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At least 1,189 records · Page 66Linked to original sources
USGS1999

Are shifts in herbicide use reflected in concentration changes in Midwestern rivers?

In many Midwestern rivers, elevated concentrations of herbicides occur during runoff events for 1-3 months following application. The highest or 'peak' herbicide concentration often occurs during one of these runoff events. Herbicide concentrations in rivers are affected by a number of factors, including herbicide use patterns within the associated basin. Changing agricultural practices, reductions in recommended and permitted herbicide applications, shifts to new herbicides, and greater environmental awareness in the agricultural community have resulted in changes to herbicide use patterns. In the Midwestern United States, alachlor use was much larger in 1989 than in 1995, while acetochlor was not used in 1989, and commonly used in 1995. Use of atrazine, cyanazine, and metolachlor was about the same in 1989 and 1995. Herbicide concentrations were measured in samples from 53 Midwestern rivers during the first major runoff event that occurred after herbicide application (postapplication) in 1989, 1990, 1994, and 1995. The median concentrations of atrazine, alachlor, cyanazine, metribuzin, metolachlor, propazine, and simazine all were significantly higher in 1989/90 than in 1994/95. The median acetochlor concentration was higher in 1995 than in 1994. Estimated daily yields for all herbicides and degradation products measured, with the exception of acetochlor, were higher in 1989/90 than in 1994/95. The differences in concentration and yield do not always parallel changes in herbicide use, suggesting that other changes in herbicide or crop management are affecting concentrations in Midwestern rivers during runoff events.In many Midwestern rivers, elevated concentrations of herbicides occur during runoff events for 1-3 months following application. The highest or `peak' herbicide concentration often occurs during one of these runoff events. Herbicide concentrations in rivers are affected by a number of factors, including herbicide use patterns within the associated basin. Changing agricultural practices, reductions in recommended and permitted herbicide applications, shifts to new herbicides, and greater environmental awareness in the agricultural community have resulted in changes to herbicide use patterns. In the Midwestern United States, alachlor use was much larger in 1989 than in 1995, while acetochlor was not used in 1989, and commonly used in 1995. Use of atrazine, cyanazine, and metolachlor was about the same in 1989 and 1995. Herbicide concentrations were measured in samples from 53 Midwestern rivers during the first major runoff event that occurred after herbicide application (postapplication) in 1989, 1990, 1994, and 1995. The median concentrations of atrazine, alachlor, cyanazine, metribuzin, metolachlor, propazine, and simazine all were significantly higher in 1989/90 than in 1994/95. The median acetochlor concentration was higher in 1995 than in 1994. Estimated daily yields for all herbicides and degradation products measured, with the exception of acetochlor, were higher in 1989/90 than in 1994/95. The differences in concentration and yield do not always parallel changes in herbicide use, suggesting that other changes in herbicide or crop management are affecting concentrations in Midwestern rivers during runoff events.

Environmental Science & Technology↗
USGS2000

Effect of a constructed wetland on disinfection byproducts: Removal processes and production of precursors

The fate of halogenated disinfection byproducts (DBPs) in treatment wetlands and the changes in the DBP formation potential as wastewater treatment plant (WWTP)-derived water moves through the wetlands were investigated. Wetland inlet and outlet samples were analyzed for total organic halide (TOX), trihalomethanes (TH M), haloacetic acids (HAA), dissolved organic carbon (DOC), and UV absorbance. Removal of DBPs by the wetland ranged from 13 to 55% for TOX, from 78 to 97% for THM, and from 67 to 96% for HAA. The 24-h and 7-day nonpurgeable total organic halide (NPTOX), THM, and HAA formation potential yields were determined at the inlet and outlet of these wetlands. The effect of wetlands on the production of DBP precursors and their DBP-formation potential yield from wastewater was dramatic. The wetlands increased DBP yield up to a factor of almost 30. Specific changes in the DOC precursors were identified using 13C NMR spectroscopy.The fate of halogenated disinfection byproducts (DBPs) in treatment wetlands and the changes in the DBP formation potential as wastewater treatment plant (WWTP)-derived water moves through the wetlands were investigated. Wetland inlet and outlet samples were analyzed for total organic halide (TOX), trihalomethanes (THM), haloacetic acids (HAA), dissolved organic carbon (DOC), and UV absorbance. Removal of DBPs by the wetland ranged from 13 to 55% for TOX, from 78 to 97% for THM, and from 67 to 96% for HAA. The 24-h and 7-day nonpurgeable total organic halide (NPTOX), THM, and HAA formation potential yields were determined at the inlet and outlet of these wetlands. The effect of wetlands on the production of DBP precursors and their DBP-formation potential yield from wastewater was dramatic. The wetlands increased DBP yield up to a factor of almost 30. Specific changes in the DOC precursors were identified using 13C NMR spectroscopy.

