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Biodegradation of the surfactant linear alkylbenzenesulfonate in sewage-contaminated groundwater: A comparison of column experiments and field tracer tests

Transport and biodegradation of linear alkylbenzenesulfonate (LAS) in sewage-contaminated groundwater were investigated for a range of dissolved oxygen concentrations. Both laboratory column and an 80-day continuous injection tracer test field experiments were conducted. The rates of LAS biodegradation increased with increasing dissolved oxygen concentrations and indicated the preferential biodegradation of the longer alkyl chain LAS homologues (i.e., C12 and C13) and external isomers (i.e., 2-and 3- phenyl). However, for similar dissolved oxygen concentrations, mass removal rates for LAS generally were 2-3 times greater in laboratory column experiments than in the field tracer test. Under low oxygen conditions (<1 mg/L) only a fraction of the LAS mixture biodegraded in both laboratory and field experiments. Biodegradation rate constants for the continuous injection field test (0.002-0.08 day-1) were comparable to those estimated for a 3-h injection (pulsed) tracer test conducted under similar biogeochemical conditions, indicating that increasing the exposure time of aquifer sediments to LAS did not increase biodegradation rates.Transport and biodegradation of linear alkylbenzenesulfonate (LAS) in sewage-contaminated groundwater were investigated for a range of dissolved oxygen concentrations. Both laboratory column and an 80-day continuous injection tracer test field experiments were conducted. The rates of LAS biodegradation increased with increasing dissolved oxygen concentrations and indicated the preferential biodegradation of the longer alkyl chain LAS homologues (i.e., C12 and C13) and external isomers (i.e., 2- and 3-phenyl). However, for similar dissolved oxygen concentrations, mass removal rates for LAS generally were 2-3 times greater in laboratory column experiments than in the field tracer test. Under low oxygen conditions (<1 mg/L) only a fraction of the LAS mixture biodegraded in both laboratory and field experiments. Biodegradation rate constants for the continuous injection field test (0.002-0.08 day-1) were comparable to those estimated for a 3-h injection (pulsed) tracer test conducted under similar biogeochemical conditions, indicating that increasing the exposure time of aquifer sediments to LAS did not increase biodegradation rates.

Environmental Science & Technology↗

Bacteriophage PRD1 and silica colloid transport and recovery in an iron oxide-coated sand aquifer

Bacteriophage PRD1 and silica colloids were co-injected into sewage-contaminated and uncontaminated zones of an iron oxide-coated sand aquifer on Cape Cod, MA, and their transport was monitored over distances up to 6 m in three arrays. After deposition, the attached PRD1 and silica colloids were mobilized by three different chemical perturbations (elevated pH, anionic surfactant, and reductant). PRD1 and silica colloids experienced less attenuation in the contaminated zone where adsorbed organic matter and phosphate may be hindering attachment of PRD1 and silica colloids to the iron oxide coatings. The PRD1 collision efficiencies agree well with collision efficiencies predicted by assuming favorable PRD1 deposition on iron oxide coatings for which the surface area coverage was measured by microprobe analysis of sediment thin sections. ζ potentials of the PRD1, silica colloids, and aquifer grains corroborated the transport results, indicating that electrostatic forces dominated the attachment of PRD1 and silica colloids. Elevated pH was the chemical perturbation most effective at mobilizing the attached PRD1 and silica colloids. Elevated surfactant concentration mobilized the attached PRD1 and silica colloids more effectively in the contaminated zone than in the uncontaminated zone.

Environmental Science & Technology↗

Enhanced dissolution of cinnabar (mercuric sulfide) by dissolved organic matter isolated from the Florida Everglades

Organic matter isolated from the Florida Everglades caused a dramatic increase in mercury release (up to 35 μM total dissolved mercury) from cinnabar (HgS), a solid with limited solubility. Hydrophobic (a mixture of both humic and fulvic) acids dissolved more mercury than hydrophilic acids and other nonacid fractions of dissolved organic matter (DOM). Cinnabar dissolution by isolated organic matter and natural water samples was inhibited by cations such as Ca 2+ . Dissolution was independent of oxygen content in experimental solutions. Dissolution experiments conducted in DI water (pH = 6.0) had no detectable (<2.5 nM) dissolved mercury. The presence of various inorganic (chloride, sulfate, or sulfide) and organic ligands (salicylic acid, acetic acid, EDTA, or cysteine) did not enhance the dissolution of mercury from the mineral. Aromatic carbon content in the isolates (determined by 13 C NMR) correlated positively with enhanced cinnabar dissolution. ζ-potential measurements indicated sorption of negatively charged organic matter to the negatively charged cinnabar (pH pzc = 4.0) at pH 6.0. Possible mechanisms of dissolution include surface complexation of mercury and oxidation of surface sulfur species by the organic matter.

