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USGS2005

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↗
USGS2006

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↗
USGS2006

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↗
USGS2006

Water and solute mass balance of five small, relatively undisturbed watersheds in the U.S.

Geochemical mass balances were computed for water years 1992-1997 (October 1991 through September 1997) for the five watersheds of the U.S. Geological Survey Water, Energy, and Biogeochemical Budgets (WEBB) Program to determine the primary regional controls on yields of the major dissolved inorganic solutes. The sites, which vary markedly with respect to climate, geology, physiography, and ecology, are: Allequash Creek, Wisconsin (low-relief, humid continental forest); Andrews Creek, Colorado (cold alpine, taiga/tundra, and subalpine boreal forest); Ri??o Icacos, Puerto Rico (lower montane, wet tropical forest); Panola Mountain, Georgia (humid subtropical piedmont forest); and Sleepers River, Vermont (humid northern hardwood forest). Streamwater output fluxes were determined by constructing empirical multivariate concentration models including discharge and seasonal components. Input fluxes were computed from weekly wet-only or bulk precipitation sampling. Despite uncertainties in input fluxes arising from poorly defined elevation gradients, lack of dry-deposition and occult-deposition measurements, and uncertain sea-salt contributions, the following was concluded: (1) for solutes derived primarily from rock weathering (Ca, Mg, Na, K, and H4SiO4), net fluxes (outputs in streamflow minus inputs in deposition) varied by two orders of magnitude, which is attributed to a large gradient in rock weathering rates controlled by climate and geologic parent material; (2) the net flux of atmospherically derived solutes (NH4, NO3, SO4, and Cl) was similar among sites, with SO4 being the most variable and NH4 and NO3 generally retained (except for NO 3 at Andrews); and (3) relations among monthly solute fluxes and differences among solute concentration model parameters yielded additional insights into comparative biogeochemical processes at the sites. ?? 2005 Elsevier B.V. All rights reserved.

Science of the Total Environment↗
USGS2006

Mercury in ground water, septage, leach-field effluent, and soils in residential areas, New Jersey coastal plain

Water samples were collected from domestic wells at an unsewered residential area in Gloucester County, New Jersey where mercury (Hg) concentrations in well water were known to exceed the USEPA maximum contaminant level (MCL) of 2000 ng/L. This residential area (the CSL site) is representative of more than 70 such areas in southern New Jersey where about 600 domestic wells, sampled previously by State and county agencies, yielded water containing Hg at concentrations that exceed the MCL. Recent studies indicate that background concentrations of Hg in water from this unconfined sand and gravel aquifer system are < 10 ng/L. Additional sampling was conducted at the CSL site in order to better understand sources of Hg and potential Hg transport mechanisms in the areas with Hg-contaminated ground water. At the CSL site, concentrations of Hg were substantially lower (although still exceeding the MCL in some cases) in filtered water samples than in the unfiltered water samples collected previously from the same wells. Surfactants and elevated concentrations of sodium, chloride, nitrate, ammonium, and phosphate in water from domestic and observation wells indicated septic-system effects on water quality; detections of sulfide indicated localized reducing conditions. Hg concentrations in septage and leach-field effluent sampled at several other households in the region were low relative to the contaminant-level Hg concentrations in water from domestic wells. Relations of Hg concentrations in leach-field effluent to iron concentrations indicate that reductive dissolution of iron hydroxides in soils may release Hg to the percolating effluent.

New Jersey↗
USGS2006

Geochemistry of bed and suspended sediment in the Mississippi river system: Provenance versus weathering and winnowing

Stream-bed sediment for the size fraction less than 150 μm, examined in 14,000 samples collected mostly from minor tributaries to the major rivers throughout the Mississippi River drainage system, is composed of 5 mineral fractions identified by factor analysis—Al-silicate minerals, quartz, calcite and dolomite, heavy minerals, and an Fe–Mn fraction. The Al-silicate fraction parallels its distribution in the regolith, emphasizing the local sediment source as a primary control to its distribution. Quartz and the heavy-mineral fraction, and associated trace elements, exhibit a complementary distribution to that of the Al-silicate fraction, with a level of enrichment in the bed sediment that is achieved through winnowing and sorting. The carbonate fraction has a distribution suggesting its dissolution during transport. Trace elements partitioned onto the Fe–Mn, possibly amorphous oxyhydride, fraction are introduced to the streams, in part, through human activity. Except for the heavy-mineral fraction, these fractions are identified in suspended sediment from the Mississippi River itself. Although comparison of the tributary bed sediment with the riverine suspended sediment is problematic, the geochemistry of the suspended sediment seems to corroborate the interpretation of the geochemistry of the bed sediment.