Environmental Science & Technology↗
USGS1999

Modelling removal mechanisms of Pb, Cu, Zn and Cd in acidic groundwater during the neutralization by ambient surface and ground waters

Removal of Pb, Cu, Zn, and Cd during neutralization of acid rock drainage is examined using model simulations of field conditions and laboratory experiments involving mixing of natural drainage and surface waters or groundwaters. The simulations consider sorption onto hydrous Fe and Al oxides and particulate organic carbon, mineral precipitation, and organic and inorganic solution complexation of metals for two physical systems where newly formed oxides and particulate organic matter are either transported or retained along the chemical pathway. The calculations indicate that metal removal is a strong function of the physical system. Relative to direct discharge of ARD into streams, lower metal removals are observed where ARD enters streamwaters during the latter stages of neutralization by ambient groundwater after most of the Fe has precipitated and been retained in the soils. The mixing experiments, which represent the field simulations, also demonstrated the importance of dissolved metal to particle Fe ratios in controlling dissolved metal removal along the chemical pathway. Finally, model calculations indicate that hydrous Fe oxides and particulate organic carbon are more important than hydrous Al oxides in removing metals and that both inorganic and organic complexation must be considered when modeling metal removal from aquatic systems that are impacted by sulfide oxidation.

Environmental Science & Technology↗
USGS1999

Using imaging spectroscopy to map acidic mine waste

The process of pyrite oxidation at the surface of mine waste may produce acidic water that is gradually neutralized as it drains away from the waste, depositing different Fe-bearing secondary minerals in roughly concentric zones that emanate from mine-waste piles. These Fe-bearing minerals are indicators of the geochemical conditions under which they form. Airborne and orbital imaging spectrometers can be used to map these mineral zones because each of these Fe-bearing secondary minerals is spectrally unique. In this way, imaging spectroscopy can be used to rapidly screen entire mining districts for potential sources of surface acid drainage and to detect acid producing minerals in mine waste or unmined rock outcrops. Spectral data from the AVIRIS instrument were used to evaluate mine waste at the California Gulch Superfund Site near Leadville, CO. Laboratory leach tests of surface samples show that leachate pH is most acidic and metals most mobile in samples from the inner jarosite zone and that leachate pH is near-neutral and metals least mobile in samples from the outer goethite zone.

Environmental Science & Technology↗
USGS1999

Spectroscopic confirmation of uranium(VI)-carbonato adsorption complexes on hematite

Evaluating societal risks posed by uranium contamination from waste management facilities, mining sites, and heavy industry requires knowledge about uranium transport in groundwater, often the most significant pathway of exposure to humans. It has been proposed that uranium mobility in aquifers may be controlled by adsorption of U(VI)−carbonato complexes on oxide minerals. The existence of such complexes has not been demonstrated, and little is known about their compositions and reaction stoichiometries. We have used attenuated total reflectance Fourier transform infrared (ATR-FTIR) and extended X-ray absorption fine structure (EXAFS) spectroscopies to probe the existence, structures, and compositions of ≡FeO surface −U(VI)−carbonato complexes on hematite throughout the pH range of uranyl uptake under conditions relevant to aquifers. U(VI)−carbonato complexes were found to be the predominant adsorbed U(VI) species at all pH values examined, a much wider pH range than previously postulated based on analogy to aqueous U(VI)−carbonato complexes, which are trace constituents at pH < 6. This result indicates the inadequacy of the common modeling assumption that the compositions and predominance of adsorbed species can be inferred from aqueous species. By extension, adsorbed carbonato complexes may be of major importance to the groundwater transport of similar actinide contaminants such as neptunium and plutonium.

