentrations (μg/g dry weight) detected were as follows (first number in each pair applies to bluegills and the second to carp): arsenic (As), 0.97 and 1.5; boron (B), 14 and 20; cadmium (Cd), 0.14 and 0.27; chromium (Cr), 2.7 and 2.2; mercury (hg), 3.3 and 2.9; molybdenum (Mo), 2.8 and 3.6; nickel (Ni), 0.87 and 2.2; lead (Pb), 0.26 and 2.3; and selenium (Se), 3.2 and 5.5. The lowest concentrations were below the levels of detection, except for Hg (0.15 in bluegills and 0.12 in carp) and Se (0.43 and 0.56). As judged by comparisons with data from the National Contaminant Biomonitoring Program and other published surveys, the concentrations of B, Hg, Mo, and Se were moderately elevated in fish from several sites in the San Joaquin Valley. However, only the Se concentrations were positively correlated with water quality variables (e.g., total alkalinity, conductivity, and turbidity) known to be influenced by irrigation return flows. Historical data from one site (Salt Slough), where trace elements in whole fish have been measured since 1969, indicated that Se concentrations increased more than twofold between 1973 and 1977, but thereafter remained near 3.0 μg g−1 (dry weight basis), presumably due to the continuing practice of disposing seleniferous tile drainage water into the most convenient stream channel.

California

Characterization of alkyl carbon in forest soils by CPMAS 13C NMR spectroscopy and dipolar dephasing

Samples obtained from forest soils at different stages of decomposition were treated sequentially with chloroform/methanol (extraction of lipids), sulfuric acid (hydrolysis), and sodium chlorite (delignification) to enrich them in refractory alkyl carbon. As revealed by NMR spectroscopy, this treatment yielded residues with high contents of alkyl carbon. In the NMR spectra of residues obtained from litter samples, resonances for carbohydrates are also present, indicating that these carbohydrates are tightly bound to the alkyl carbon structures. During decomposition in the soils this resistant carbohydrate fraction is lost almost completely. In the litter samples the alkyl carbon shows a dipolar dephasing behavior indicative of two structural components, a rigid and a more mobile component. As depth and decomposition increase, only the rigid component is observed. This fact could be due to selective degradation of the mobile component or to changes in molecular mobility during decomposition, e.g., because of an increase in cross linking or contact with the mineral matter of the soil.

Science of the Total Environment

Application of INEPT nitrogen-15 and silicon-29 nuclear magnetic resonance spectrometry to derivatized fulvic acids

Use of the INEPT experiment has been examined in two derivatization studies of the Suwannee River fulvic acid. In the first study, the fulvic acid was derivatized with 15N enriched hydroxylamine. The quantitative 15N NMR spectrum, acquired with a 45° pulse angle, 2.0 second pulse delay and inverse gated decoupling, showed that oximes (390-340 ppm) were the major derivatives, followed by nitriles (270-240 ppm), hydroxamic acids (170-160 ppm), secondary amides (150-115 ppm), and lactams (115-90 ppm). The INEPT 15N NMR spectrum was acquired using refocussing delays and polarization transfer times optimized for signal enhancement of singly protonated nitrogens. INEPT greatly enhanced the amide and lactam resonances, and showed that resonances downfield of 180 ppm in the quantitative spectrum represented nonprotonated nitrogens. In the second study, the fulvic acid was first methylated with diazomethane and then silylated with hexamethyldisilazane. The 29Si NMR spectra exhibited two major peaks, from approximately 33 to 22 ppm, representing silyl esters of carboxylic acids, and from 22 to 13 ppm, representing silyl ethers of alcohols and phenols. The INEPT 29Si NMR spectrum was virtually identical to the quantitative 29Si spectrum, acquired with a 90° pulse angle, 5.0 second pulse delay, inverse gated decoupling, and relaxation reagent. INEPT therefore can be used for quantitative analysis of trimethylsilyl derivatives of the fulvic acid, saving spectrometer time and eliminating the need for relaxation reagents.