Florida↗

N2O emissions from a nitrogen-enriched river

Nitrous oxide (N2O) emissions from the South Platte River in Colorado were measured using closed chambers in the fall, winter, and summer of 1994- 1995. The South Platte River was enriched in inorganic N (9-800 ??M) derived from municipal wastewater effluent and groundwater return flows from irrigated agricultural fields. River water was as much as 2500% supersaturated with N2O, and median N2O emission rates from the river surface ranged from less than 90 to 32 600 ??g-N m-2 d-1. Seventy-nine percent of the variance in N2O emission rates was explained by concentrations of total inorganic N in river water and by water temperature. The estimated total annual N2O emissions from the South Platte River were 2 x 1013-6 x 1013 ??g-N yr-1. This amount of annual N2O emissions was similar to the estimated annual N2O emissions from all primary municipal wastewater treatment processes in the United States (1). Results from this study indicate that N-enriched rivers could be important anthropogenic sources of N2O to the atmosphere. However, N2O emission measurements from other N-enriched rivers are needed to better quantify this source.Nitrous oxide (N2O) emissions from the South Platte River in Colorado were measured using closed chambers in the fall, winter, and summer of 1994-1995. The South Platte River was enriched in inorganic N (9-800 ??M) derived from municipal wastewater effluent and groundwater return flows from irrigated agricultural fields. River water was as much as 2500% supersaturated with N2O, and median N2O emission rates from the river surface ranged from less than 90 to 32 600 ??g-N m-2 d-1. Seventy-nine percent of the variance in N2O emission rates was explained by concentrations of total inorganic N in river water and by water temperature. The estimated total annual N2O emissions from the South Platte River were 2??1013-6??1013 ??g-N yr-1. This amount of annual N2O emissions was similar to the estimated annual N2O emissions from all primary municipal wastewater treatment processes in the United States. Results from this study indicate that N-enriched rivers could be important anthropogenic sources of N2O to the atmosphere. However, N2O emission measurements from other N-enriched rivers are needed to better quantify this source.

Environmental Science & Technology↗

New method for the direct determination of dissolved Fe(III) concentration in acid mine waters

A new method for direct determination of dissolved Fe(III) in acid mine water has been developed. In most present methods, Fe(III) is determined by computing the difference between total dissolved Fe and dissolved Fe(II). For acid mine waters, frequently Fe(II) ≫ Fe(III); thus, accuracy and precision are considerably improved by determining Fe(III) concentration directly. The new method utilizes two selective ligands to stabilize Fe(III) and Fe(II), thereby preventing changes in Fe reduction−oxidation distribution. Complexed Fe(II) is cleanly removed using a silica-based, reversed-phase adsorbent, yielding excellent isolation of the Fe(III) complex. Iron(III) concentration is measured colorimetrically or by graphite furnace atomic absorption spectrometry (GFAAS). The method requires inexpensive commercial reagents and simple procedures that can be used in the field. Calcium(II), Ni(II), Pb(II), Al(III), Zn(II), and Cd(II) cause insignificant colorimetric interferences for most acid mine waters. Waters containing >20 mg of Cu/L could cause a colorimetric interference and should be measured by GFAAS. Cobalt(II) and Cr(III) interfere if their molar ratios to Fe(III) exceed 24 and 5, respectively. Iron(II) interferes when its concentration exceeds the capacity of the complexing ligand (14 mg/L). Because of the GFAAS elemental specificity, only Fe(II) is a potential interferent in the GFAAS technique. The method detection limit is 2 μg/L (40 nM) using GFAAS and 20 μg/L (0.4 μM) by colorimetry.