Environmental Science & Technology↗
USGS1999

Trace-element concentrations in streambed sediment across the conterminous United States

Trace-element concentrations in 541 streambed-sediment samples collected from 20 study areas across the conterminous United States were examined as part of the National Water-Quality Assessment Program of the U.S. Geological Survey. Sediment samples were sieved and the <63-μm fraction was retained for determination of total concentrations of trace elements. Aluminum, iron, titanium, and organic carbon were weakly or not at all correlated with the nine trace elements examined: arsenic, cadmium, chromium, copper, lead, mercury, nickel, selenium, and zinc. Four different methods of accounting for background/baseline concentrations were examined; however, normalization was not required because field sieving removed most of the background differences between samples. The sum of concentrations of trace elements characteristic of urban settings - copper, mercury, lead, and zinc - was well correlated with population density, nationwide. Median concentrations of seven trace elements (all nine examined except arsenic and selenium) were enriched in samples collected from urban settings relative to agricultural or forested settings. Forty-nine percent of the sites sampled in urban settings had concentrations of one or more trace elements that exceeded levels at which adverse biological effects could occur in aquatic biota.

Environmental Science & Technology↗
USGS1999

Aerobic mineralization of MTBE and tert-butyl alcohol by stream-bed sediment microorganisms

Microorganisms indigenous to the stream-bed sediments at two gasoline- contaminated groundwater sites demonstrated significant mineralization of the fuel oxygenates, methyl tert-butyl ether (MTBE) and tert-butyl alcohol (TBA). Up to 73% of [U-14C]-MTBE and 84% of [U-14C]-TBA were degraded to 14CO2 under mixed aerobic/anaerobic conditions. No significant mineralization was observed under strictly anaerobic conditions. The results indicate that, under the mixed aerobic/anaerobic conditions characteristic of stream-bed sediments, microbial processes may provide a significant environmental sink for MTBE and TBA delivered to surface water bodies by contaminated groundwater or by other sources.Microorganisms indigenous to the stream-bed sediments at two gasoline-contaminated groundwater sites demonstrated significant mineralization of the fuel oxygenates, methyl tert-butyl ether (MTBE) and tert-butyl alcohol (TBA). Up to 73% of [U-14C]-MTBE and 84% of [U-14C]-TBA were degraded to 14CO2 under mixed aerobic/anaerobic conditions. No significant mineralization was observed under strictly anaerobic conditions. The results indicate that, under the mixed aerobic/anaerobic conditions characteristic of stream-bed sediments, microbial processes may provide a significant environmental sink for MTBE and TBA delivered to surface water bodies by contaminated groundwater or by other sources.

Environmental Science & Technology↗
USGS2000

Selenium stable isotope ratios as indicators of sources and cycling of selenium: Results from the northern reach of San Francisco Bay

Selenium stable isotope ratios can serve as indicators of Se sources and reduction of Se oxyanions, much as sulfur and nitrogen isotope ratios do in sulfur and nitrogen biogeochemical studies. A new analytical method, which allows precise Se isotope ratio measurements on 500 ng of Se, greatly enhances analysis of environmental samples. This paper presents the first environmental study to use Se stable isotopes. 80Se/76Se ratios, relative to a provisional standard, were measured in water, oil refinery wastewater, total sediment digest, and sediment extracts from the Carquinez area in the San Francisco Bay Estuary, Se isotope ratios in total sediment Se and in extracts designed to recover Se0 are slightly (about 2???) enriched in the lighter isotope relative to local bay water Se. This difference is smaller than the isotopic fractionations expected upon reduction of Se(VI) or Se(IV) to Se(0) and suggests that reduction of soluble selenium from the overlying waters is not the dominant process by which Se is incorporated into the sediments. Consistent isotopic differences between riverine and refinery inputs were not observed, and thus tracing of refinery inputs with Se isotopes is not possible in this system.Selenium stable isotope ratios can serve as indicators of Se sources and reduction of Se oxyanions, much as sulfur and nitrogen isotope ratios do in sulfur and nitrogen biogeochemical studies. A new analytical method, which allows precise Se isotope ratio measurements on 500 ng of Se, greatly enhances analysis of environmental samples. This paper presents the first environmental study to use Se stable isotopes. 80Se/76Se ratios, relative to a provisional standard, were measured in water, oil refinery wastewater, total sediment digests, and sediment extracts from the Carquinez area in the San Francisco Bay Estuary. Se isotope ratios in total sediment Se and in extracts designed to recover Se0 are slightly (about 2 per mil) enriched in the lighter isotope relative to local bay water Se. This difference is smaller than the isotopic fractionations expected upon reduction of Se(VI) or Se(IV) to Se(0) and suggests that reduction of soluble selenium from the overlying waters is not the dominant process by which Se is incorporated into the sediments. Consistent isotopic differences between riverine and refinery inputs were not observed, and thus tracing of refinery inputs with Se isotopes is not possible in this system.