Arkansas basin, Ohio basin Tennessee basin, Lower ↗
USGS2006

Occurrence of antibiotics in wastewater treatment facilities in Wisconsin, USA

Samples from several wastewater treatment facilities in Wisconsin were screened for the presence of 21 antibiotic compounds. These facilities spanned a range of community size served (average daily flow from 0.0212 to 23.6 million gallons/day), secondary treatment processes, geographic locations across the state, and they discharged the treated effluents to both surface and ground waters (for ground water after a soil passage). A total of six antibiotic compounds were detected (1–5 compounds per site), including two sulfonamides (sulfamethazine, sulfamethoxazole), one tetracycline (tetracycline), fluoroquinolone (ciprofloxacin), macrolide (erythromycin-H 2 O) and trimethoprim. The frequency of detection of antibiotics was in the following order: tetracycline and trimethoprim (80%) > sulfamethoxazole (70%) > erythromycin-H 2 O (45%) > ciprofloxacin (40%) > sulfamethazine (10%). However, the soluble concentrations were in the parts-per-billion (ppb) range (≤ 1.3 μg/L), and importantly were unaffected by the size of the wastewater treatment facility. The concentrations detected were within an order of magnitude of those reported for similar systems in Europe and Canada: they were within a factor of two in comparison to those reported for Canada but generally lower relative to those measured in wastewater systems in Europe. Only sulfamethoxazole and tetracycline were detected in groundwater monitoring wells adjacent to the treatment systems. Future intensive wastewater monitoring programs in Wisconsin may be limited to the six antibiotic compounds detected in this study.

Science of the Total Environment↗
USGS2006

Comparative evaluation of short-term leach tests for heavy metal release from mineral processing waste

Evaluation of metal leaching using a single leach test such as the Toxicity Characteristic Leaching Procedure (TCLP) is often questionable. The pH, redox potential (Eh), particle size and contact time are critical variables in controlling metal stability, not accounted for in the TCLP. This paper compares the leaching behavior of metals in mineral processing waste via short-term extraction tests such as TCLP, Field Leach Test (FLT) used by USGS and deionized water extraction tests. Variation in the extracted amounts was attributed to the use of different particle sizes, extraction fluid and contact time. In the controlled pH experiments, maximum metal extraction was obtained at acidic pH for cationic heavy metals such as Cu, Pb and Zn, while desorption of Se from the waste resulted in high extract concentrations in the alkaline region. Precipitation of iron, caused by a pH increase, probably resulted in co-precipitation and immobilization of Cu, Pb and Zn in the alkaline pH region. A sequential extraction procedure was performed on the original waste and the solid residue from the Eh-pH experiments to determine the chemical speciation and distribution of the heavy metals. In the as-received waste, Cu existed predominantly in water soluble or sulfidic phases, with no binding to carbonates or iron oxides. Similar characteristics were observed for Pb and Zn, while Se existed mostly associated with iron oxides or sulfides. Adsorption/co-precipitation of Cu, Se and Pb on precipitated iron hydroxides was observed in the experimental solid residues, resulting in metal immobilization above pH 7.

Science of the Total Environment↗
USGS2006

Environmental contaminants and biomarker responses in fish from the Columbia River and its tributaries: spatial and temporal trends