Environmental Science & Technology↗

Occurrence and behavior of the herbicide Prometon in the hydrologic system

Prometon, a triazine herbicide, is used for total vegetation control on industrial sites, on noncrop areas on farms, in and under asphalt, and to a small extent by homeowners. Prometon has often been detected in surface water and groundwater in studies reported in the literature, but its presence is seldom discussed, partly because of its infrequent inclusion on lists of herbicides used in either agricultural or urban areas. In recent large-scale studies by the U.S. Geological Survey, prometon has been the most commonly detected herbicide in surface water and groundwater in urban areas and the third and fourth most commonly detected herbicide in groundwater and surface water, respectively, in agricultural areas. It also has been detected in rain. The frequent detection of prometon in the environment is discussed in relation to its use practices and predicted environmental behavior. Prometon is compared to atrazine, a structurally similar agricultural triazine herbicide that is one of the most studied and most commonly detected herbicides found in the hydrologic environment. The environmental data presented here demonstrate the wide-scale occurrence of prometon in all components of the hydrologic system, particularly in the surface water and groundwater of urban areas.Prometon, a triazine herbicide, is used for total vegetation control on industrial sites, on noncrop areas on farms, in and under asphalt, and to a small extent by homeowners. Prometon has often been detected in surface water and groundwater in studies reported in the literature, but its presence is seldom discussed, partly because of its infrequent inclusion on lists of herbicides used in either agricultural or urban areas. In recent large-scale studies by the U.S. Geological Survey, prometon has been the most commonly detected herbicide in surface water and groundwater in urban areas and the third and fourth most commonly detected herbicide in groundwater and surface water, respectively, in agricultural areas. It also has been detected in rain. The frequent detection of prometon in the environment is discussed in relation to its use practices and predicted environmental behavior. Prometon is compared to atrazine, a structurally similar agricultural triazine herbicide that is one of the most studied and most commonly detected herbicides found in the hydrologic environment. The environmental data presented here demonstrate the wide-scale occurrence of prometon in all components of the hydrologic system, particularly in the surface water and groundwater of urban areas.

Environmental Science & Technology↗

Correlation of soil and sediment organic matter polarity to aqueous sorption of nonionic compounds

Polarities of the soiL/sediment organic matter (SOM) in 19 soil and 9 freshwater sediment sam pies were determined from solid-state 13C-CP/MAS NMR spectra and compared with published partition coefficients (K(oc)) of carbon tetrachloride (CT) from aqueous solution. Nondestructive analysis of whole samples by solid-state NMR permits a direct assessment of the polarity of SOM that is not possible by elemental analysis. The percent of organic carbon associated with polar functional groups was estimated from the combined fraction of carbohydrate and carboxylamide-ester carbons. A plot of the measured partition coefficients (K(oc)) of carbon tetrachloride (CT) vs. percent polar organic carbon (POC) shows distinctly different populations of soils and sediments as well as a roughly inverse trend among the soil/sediment populations. Plots of K(oc) values for CT against other structural group carbon fractions did not yield distinct populations. The results indicate that the polarity of SOM is a significant factor in accounting for differences in K(oc) between the organic matter in soils and sediments. The alternate direct correlation of the sum of aliphatic and aromatic structural carbons with K(oc) illustrates the influence of nonpolar hydrocarbon on solute partition interaction. Additional elemental analysis data of selected samples further substantiate the effect of the organic matter polarity on the partition efficiency of nonpolar solutes. The separation between soil and sediment samples based on percent POC reflects definite differences of the properties of soil and sediment organic matters that are attributable to diagenesis.Polarities of the soil/sediment organic matter (SOM) in 19 soil and 9 freshwater sediment samples were determined from solid-state 13C-CP/MAS NMR spectra and compared with published partition coefficients (Koc) of carbon tetrachloride (CT) from aqueous solution. Nondestructive analysis of whole samples by solid-state NMR permits a direct assessment of the polarity of SOM that is not possible by elemental analysis. The percent of organic carbon associated with polar functional groups was estimated from the combined fraction of carbohydrate and carboxyl-amide-ester carbons. A plot of the measured partition coefficients (Koc) of carbon tetrachloride (CT) vs. percent polar organic carbon (POC) shows distinctly different populations of soils and sediments as well as a roughly inverse trend among the soil/sediment populations. Plots of Koc values for CT against other structural group carbon fractions did not yield distinct populations. The results indicate that the polarity of SOM is a significant factor in accounting for differences in Koc between the organic matter in soils and sediments. The alternate direct correlation of the sum of aliphatic and aromatic structural carbons with Koc illustrates the influence of nonpolar hydrocarbon on solute partition interaction. Additional elemental analysis data of selected samples further substantiate the effect of the organic matter polarity on the partition efficiency of nonpolar solutes. The separation between soil and sediment samples based on percent POC reflects definite differences of the properties of soil and sediment organic matters that are attributable to diagenesis.