Science of the Total Environment

Selenium and other elements in freshwater fishes from the irrigated San Joaquin valley, California

Arsenic (As), chromium (Cr), mercury (Hg), and selenium (Se) were measured in composite whole-body samples of five fishes — bluegill ( Lepomis macrochirus ), common carp ( Cyprinus carpio ), mosquitofish ( Gambusia affinis ), largemouth bass ( Micropterus salmoides ), and Sacramento blackfish ( Orthodon microlepidotus ) — from the San Joaquin River system to determine if concentrations were elevated from exposure to agricultural subsurface (tile) drainage. Except for Cr, the concentrations of these elements in fishes from one or more sites were elevated; however, only Se approached concentrations that may adversely affect survival, growth, or reproduction in warm water fishes. Moreover, only Se among the four measured elements exhibited a geographic (spatial) pattern that coincided with known inflows of tile drainage to the San Joaquin River and its tributaries. Historical data from the Grassland Water District (Grasslands; a region exposed to concentrated tile drainage) suggested that concentrations of Se in fishes were at maximum during or shortly after 1984 and have been slightly lower since then. The recent decline of Se concentrations in fishes from the Grasslands could be temporary if additional acreages of irrigated lands in this portion of the San Joaquin Valley must be tile-drained to protect agricultural crops from rising groundwater tables

California

Testing and validating environmental models

Generally accepted standards for testing and validating ecosystem models would benefit both modellers and model users. Universally applicable test procedures are difficult to prescribe, given the diversity of modelling approaches and the many uses for models. However, the generally accepted scientific principles of documentation and disclosure provide a useful framework for devising general standards for model evaluation. Adequately documenting model tests requires explicit performance criteria, and explicit benchmarks against which model performance is compared. A model's validity, reliability, and accuracy can be most meaningfully judged by explicit comparison against the available alternatives. In contrast, current practice is often characterized by vague, subjective claims that model predictions show 'acceptable' agreement with data; such claims provide little basis for choosing among alternative models. Strict model tests (those that invalid models are unlikely to pass) are the only ones capable of convincing rational skeptics that a model is probably valid. However, 'false positive' rates as low as 10% can substantially erode the power of validation tests, making them insufficiently strict to convince rational skeptics. Validation tests are often undermined by excessive parameter calibration and overuse of ad hoc model features. Tests are often also divorced from the conditions under which a model will be used, particularly when it is designed to forecast beyond the range of historical experience. In such situations, data from laboratory and field manipulation experiments can provide particularly effective tests, because one can create experimental conditions quite different from historical data, and because experimental data can provide a more precisely defined 'target' for the model to hit. We present a simple demonstration showing that the two most common methods for comparing model predictions to environmental time series (plotting model time series against data time series, and plotting predicted versus observed values) have little diagnostic power. We propose that it may be more useful to statistically extract the relationships of primary interest from the time series, and test the model directly against them.

Science of the Total Environment

Bromine incorporation factors for trihalomethane formation for the Mississippi, Missouri, and Ohio Rivers

The bromine incorporation factor describes the distribution of the four trihalomethane compounds in the mixture formed when a natural water is chlorinated. This factor was determined for the Mississippi, Missouri, and Ohio Rivers by chlorinating water samples at three levels each of pH and free chlorine concentration. Samples were collected during the summer, fall, and spring seasons of the year at 12 sites on the Mississippi River from Minneapolis, MN, to New Orleans, LA, and on the Missouri and Ohio Rivers 1.6 kilometers upstream from their confluences with the Mississippi. The bromine incorporation factor increased as the bromide concentration increased, and decreased as the pH, initial free-chlorine and dissolved organic-carbon concentrations increased. Variation of the bromine incorporation factor with distance along the Mississippi River approximately paralleled the variation of the bromide concentration with distance along the river, with the Missouri River samples having the highest bromine incorporation factors for all combinations of pH and free-chlorine concentration.