Fish were collected from 16 sites on rivers in the Columbia River Basin (CRB) from September 1997 to April 1998 to document temporal and spatial trends in the concentrations of accumulative contaminants and to assess contaminant effects on the fish. Sites were located on the mainstem of the Columbia River and on the Snake, Willamette, Yakima, Salmon, and Flathead Rivers. Common carp (Cyprinus carpio), black bass (Micropterus sp.), and largescale sucker (Catostomus macrocheilus) were the targeted species. Fish were field-examined for external and internal lesions, selected organs were weighed to compute somatic indices, and tissue and fluid samples were preserved for fish health and reproductive biomarker analyses. Composite samples of whole fish, grouped by species and gender, from each site were analyzed for organochlorine 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, pesticide concentrations were greatest in fish from lower CRB sites and elemental concentrations were greatest in fish from upper CRB sites. These patterns reflected land uses. Lead (Pb) concentrations in fish from the Columbia River at Northport and Grand Coulee, Washington (WA) exceeded fish and wildlife toxicity thresholds (> 0.4 ??g/g). Selenium (Se) concentrations in fish from the Salmon River at Riggins, Idaho (ID), the Columbia River at Vernita Bridge, WA, and the Yakima River at Granger, WA exceeded toxicity thresholds for piscivorous wildlife (> 0.6 ??g/g). Mercury (Hg) concentrations in fish were elevated throughout the basin but were greatest (> 0.4 ??g/g) in predatory fish from the Salmon River at Riggins, ID, the Yakima River at Granger, WA, and the Columbia River at Warrendale, Oregon (OR). Residues of p,p???-DDE were greatest (> 0.8 ??g/g) in fish from agricultural areas of the Snake, Yakima, and Columbia River basins but were not detected in upper CRB fish. Other organochlorine pesticides did not exceed toxicity thresholds in fish or were detected infrequently. Total polychlorinated biphenyls (PCBs; > 0.11 ??g/g) and TCDD-EQs (> 5 pg/g) exceeded wildlife guidelines in fish from the middle and lower CRB, and ethoxyresorufin O-deethylase (EROD) activity was also elevated at many of the same sites. Temporal trend analysis indicated decreasing or stable concentrations of Pb, Se, Hg, p,p???-DDE, and PCBs at most sites where historical data were available. Altered biomarkers were noted in fish throughout the CRB. Fish from some stations had responded to chronic contaminant exposure as indicated by fish health and reproductive biomarker results. Although most fish from some sites had grossly visible external or internal lesions, histopathological analysis determined these to be inflammatory responses associated with helminth or myxosporidian parasites. Many largescale sucker from the Columbia River at Northport and Grand Coulee, WA had external lesions and enlarged spleens, which were likely associated with infections. Intersex male smallmouth bass (Micropterus dolomieu) were found in the Snake River at Lewiston, ID and the Columbia River at Warrendale, OR. Male bass, carp, and largescale sucker containing low concentrations of vitellogenin were common in the CRB, and comparatively high concentrations (> 0.3 mg/mL) were measured in male fish from the Flathead River at Creston, Montana, the Snake River at Ice Harbor Dam, WA, and the Columbia River at Vernita Bridge, WA and Warrendale, OR. Results from our study and other investigations indicate that continued monitoring in the CRB is warranted to identify consistently degraded sites and those with emerging problems. ?? 2005 Elsevier B.V. All rights reserved.

Columbia River Basin↗
USGS2006

Atmospheric mercury speciation in Yellowstone National Park

Atmospheric concentrations of elemental mercury (Hg 0 ), reactive gaseous Hg (RGM), and particulate Hg (pHg) concentrations were measured in Yellowstone National Park (YNP), U.S.A. using high resolution, real time atmospheric mercury analyzers (Tekran 2537A, 1130, and 1135). A survey of Hg 0 concentrations at various locations within YNP showed that concentrations generally reflect global background concentrations of 1.5–2.0 ng m − 3 , but a few specific locations associated with concentrated geothermal activity showed distinctly elevated Hg 0 concentrations (about 9.0 ng m − 3 ). At the site of intensive study located centrally in YNP (Canyon Village), Hg 0 concentrations did not exceed 2.5 ng m − 3 ; concentrations of RGM were generally below detection limits of 0.88 pg m − 3 and never exceeded 5 pg m − 3 . Concentrations of pHg ranged from below detection limits to close to 30 pg m −3 . RGM and pHg concentrations were not correlated with any criteria gases (SO 2 , NO x , O 3 ); however pHg was weakly correlated with the concentration of atmospheric particles. We investigated three likely sources of Hg at the intensive monitoring site: numerous geothermal features scattered throughout YNP, re-suspended soils, and wildfires near or in YNP. We examined relationships between the chemical properties of aerosols (as measured using real time, single particle mass spectrometry; aerosol time-of-flight mass spectrometer; ATOFMS) and concentrations of atmospheric pHg. Based on the presence of particles with distinct chemical signatures of the wildfires, and the absence of signatures associated with the other sources, we concluded that wildfires in the park were the main source of aerosols and associated pHg to our sampling site.