Environmental Science & Technology↗
USGS1999

Bioassessment of mercury, cadmium, polychlorinated biphenyls, and pesticides in the upper Mississippi river with Zebra mussels (Dreissena polymorpha)

Zebra mussels ( Dreissena polymorpha ) were sampled from artificial substrates deployed from May 30 to October 19, 1995, at 19 locks and dams from Minneapolis, MN, to Muscatine, IA. Analyses of composite tissue samples of zebra mussels (10−20-mm length) revealed accumulation of mercury (Hg), cadmium (Cd), and polychlorinated biphenyls (PCBs) during a 143-d exposure period. Concentrations of total Hg ranged from 2.6 to 6.1 ng/g wet weight and methylmercury (CH 3 Hg) from 1.0 to 3.3 ng/g wet weight. About 50% (range 30−70%) of the mean total Hg in zebra mussels was CH 3 Hg. Cadmium ranged from 76 to 213 ng/g wet weight. Concentrations of total PCBs (Aroclor 1254) in zebra mussels varied longitudinally (range 1000−7330 ng/g lipid weight), but the composition of PCB congeners (total of 21 measured) was similar throughout the river. Chlordane and dieldrin were the only two pesticides detected of the 15 analyzed. Zebra mussels are sentinels of contaminant bioavailability in the Upper Mississippi River and may be an important link in the trophic transfer of contaminants in the river because of their increasing importance in the diets of certain fish and waterfowl.

Illinois, Iowa, Minnesota, Missouri, Wisconsin↗
USGS2000

Sorption of selected organic compounds from water to a peat soil and its humic-acid and humin fractions: Potential sources of the sorption nonlinearity

The sorption isotherms of ethylene dibromide (EDB), diuron (DUN), and 3,5-dichlorophenol (DCP) from water on the humic acid and humin fractions of a peat soil and on the humic-acid of a muck soil have been measured. The data were compared with those of the solutes with the whole peat from which the humic-acid (HA) and humin (HM) fractions were derived and on which the sorption of the solutes exhibited varying extents of nonlinear capacities at low relative concentrations (C(e)/S(w)). The HA fraction as prepared by the density-fractionated method is relatively pure and presumably free of high- surface-area carbonaceous material (HSACM) that is considered to be responsible for the observed nonlinear sorption for nonpolar solutes (e.g., EDB) on the peat; conversely, the base-insoluble HM fraction as prepared is presumed to be enriched with HSACM, as manifested by the greatly higher BET- (N2) surface area than that of the whole peat. The sorption of EDB on HA exhibits no visible nonlinear effect, whereas the sorption on HM shows an enhanced nonlinearity over that on the whole peat. The sorption of polar DUN and DCP on HA and HM display nonlinear effects comparable with those on the whole peat; the effects are much more significant than those with nonpolar EDB. These results conform to the hypothesis that adsorption onto a small amount of strongly adsorbing HSACM is largely responsible for the nonlinear sorption of nonpolar solutes on soils and that additional specific interactions with the active groups of soil organic matter are responsible for the generally higher nonlinear sorption of the polar solutes.