Science of the Total Environment

Historical trends in occurrence and atmospheric inputs of halogenated volatile organic compounds in untreated ground water used as a source of drinking water

Analyses of samples of untreated ground water from 413 community-, non-community- (such as restaurants), and domestic-supply wells throughout the US were used to determine the frequency of detection of halogenated volatile organic compounds (VOCs) in drinking-water sources. The VOC data were compiled from archived chromatograms of samples analyzed originally for chlorofluorocarbons (CFCs) by purge-and-trap gas chromatography with an electron-capture detector (GC-ECD). Concentrations of the VOCs could not be ascertained because standards were not routinely analyzed for VOCs other than trichloromonofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12) and 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113). Nevertheless, the peak areas associated with the elution times of other VOCs on the chromatograms can be classified qualitatively to assess concentrations at a detection limit on the order of parts per quadrillion. Three or more VOCs were detected in 100% (percent) of the chromatograms, and 77.2% of the samples contained 10 or more VOCs. The maximum number of VOCs detected in any sample was 24. Modeled ground-water residence times, determined from concentrations of CFC-12, were used to assess historical trends in the cumulative occurrence of all VOCs detected in this analysis, as well as the occurrence of individual VOCs, such as CFC-11, carbon tetrachloride (CCl 4 ), chloroform and tetrachloroethene (PCE). The detection frequency for all of the VOCs detected has remained relatively constant from approximately 1940 to 2000; however, the magnitude of the peak areas on the chromatograms for the VOCs in the water samples has increased from 1940 to 2000. For CFC-11, CCl 4 , chloroform and PCE, small peaks decrease from 1940 to 2000, and large peaks increase from 1940 to 2000. The increase in peak areas on the chromatograms from analyses of more recently recharged water is consistent with reported increases in atmospheric concentrations of the VOCs. Approximately 44% and 6.7% of the CCl 4 and PCE detections, respectively, in pre-1940 water, and 68% and 62% of the CCl 4 and PCE detections, respectively, in water recharged in 2000 exceed solubility equilibrium with average atmospheric concentrations. These exceedences can be attributed to local atmospheric enrichment or direct contaminant input to ground-water flow systems. The detection of VOCs at concentrations indicative of atmospheric sources in 100% of the samples indicates that untreated drinking water from ground-water sources in the US recharged within the past 60 years has been affected by anthropogenic activity. Additional inputs from a variety of sources such as spills, underground injections and leaking landfills or storage tanks increasingly are providing additional sources of contamination to ground water used as drinking-water sources.

Science of the Total Environment

Distribution of total and methyl mercury in sediments along Steamboat Creek (Nevada, USA)

In the late 1800s, mills in the Washoe Lake area, Nevada, used elemental mercury to remove gold and silver from the ores of the Comstock deposit. Since that time, mercury contaminated waste has been distributed from Washoe Lake, down Steamboat Creek, and to the Truckee River. The creek has high mercury concentrations in both water and sediments, and continues to be a constant source of mercury to the Truckee River. The objective of this study was to determine concentrations of total and methyl mercury (MeHg) in surface sediments and characterize their spatial distribution in the Steamboat Creek watershed. Total mercury concentrations measured in channel and bank sediments did not decrease downstream, indicating that mercury contamination has been distributed along the creek's length. Total mercury concentrations in sediments (0.01–21.43 μg/g) were one to two orders of magnitude higher than those in pristine systems. At 14 out of 17 sites, MeHg concentrations in streambank sediments were higher than the concentrations in the channel, suggesting that low banks with wet sediments might be important sites of mercury methylation in this system. Both pond/wetland and channel sites exhibited high potential for mercury methylation (6.4–30.0 ng g −1 day −1 ). Potential methylation rates were positively correlated with sulfate reduction rates, and decreased as a function of reduced sulfur and MeHg concentration in the sediments. Potential demethylation rate appeared not to be influenced by MeHg concentration, sulfur chemistry, DOC, sediment grain size or other parameters, and showed little variation across the sites (3.7–7.4 ng g −1 day −1 ).