Science of the Total Environment↗
USGS2006

Application of artificial neural networks to assess pesticide contamination in shallow groundwater

In this study, a feed-forward back-propagation neural network (BPNN) was developed and applied to predict pesticide concentrations in groundwater monitoring wells. Pesticide concentration data are challenging to analyze because they tend to be highly censored. Input data to the neural network included the categorical indices of depth to aquifer material, pesticide leaching class, aquifer sensitivity to pesticide contamination, time (month) of sample collection, well depth, depth to water from land surface, and additional travel distance in the saturated zone (i.e., distance from land surface to midpoint of well screen). The output of the neural network was the total pesticide concentration detected in the well. The model prediction results produced good agreements with observed data in terms of correlation coefficient (R = 0.87) and pesticide detection efficiency (E = 89%), as well as good match between the observed and predicted "class" groups. The relative importance of input parameters to pesticide occurrence in groundwater was examined in terms of R, E, mean error (ME), root mean square error (RMSE), and pesticide occurrence "class" groups by eliminating some key input parameters to the model. Well depth and time of sample collection were the most sensitive input parameters for predicting the pesticide contamination potential of a well. This infers that wells tapping shallow aquifers are more vulnerable to pesticide contamination than those wells tapping deeper aquifers. Pesticide occurrences during post-application months (June through October) were found to be 2.5 to 3 times higher than pesticide occurrences during other months (November through April). The BPNN was used to rank the input parameters with highest potential to contaminate groundwater, including two original and five ancillary parameters. The two original parameters are depth to aquifer material and pesticide leaching class. When these two parameters were the only input parameters for the BPNN, they were not able to predict contamination potential. However, when they were used with other parameters, the predictive performance efficiency of the BPNN in terms of R, E, ME, RMSE, and pesticide occurrence "class" groups increased. Ancillary data include data collected during the study such as well depth and time of sample collection. The BPNN indicated that the ancillary data had more predictive power than the original data. The BPNN results will help researchers identify parameters to improve maps of aquifer sensitivity to pesticide contamination. ?? 2006 Elsevier B.V. All rights reserved.

Science of the Total Environment↗
USGS2006

Mobilization of lead and other trace elements following shock chlorination of wells

Many owners of domestic wells shock chlorinate their wells to treat for bacterial contamination or control bad odors from sulfides. Analysis of well water with four wells from Fallon, Nevada, showed that following recommended procedures for shock chlorinating wells can cause large, short-lasting increases in trace-element concentrations in ground water, particularly for Cu, Fe, Pb, and Zn. Lead concentrations increased up to 745 fold between samples collected just before the well was shock chlorinated and the first sample collected 22-24??h later; Zn concentrations increased up to 252 fold, Fe concentrations increased up to 114 fold, and Cu concentrations increased up to 29 fold. Lead concentrations returned to near background levels following pumping of about one casing volume, however, in one well an estimated 120??mg of excess Pb were pumped before concentrations returned to prechlorination levels. Total Pb concentrations were much greater than filtered (0.45????m) concentrations, indicating the excess Pb is principally particulate. Recommended procedures for purging treated wells following shock chlorination may be ineffective because a strong NaOCl solution can remain in the casing above the pump even following extended pumping. Only small changes in gross alpha and beta radioactivity occurred following shock chlorination. USEPA has not promulgated drinking-water standards for 210Pb, however, measured 210Pb activities in the study area typically were less than the Canadian Maximum Acceptable Concentration of 100??mBq/L. By consuming well water shortly after shock chlorination the public may inadvertently be exposed to levels of Pb, and possibly 210Pb, that exceed drinking-water standards.