Environmental Science & Technology↗
USGS1999

The urban environmental gradient: Anthropogenic influences on the spatial and temporal distributions of lead and zinc in sediments

U rban settings are a focal point for environmental contamination due to emissions from industrial and municipal activities and the widespread use of motor vehicles. As part of the National Water-Quality Assessment Program of the U.S. Geological Survey, streambed-sediment and dated reservoir-sediment samples were collected from the Chattahoochee River Basin and analyzed for total lead (Pb) and zinc (Zn) concentrations. The sampling transect extends from northern Georgia, through Atlanta, to the Gulf of Mexico and reflects a steep gradient in population density from nearly 1000 people/km 2 in the Atlanta Metropolitan Area to fewer than 50 people/km 2 in rural areas of southern Georgia and northern Florida. Correlations among population density, traffic density, and total and anthropogenic Pb and Zn concentrations indicate that population density is strongly related to traffic density and is a predictor of Pb and Zn concentrations in the environment derived from anthropogenic activities. Differences in the distributions of total Pb and Zn concentrations along the urban−suburban−rural gradient from Atlanta to the Florida Panhandle are related to temporal and spatial processes. That is, with the removal of leaded gasoline starting in the late 1970s, peak Pb concentrations have decreased to the present. Conversely, increased vehicular usage has kept Zn concentrations elevated in runoff from population centers, which is reflected in the continued enrichment of Zn in aquatic sediments. Sediments from rural areas also contain elevated concentrations of Zn, possibly in response to substantial power plant emissions for the region, as well as vehicular traffic.

Georgia, Florida↗
USGS1999

Variation in net trophic transfer efficiencies among 21 PCB congeners

We tested the hypothesis that the efficiency with which fish retain polychlorinated biphenyl (PCB) congeners from their food strongly depends on K ow and degree of chlorination of the congener. We used diet information, determinations of concentrations of individual PCB congeners in both coho salmon ( Oncorhynchus kisutch ) and their prey, and bioenergetics modeling to estimate the efficiencies with which Lake Michigan coho salmon retain various PCB congeners from their food. The retention efficiency for the tetrachloro congeners averaged 38%, whereas retention efficiencies for higher chlorinated congeners ranged from 43 to 56%. Not including tetrachloro congeners, we found neither decreasing nor increasing trends in the efficiencies with which the coho salmon retained the PCB congeners from their food with either increasing K ow or increasing degree of chlorination of the PCB congeners. We concluded that (a) for PCB congeners with 5&minus;8 chlorine atoms/molecule, K ow and degree of chlorination had little influence on the efficiency with which coho salmon retained the various PCB congeners in their food, and (b) the efficiency with which coho salmon retained tetrachloro PCB congeners in their food appeared to be slightly lower than that for higher chlorinated PCB congeners.

Environmental Science & Technology↗
USGS1999

Role for acetotrophic methanogens in methanogenic biodegradation of vinyl chloride

Under methanogenic conditions, stream-bed sediment microorganisms rapidly degraded [1,2-14C]vinyl chloride to 14CH4 and 14CO2. Amendment with 2-bromoethanesulfonic acid eliminated 14CH4 production and decreased 14CO2 recovery by an equal molar amount. Results obtained with [14C]ethene, [14C]acetate, or 14CO2 as substrates indicated that acetotrophic methanogens were responsible for the production of 14CH4 during biodegradation of [1,2-14C]VC.Under methanogenic conditions, stream-bed sediment microorganisms rapidly degraded [1,2-14C]vinyl chloride to 14CH4 and 14CO2. Amendment with 2-bromoethanesulfonic acid eliminated 14CH4 production and decreased 14CO2 recovery by an equal molar amount. Results obtained with [14C]-ethene, [14C]acetate, or 14CO2 as substrates indicated that acetotrophic methanogens were responsible for the production of 14CH4, during biodegradation of [1,2-14C]VC.

Environmental Science & Technology↗
USGS1999

Determination of uptake kinetics (sampling rates) by lipid-containing semipermeable membrane devices (SPMDs) for polycyclic aromatic hydrocarbons (PAHs) in water