Nevada

The geochemistry of Seine River Basin particulate matter: Distribution of an integrated metal pollution index

Spatial analysis (1994-2001) and temporal trends (1980-2000) for particulate-associated metals at key stations in the Seine River Basin have been determined using a new metal pollution index (MPI). The MPI is based on the concentrations of Cd, Cu, Hg, Pb and Zn, normalized to calculated background levels estimated for each particulate matter samples for four fractions (clays and other aluminosilicates, carbonates, organic matter, and quartz). Background levels ascribed to each fraction were determined from a specific set of samples collected from relatively pristine areas in the upper Seine basin and validated on prehistoric samples. The unitless MPI is designed to vary between 0 for pristine samples to 100 for the ones extremely impacted by human activities and to assess the trends of general metal contamination and its mapping. Throughout the Seine basin, MPI currently range from 1 to 40, but values exceeding 100 have been found in periurban streams and the Eure tributary. Based on the MPI spatial distribution, the Seine River Basin displays a wide range of anthropogenic impacts linked to variations in population density, stream order, wastewater discharges and industrial activities. Correlations between the MPI and other trace elements indicate that anthropogenic impacts also strongly affect the concentrations of Ag, Sb, and P, marginally affect the concentrations of Ba, Ni, and Cr, and appear to have little effect on the concentrations of Li, Be, V, Co, and the major elements. Temporal MPI trends can also be reconstituted from past regulatory surveys. In the early 1980s, MPI were 2-5 times higher than nowadays at most locations, particularly downstream of Greater Paris where it reached levels as high as 250 (now 40), a value characteristic of present Paris urban sewage. The exceptional contamination of the Seine basin is gradually improving over the last 20 years but remains very high. ?? 2004 Elsevier B.V. All rights reserved.

Science of the Total Environment

Persistence of pharmaceutical compounds and other organic wastewater contaminants in a conventional drinking-water-treatment plant

In a study conducted by the US Geological Survey and the Centers for Disease Control and Prevention, 24 water samples were collected at selected locations within a drinking-water-treatment (DWT) facility and from the two streams that serve the facility to evaluate the potential for wastewater-related organic contaminants to survive a conventional treatment process and persist in potable-water supplies. Stream-water samples as well as samples of raw, settled, filtered, and finished water were collected during low-flow conditions, when the discharge of effluent from upstream municipal sewage-treatment plants accounted for 37–67% of flow in stream 1 and 10–20% of flow in stream 2. Each sample was analyzed for 106 organic wastewater-related contaminants (OWCs) that represent a diverse group of extensively used chemicals. Forty OWCs were detected in one or more samples of stream water or raw-water supplies in the treatment plant; 34 were detected in more than 10% of these samples. Several of these compounds also were frequently detected in samples of finished water; these compounds include selected prescription and non-prescription drugs and their metabolites, fragrance compounds, flame retardants and plasticizers, cosmetic compounds, and a solvent. The detection of these compounds suggests that they resist removal through conventional water-treatment processes. Other compounds that also were frequently detected in samples of stream water and raw-water supplies were not detected in samples of finished water; these include selected prescription and non-prescription drugs and their metabolites, disinfectants, detergent metabolites, and plant and animal steroids. The non-detection of these compounds indicates that their concentrations are reduced to levels less than analytical detection limits or that they are transformed to degradates through conventional DWT processes. Concentrations of OWCs detected in finished water generally were low and did not exceed Federal drinking-water standards or lifetime health advisories, although such standards or advisories have not been established for most of these compounds. Also, at least 11 and as many as 17 OWCs were detected in samples of finished water. Drinking-water criteria currently are based on the toxicity of individual compounds and not combinations of compounds. Little is known about potential human-health effects associated with chronic exposure to trace levels of multiple OWCs through routes such as drinking water. The occurrence in drinking-water supplies of many of the OWCs analyzed for during this study is unregulated and most of these compounds have not been routinely monitored for in the Nation's source- or potable-water supplies. This study provides the first documentation that many of these compounds can survive conventional water-treatment processes and occur in potable-water supplies. It thereby provides information that can be used in setting research and regulatory priorities and in designing future monitoring programs. The results of this study also indicate that improvements in water-treatment processes may benefit from consideration of the response of OWCs and other trace organic contaminants to specific physical and chemical treatments.