Science of the Total Environment↗
USGS2006

Occurrence of organic wastewater compounds in effluent-dominated streams in Northeastern Kansas

Fifty-nine stream-water samples and 14 municipal wastewater treatment facility (WWTF) discharge samples in Johnson County, northeastern Kansas, were analyzed for 55 compounds collectively described as organic wastewater compounds (OWCs). Stream-water samples were collected upstream, in, and downstream from WWTF discharges in urban and rural areas during base-flow conditions. The effect of secondary treatment processes on OWC occurrence was evaluated by collecting eight samples from WWTF discharges using activated sludge and six from WWTFs samples using trickling filter treatment processes. Samples collected directly from WWTF discharges contained the largest concentrations of most OWCs in this study. Samples from trickling filter discharges had significantly larger concentrations of many OWCs (p-value < 0.05) compared to samples collected from activated sludge discharges. OWC concentrations decreased significantly in samples from WWTF discharges compared to stream-water samples collected from sites greater than 2000??m downstream. Upstream from WWTF discharges, base-flow samples collected in streams draining predominantly urban watersheds had significantly larger concentrations of cumulative OWCs (p-value = 0.03), caffeine (p-value = 0.01), and tris(2-butoxyethyl) phosphate (p-value < 0.01) than those collected downstream from more rural watersheds.

Science of the Total Environment↗
USGS2007

Factors to consider for trace element deposition biomonitoring surveys with lichen transplants

A trace element deposition biomonitoring experiment with transplants of the fruticose lichen Evernia prunastri was developed, aimed at monitoring the effects of different exposure parameters (exposure orientation and direct rain) and to the elements Ti, V, Cr, Co, Cu, Zn, Rb, Cd, Sb and Pb. Accumulations were observed for most of the elements, confirming the ability of Evernia transplants for atmospheric metal deposition monitoring. The accumulation trends were mainly affected by the exposure orientation and slightly less so by the protection from rain. The zonation of the trace elements inside the thallus was also studied. It was concluded that trace element concentrations were not homogeneous in Evernia, thus imposing some cautions on the sampling approach. A nuclear microprobe analysis of an E. prunastri transplanted thallus in thin cross-sections concluded that the trace elements were mainly concentrated on the cortex of the thallus, except Zn, Ca and K which were also present in the internal layers. The size of the particles deposited or entrapped on the cortex surface averaged 7????m. A list of key parameters to ensure the comparability of surveys aiming at observing temporal or spatial deposition variation is presented. ?? 2006 Elsevier B.V. All rights reserved.

Tête Ronde, Gif-sur-Yvette↗
USGS2007

Age and trophic position dominate bioaccumulation of mercury and organochlorines in the food web of Lake Washington

Understanding the mechanisms of bioaccumulation in food webs is critical to predicting which food webs are at risk for higher rates of bioaccumulation that endanger the health of upper-trophic predators, including humans. Mercury and organochlorines were measured concurrently with stable isotopes of nitrogen and carbon in key fishes and invertebrates of Lake Washington to explore important pathways of bioaccumulation in this food web. Across the food web, age and trophic position together were highly significant predictors of bioaccumulation. Trophic position was more important than age for predicting accumulation of mercury, ???DDT, and ???-chlordane, whereas age was more important than trophic position for predicting ???PCB. Excluding age from the analysis inflated the apparent importance of trophic position to bioaccumulation for all contaminants. Benthic and pelagic habitats had similar potential to bioaccumulate contaminants, although higher ???-chlordane concentrations in organisms were weakly associated with more benthic carbon signals. In individual fish species, contaminant concentrations increased with age, size, and trophic position (??15N), whereas relationships with carbon source (??13C) were not consistent. Lipid concentrations were correlated with contaminant concentrations in some but not all fishes, suggesting that lipids were not involved mechanistically in bioaccumulation. Contaminant concentrations in biota did not vary among littoral sites. Collectively, these results suggest that age may be an important determinant of bioaccumulation in many food webs and could help explain a significant amount of the variability in apparent biomagnification rates among food webs. As such, effort should be made when possible to collect information on organism age in addition to stable isotopes when assessing food webs for rates of biomagnification. ?? 2006 Elsevier B.V. All rights reserved.