The use of lipid-containing semipermeable membrane devices (SPMDs) is becoming commonplace, but very little sampling rate data are available for the estimation of ambient contaminant concentrations from analyte levels in exposed SPMDs. We determined the aqueous sampling rates (R(s)s; expressed as effective volumes of water extracted daily) of the standard (commercially available design) 1-g triolein SPMD for 15 of the priority pollutant (PP) polycyclic aromatic hydrocarbons (PAHs) at multiple temperatures and concentrations. Under the experimental conditions of this study, recovery- corrected R(s) values for PP PAHs ranged from ???1.0 to 8.0 L/d. These values would be expected to be influenced by significant changes (relative to this study) in water temperature, degree of biofouling, and current velocity- turbulence. Included in this paper is a discussion of the effects of temperature and octanol-water partition coefficient (K(ow)); the impacts of biofouling and hydrodynamics are reported separately. Overall, SPMDs responded proportionally to aqueous PAH concentrations; i.e., SPMD R(s) values and SPMD-water concentration factors were independent of aqueous concentrations. Temperature effects (10, 18, and 26 ??C) on Rs values appeared to be complex but were relatively small.The use of lipid-containing semipermeable membrane devices (SPMDs) is becoming commonplace, but very little sampling rate data are available for the estimation of ambient contaminant concentrations from analyte levels in exposed SPMDs. We determined the aqueous sampling rates (Rss; expressed as effective volumes of water extracted daily) of the standard (commercially available design) 1-g triolein SPMD for 15 of the priority pollutant (PP) polycyclic aromatic hydrocarbons (PAHs) at multiple temperatures and concentrations. Under the experimental conditions of this study, recovery-corrected Rs values for PP PAHs ranged from ???1.0 to 8.0 L/d. These values would be expected to be influenced by significant changes (relative to this study) in water temperature, degree of biofouling, and current velocity-turbulence. Included in this paper is a discussion of the effects of temperature and octanol-water partition coefficient (KOW); the impacts of biofouling and hydrodynamics are reported separately. Overall, SPMDs responded proportionally to aqueous PAH concentrations; i.e., SPMD RS values and SPMD-water concentration factors were independent of aqueous concentrations. Temperature effects (10, 18, and 26??C) on RS values appeared to be complex but were relatively small.

Environmental Science & Technology↗
USGS1999

Inhibition of hydroxyl radical reaction with aromatics by dissolved natural organic matter

Reaction of aromatic compounds with hydroxyl radical is inhibited by dissolved natural organic matter (NOM). The degree of inhibition is significantly greater than that expected based on a simple model in which aromatic compound molecules bound to NOM are considered to be unreactive. In this study, hydroxyl radical was produced at steady-state concentrations using Fenton chemistry (H2O2 + Fe2+ ??? Fe3+ + HO- + HO??). Suwannee River fulvic acid and humic acid were used as NOM. The most likely mechanism for the observed inhibition is that hydroxyl radical formation occurs in microenvironmental sites remote from the aromatic compounds. In addition to changes in kinetics, pyrene hydroxyl radical reaction also exhibited a mechanistic change in the presence of fulvic acid. The mechanism changed from a reaction that was apparently firstorder in pyrene to one that was apparently secondorder in pyrene, indicating that pyrene self-reaction may have become the dominant mechanism in the presence of fulvic acid. Dissolved NOM causes significant changes in the rate and mechanism of hydroxyl radical degradation of aromatic compounds. Consequently, literature rate constants measured in pure water will not be useful for predicting the degradation of pollutants in environmental systems. The kinetic and mechanistic information in this study will be useful for developing improved degradation methods involving Fenton chemistry.Reaction of aromatic compounds with hydroxyl radical is inhibited by dissolved natural organic matter (NOM). The degree of inhibition is significantly greater than that expected based on a simple model in which aromatic compounds molecules bounds to NOM are considered to be unreactive. In this study, hydroxyl radical was produced at steady-state concentrations using Fenton chemistry (H2O2 + Fe2+ ??? Fe3+ + HO- + HO??). Suwannee River fulvic acid and humic acid were used as NOM. The most likely mechanisms for the observed inhibition is that hydroxyl radical formation occurs in microenvironmental sites remote from the aromatic compounds. In addition to changes in kinetics, pyrene hydroxyl radical reaction also exhibited a mechanistic change in the presence of fulvic acid. The mechanism changed from a reaction that was apparently first-order in pyrene to one that was apparently second-order in pyrene, indicating that pyrene self-reaction may have become the dominant mechanism in the presence of fulvic acid. Dissolved NOM causes significant changes in the rate and mechanism of hydroxyl radical degradation of aromatic compounds. Consequently, literature rate constants measured in pure water will not be useful for predicting the degradation of pollutants in environmental systems. The kinetic and mechanistic information in this study will be useful for developing improved degradation methods involving Fenton chemistry.