Science of the Total Environment

Trace elements in moose (Alces alces) found dead in Northwestern Minnesota, USA

The moose ( Alces alces ) population in bog and forest areas of Northwestern Minnesota has declined for more than 25 years, and more recently the decline is throughout Northwestern Minnesota. Both deficiencies and elevations in trace elements have been linked to the health of moose worldwide. The objective of this study was to evaluate whether trace element toxicity or deficiency may have contributed to the decline of moose in Northwestern Minnesota. Livers of 81 moose found dead in Northwestern Minnesota in 1998 and 1999 were analyzed for trace elements. With the exception of selenium (Se) and copper (Cu), trace elements were not at toxic or deficient levels based on criteria set for cattle. Selenium concentrations in moose livers based on criteria set for cattle were deficient in 3.7% of livers and at a chronic toxicity level in 16% of livers. Copper concentrations based on criteria set for cattle were deficient in 39.5% of livers, marginally deficient in 29.5% of livers and adequate in 31% of livers. Moose from agricultural areas had higher concentrations, on average, of Cd, Cu, Mo and Se in their livers than moose from bog and forest areas. Older moose had higher concentrations of Cd and Zn, and lower concentrations of Cu than younger moose. Copper deficiency, which has been associated with population declines of moose in Alaska and Sweden, may be a factor contributing to the decline of moose in Northwestern Minnesota. (C) 2004 Elsevier B.V. All rights reserved.

Minnesota

Elemental content of lichens of the Point Reyes Peninsula, northern California

The Point Reyes peninsula in northern California is about 45 km northwest of San Francisco and occasionally receives air masses from the city contributing to haze and lowered visibility. Although gaseous pollutants are not a problem, fine particulates containing carbon and other elements are measurable at the park. In this study, five lichen species were sampled along a 40-km linear transect from southeast to northwest from the town of Bolinas at the southern end of the peninsula. Elevated levels of Na and S and the Na/S ratio at localities nearer the ocean confirmed there is a definite marine aerosol influence on lichen elemental content. Elevated potassium and mercury concentrations were also found at high elevation sites that intercept fog. However, arsenic and lead were found to decrease with distance from Bolinas along the transect, suggesting these two elements originate in the fine particulate haze that enters the park from San Francisco. Concentrations of elements were not at enriched levels for other lichen species. A possible local influence of roads on element content needs further study.

California

Urban contributions of glyphosate and its degradate AMPA to streams in the United States

Glyphosate is the most widely used herbicide in the world, being routinely applied to control weeds in both agricultural and urban settings. Microbial degradation of glyphosate produces aminomethyl phosphonic acid (AMPA). The high polarity and water-solubility of glyphosate and AMPA has, until recently, made their analysis in water samples problematic. Thus, compared to other herbicides (e.g. atrazine) there are relatively few studies on the environmental occurrence of glyphosate and AMPA. In 2002, treated effluent samples were collected from 10 wastewater treatment plants (WWTPs) to study the occurrence of glyphosate and AMPA. Stream samples were collected upstream and downstream of the 10 WWTPs. Two reference streams were also sampled. The results document the apparent contribution of WWTP effluent to stream concentrations of glyphosate and AMPA, with roughly a two-fold increase in their frequencies of detection between stream samples collected upstream and those collected downstream of the WWTPs. Thus, urban use of glyphosate contributes to glyphosate and AMPA concentrations in streams in the United States. Overall, AMPA was detected much more frequently (67.5%) compared to glyphosate (17.5%).