Science of the Total Environment↗
USGS2007

Persistence of pharmaceuticals and other organic compounds in chlorinated drinking water as a function of time

Ninety eight pharmaceuticals and other organic compounds (POOCs) that were amended to samples of chlorinated drinking-water were extracted and analyzed 1, 3, 6, 8, and 10 days after amendment to determine whether the total chlorine residual reacted with the amended POOCs in drinking water in a time frame similar to the residence time of drinking water in a water distribution system. Results indicated that if all 98 were present in the finished drinking water from a drinking-water treatment plant using free chlorine at 1.2 mg/L as the distribution system disinfectant residual, 52 POOCs would be present in the drinking water after 10 days at approximately the same concentration as in the newly finished drinking water. Concentrations of 16 POOCs would be reduced by 32% to 92%, and 22 POOCs would react completely with residual chlorine within 24 h. Thus, the presence of free chlorine residual is an effective means for transforming some POOCs during distribution.

Science of the Total Environment↗
USGS2007

Diel mercury-concentration variations in streams affected by mining and geothermal discharge

Diel variations of concentrations of unfiltered and filtered total Hg and filtered methyl Hg were documented during 24-h sampling episodes in water from Silver Creek, which drains a historical gold-mining district near Helena, Montana, and the Madison River, which drains the geothermal system of Yellowstone National Park. The concentrations of filtered methyl Hg had relatively large diel variations (increases of 68 and 93% from morning minima) in both streams. Unfiltered and filtered (0.1-μm filtration) total Hg in Silver Creek had diel concentration increases of 24% and 7%, respectively. In the Madison River, concentrations of unfiltered and filtered total Hg did not change during the sampling period. The concentration variation of unfiltered total Hg in Silver Creek followed the diel variation in suspended-particle concentration. The concentration variation of filtered total and methyl Hg followed the solar photocycle, with highest concentrations during the early afternoon and evening and lowest concentrations during the morning. None of the diel Hg variations correlated with diel variation in streamflow or major ion concentrations. The diel variation in filtered total Hg could have been produced by adsorption–desorption of Hg 2+ or by reduction of Hg(II) to Hg 0 and subsequent evasion of Hg 0 . The diel variation in filtered methyl Hg could have been produced by sunlight- and temperature-dependent methylation. This study is the first to examine diel Hg cycling in streams, and its results reinforce previous conclusions that diel trace-element cycling in streams is widespread but often not recognized and that parts of the biogeochemical Hg cycle respond quickly to the daily photocycle.

Montana↗
USGS2007

Arsenic attenuation by oxidized aquifer sediments in Bangladesh

Recognition of arsenic (As) contamination of shallow fluvio-deltaic aquifers in the Bengal Basin has resulted in increasing exploitation of groundwater from deeper aquifers that generally contain low concentrations of dissolved As. Pumping-induced infiltration of high-As groundwater could eventually cause As concentrations in these aquifers to increase. This study investigates the adsorption capacity for As of sediment from a low-As aquifer near Dhaka, Bangladesh. A shallow, chemically-reducing aquifer at this site extends to a depth of 50 m and has maximum As concentrations in groundwater of 900 μg/L. At depths greater than 50 m, geochemical conditions are more oxidizing and groundwater has < 5 μg/L As. There is no thick layer of clay at this site to inhibit vertical transport of groundwater. Arsenite [As(III)] is the dominant oxidation state in contaminated groundwater; however, data from laboratory batch experiments show that As(III) is oxidized to arsenate [As(V)] by manganese (Mn) minerals that are present in the oxidized sediment. Thus, the long-term viability of the deeper aquifers as a source of water supply is likely to depend on As(V) adsorption. The adsorption capacity of these sediments is a function of the oxidation state of As and the concentration of other solutes that compete for adsorption sites. Arsenite that was not oxidized did adsorb, but to a much lesser extent than As(V). Phosphate (P) caused a substantial decrease in As(V) adsorption. Increasing pH and concentrations of silica (Si) had lesser effects on As(V) adsorption. The effect of bicarbonate (HCO 3 ) on As(V) adsorption was negligible. Equilibrium constants for adsorption of As(V), As(III), P, Si, HCO 3 , and H were determined from the experimental data and a quantitative model developed. Oxidation of As(III) was modeled with a first-order rate constant. This model was used to successfully simulate As(V) adsorption in the presence of multiple competing solutes. Results from these experiments show that oxidized sediments have a substantial but limited capacity for removal of As from groundwater.

Dhaka↗