Environmental Science & Technology↗
USGS1999

Negative pH and extremely acidic mine waters from Iron Mountain, California

Extremely acidic mine waters with pH values as low as -3.6, total dissolved metal concentrations as high as 200 g/L, and sulfate concentrations as high as 760 g/L, have been encountered underground in the Richmond Mine at Iron Mountain, CA. These are the most acidic waters known. The pH measurements were obtained by using the Pitzer method to define pH for calibration of glass membrane electrodes. The calibration of pH below 0.5 with glass membrane electrodes becomes strongly nonlinear but is reproducible to a pH as low as -4. Numerous efflorescent minerals were found forming from these acid waters. These extreme acid waters were formed primarily by pyrite oxidation and concentration by evaporation with minor effects from aqueous ferrous iron oxidation and efflorescent mineral formation.

Environmental Science & Technology↗
USGS2000

Anthropogenic platinum and palladium in the sediments of Boston Harbor

Anthropogenic activity has increased recent sediment concentrations of Pt and Pd in Boston Harbor by approximately 5 times background concentrations. Surface sediments and downcore profiles were investigated to evaluate Pt and Pd accumulation and behavior in urban coastal sediments. There is no clear correlation between temporal changes in Pt and Pd consumption and sediment concentration. However, Pt/Pb and Pd/Pb ratios suggest that Pt and Pd flux into the Harbor may not be decreasing with cessation of sludge input as rapidly as other metals. This is supported by the large discrepancy between fluxes associated with sludge and effluent release and those calculated from surface sediment concentrations. This evidence supports catalytic converters as a major source of Pd and Pt to Boston Harbor but cannot preclude other sources. Pd does not exhibit signs of post-burial remobilization below the mixed layer in the sediment cores, although near-surface variability in Pd concentrations may indicate a labile Pd component. Pt displays an inverse correlation with Mn above the oxic/suboxic transition, similar to behavior seen in pristine sediments where Pt is thought to be chemically mobile. This study does not support the use of Pd and Pt as tracers of recent contaminated sedimentation. However, the possibility of a labile Pt and Pd in these sediments highlights the need for further study of the biological uptake of these metals.

Environmental Science & Technology↗
USGS1999

Metolachlor and alachlor breakdown product formation patterns in aquatic field mesocosms

The transformation of metolachlor [2-chloro- N -(2-ethyl-6-methylphenyl)- N -(2-methoxy-1-methylethyl)acetamide] and alachlor [2-chloro- N -(2,6-diethylphenyl)- N -(methoxymethyl)acetamide] in aquatic systems was investigated using outdoor tank mesocosms. Metolachlor and alachlor levels and their ethane sulfonic acid (ESA) and oxanillic acid breakdown products were monitored over time under five experimental treatments (each in quadruplicate). Background water conditions were identical in all treatments with each treatment differing based on the level and type(s) of herbicide present. Treatments included a no-herbicide control, 10 μg/L metolachlor, 25 μg/L metolachlor, 25 μg/L alachlor, and 25 μg/L alachlor plus 25 μg/L metolachlor in combination. The experiment was initiated by adding herbicide(s) to the units to the target concentrations; herbicide and breakdown product levels and other chemical parameters were then monitored for 85 days. In general, metolachlor half-lives were longer than alachlor half-lives under all treatments, although the differences were not statistically significant. Metolachlor half-lives (±95% confidence limits) ranged from 33.0 d (±14.1 d) to 46.2 d (±40.0 d), whereas alachlor half-lives ranged from 18.7 d (±3.5 d) to 21.0 d (±6.5 d) for different treatments. Formation patterns of ESA were similar in all treatments, whereas oxanillic acid formation differed for the two herbicides. Alachlor oxanillic acid was produced in larger quantities than metolachlor oxanillic acid and either ESA under equivalent conditions. Our results suggest that the transformation pathways for alachlor and metolachlor in aquatic systems are similar and resemble the acetochlor pathway in soils proposed by Feng ( Pestic. Biochem. Physiol . 1991 , 34 , 136); however, the oxanillic acid branch of the pathway is favored for alachlor as compared with metolachlor.

Environmental Science & Technology↗