Science of the Total Environment

Environmental contaminants and biomarker responses in fish from the Rio Grande and its U.S. tributaries: Spatial and temporal trends

We collected, examined, and analyzed 368 fish of seven species from 10 sites on rivers of the Rio Grande Basin (RGB) during late 1997 and early 1998 to document temporal and geographic trends in the concentrations of accumulative contaminants and to assess contaminant effects on the fish. Sites were located on the mainstem of the Rio Grande and on the Arroyo Colorado and Pecos River in Texas (TX), New Mexico (NM), and Colorado. Common carp (Cyprinus carpio) and largemouth bass (Micropterus salmoides) were the targeted species. Fish were examined in the field for internal and external visible gross lesions, selected organs were weighed to compute ponderal and organosomatic indices, and samples of tissues and fluids were obtained and preserved for analysis of fish health and reproductive biomarkers. Whole fish from each station were composited by species and gender and analyzed for organochlorine chemical residues and elemental contaminants using instrumental methods, and for 2,3,7,8-tetrachloro dibenzo-p-dioxin-like activity (TCDD-EQ) using the H4IIE rat hepatoma cell bioassay. Overall, fish from lower RGB stations contained greater concentrations of organochlorine pesticide residues and appeared to be less healthy than those from sites in the central and upper parts of the basin, as indicated by a general gradient of residue concentrations and biomarker responses. A minimal number of altered biomarkers and few or no elevated contaminant concentrations were noted in fish from the upper RGB. The exception was elevated concentrations [up to 0.46 ??g/g wet-weight (ww)] of total mercury (Hg) in predatory species from the Rio Grande at Elephant Butte Reservoir, NM, a condition documented in previous studies. Arsenic (As) and selenium (Se) concentrations were greatest in fish from sites in the central RGB; Se concentrations in fish from the Pecos River at Red Bluff Lake, TX and from the Rio Grande at Langtry, TX and Amistad International Reservoir, TX exceeded published fish and wildlife toxicity thresholds. In the lower RGB, residues of p,p???-DDT metabolites (???1.69 ??g/g ww), chlordane-related compounds (???0.21 ??g/g ww), dieldrin (???0.0.05 ??g/g ww), and toxaphene (???2.4 ??g/g ww) were detected in fish from most sites; maximum concentrations were in channel catfish (Ictalurus punctatus) from the Arroyo Colorado at Harlingen, TX. Concentrations of one or more residues exceeded toxicity thresholds for fish and wildlife in fish from this site and from the Rio Grande at Mission, TX and Brownsville, TX; however, concentrations were lower than those reported by previous studies. In addition, the proportional concentrations of p,p???-DDT at all sites were low, indicating weathered DDT rather than the influx of new material. Concentrations of total PCBs (<0.05 ??g/g ww) and TCDD-EQ (???6 pg/g ww) were comparatively low in all samples. Hepatic ethoxyresorufin O-deethylase (EROD) activity in some fish was elevated relative to reference rates at most sites, but was generally lower than previously reported activity in fish from heavily contaminated locations. The comparatively low PCB and TCDD-EQ concentrations together with elevated EROD activity may reflect exposure to polycyclic aromatic hydrocarbons. Reproductive biomarkers were consistent with chronic contaminant exposure at lower RGB sites; comparatively large percentages of intersex male largemouth bass, relatively low gonadosomatic indices, and elevated plasma vitellogenin concentrations in male fish were noted at three of the four stations. Large percentages of atretic eggs were also observed in the ovaries of female common carp from the Rio Grande at Brownsville, TX. Although many of the conditions noted may have other causes in addition to contaminant exposure, the biomarker results for the lower RGB sites are consistent with subtle responses of fish to contaminants, an interpretation supported by the chemical data of this and other investigations.

Science of the Total Environment

The spatial and temporal trends of Cd, Cu, Hg, Pb and Zn in Seine River floodplain deposits (1994-2000)

Fresh floodplain deposits (FD), from 11 key stations, covering the Seine mainstem and its major tributaries (Yonne, Marne and Oise Rivers), were sampled from 1994 to 2000. Background levels for Cd, Cu, Hg, Pb, and Zn were established using prehistoric FD and actual bed sediments collected in small forested sub-basins in the most upstream part of the basin. Throughout the Seine River Basin, FD contain elevated concentrations of Cd, Cu, Hg, Pb and Zn compared to local background values (by factors > twofold). In the Seine River Basin, trace element concentrations display substantial downstream increases as a result of increasing population densities, particularly from Greater Paris (10 million inhabitants), and reach their maxima at the river mouth (Poses). These elevated levels make the Seine one of the most heavily impacted rivers in the world. On the other hand, floodplain-associated trace element levels have declined over the past 7 years. This mirrors results from contemporaneous suspended sediment surveys at the river mouth for the 1984-1999 period. Most of these temporal declines appear to reflect reductions in industrial and domestic solid wastes discharged from the main Parisian sewage plant (Seine Aval). ?? 2005 Elsevier B.V. All rights reserved.

Science of the Total Environment

Response to comment on “Persistence of pharmaceutical compounds and other organic wastewater contaminants in a conventional drinking-water-treatment plant”

The U.S. Geological Survey (USGS) and the Centers for Disease Control thank Dr. Till for her comments concerning our research ( Till, 2005 ) and welcome the opportunity to respond. The primary objective of our study was to evaluate the potential for organic wastewater-related contaminants (OWCs), including pharmaceuticals, to survive a conventional drinking-water-treatment process and persist in potable-water supplies ( Stackelberg et al., 2004 ). Our study was supported by two USGS laboratories: the National Water Quality Laboratory (NWQL), which provided the HPLC/ESI-MS and CLLE GC/MS data and the Ocala Water Quality and Research Laboratory (OWQRL), which provided the LC/MS data ( Stackelberg et al., 2004 ). Although discussed as distinct techniques by Dr. Till and indicated by differing acronyms to distinguish the laboratories producing the data, as described in our paper, the two LC/MS methods are very similar; they consist of a solid-phase extraction method with analysis of the extract produced using high-performance liquid chromatography coupled to an electrospray ionization mass spectrometer operated in the positive mode. The NWQL and OWQRL report ‘trace’ and ‘ultratrace’ determinations of analytes that provide significant benefit for describing the presence and fate of low-level contaminants. For mass spectral methods, an analyte is qualitatively identified by its retention time on the chromatographic column as well as the presence of two or more confirming ions with area ratios that match that of the reference standard compounds. Because of a recognized increased risk of false positives, these qualitative identification criteria are used in conjunction with abundant quality-control samples (detailed below) to confirm detection prior to making an estimate of the concentration. These qualitative identification criteria must be met before a compound is considered present (or detected) in a sample ( Oblinger Childress et al., 1999 ). When a compound has been qualitatively identified in an environmental sample (whether above or below its reporting level [RL]), it is assessed in context with associated field and laboratory blanks, field and laboratory replicates, and other data, such as appropriate laboratory reagent spikes. An environmental concentration is calculated only after determining that field and laboratory procedures did not contaminate the samples. The concentrations are then calculated from 5- to 8-point calibration curves using internal standard quantitation. Our lowest calibration standard is intentionally much lower than the RL, typically 10 times lower. The most abundant molecular or fragment ion is used for quantitation, and, for the two LC/MS methods, at least one, and where possible two, qualifier ions are used for confirmation. For the GC/MS method, with its greater degree of fragmentation, one quantitation and two qualifier ions are used. When any of the abovementioned qualitative identification criteria are not met, the analyte is considered not present and is reported as “less than” the RL.

Science of the Total Environment