Environmental Science & Technology↗

Assessing the influence of reacting pyrite and carbonate minerals on the geochemistry of drainage in the Coeur d'Alene mining district

The relative abundance of minerals that react to generate or consume acid in mineralized areas is critical in determining the quality of water draining from such areas. This work examines the fundamental reactions that influence the pH and composition of drainage from mine adits and tailings piles. We construct triangle diagrams that predict stoichiometric relationships between concentrations of dissolved SO4 dissolved Ca and Mg, and either alkalinity or acidity by considering reactions involving the oxidation of pyrite, dissolution of carbonate minerals, and precipitation of iron oxide and iron hydroxysulfate minerals. Drainage data from the Coeur d'Alene mining district are used to test our stoichiometric approach. Comparisons between theoretical predictions and drainage data indicate that the range of pH values in the mining district is due to reacting pyrite to carbonate mineral ratios that range from near 0/1 to 1/1. Calcite and ankerite are the dominant carbonate minerals that buffer the acid produced during pyrite oxidation and ferrihydrite or schwertmannite precipitation.The relative abundance of minerals that react to generate or consume acid in mineralized areas is critical in determining the quality of water draining from such areas. This work examines the fundamental reactions that influence the pH and composition of drainage from mine adits and tailings piles. We construct triangle diagrams that predict stoichiometric relationships between concentrations of dissolved SO4, dissolved Ca and Mg, and either alkalinity or acidity by considering reactions involving the oxidation of pyrite, dissolution of carbonate minerals, and precipitation of iron oxide and iron hydroxysulfate minerals. Drainage data from the Coeur d'Alene mining district are used to test our stoichiometric approach. Comparisons between theoretical predictions and drainage data indicate that the range of pH values in the mining district is due to reacting pyrite to carbonate mineral ratios that range from near 0/1 to 1/1. Calcite and ankerite are the dominant carbonate minerals that buffer the acid produced during pyrite oxidation and ferrihydrite or schwertmannite precipitation.

Idaho↗

Binding of polychlorinated biphenyls to aquatic humic substances: The role of substrate and sorbate properties on partitioning

Two ortho- (2,2‘,5 and 2,2‘,5,6‘) and a non-ortho- (3,3‘,4,4‘) substituted polychlorinated biphenyl (PCB) congeners were used to study the effects of sorbate structure in binding processes to two lacustrine fulvic acids. Binding constants were determined by solubility enhancement of the solutes by the fulvic acids. The binding of the ortho-trichlorobiphenyl was significantly less than the non-ortho-substituted tetrachlorobiphenyl to both fulvic acids. Surprisingly, the measured ortho-trichlorobiphenyl binding constant to both fulvic acids was approximately the same as the ortho-substituted tetrachlorobiphenyl. The effect of the chlorines in the ortho position inhibits free rotation around the 1,1‘ carbon bond, thereby making the molecule less able to interact effectively with the fulvic acid substrate relative to its non-ortho-substituted congeners. Finally, binding of all three PCBs to the Great Dismal Swamp fulvic acid was significantly higher than for the Pony Lake sample. This observation is attributable to the former substrate's higher degree of aromaticity and polarizability, which can potentially interact more favorably with the PCBs through an increase in van der Waals type interactions.

Environmental Science & Technology↗

Chlorinated ethenes from groundwater in tree trunks

The purpose of this investigation was to determine whether tree-core analysis could be used to delineate shallow groundwater contamination by chlorinated ethenes. Analysis of tree cores from bald cypress [ Taxodium distichum (L.) Rich], tupelo ( Nyssa aquatica L.), sweet gum ( Liquidambar stryaciflua L.), oak ( Quercus spp.), sycamore ( Platanus occidentalis L.), and loblolly pine ( Pinus taeda L.) growing over shallow groundwater contaminated with cis- 1,2-dichloroethene ( c DCE) and trichloroethene (TCE) showed that those compounds also were present in the trees. The cores were collected and analyzed by headspace gas chromatography. Bald cypress, tupelo, and loblolly pine contained the highest concentrations of TCE, with lesser amounts in nearby oak and sweet gum. The concentrations of c DCE and TCE in various trees appeared to reflect the configuration of the chlorinated-solvent groundwater contamination plume. Bald cypress cores collected along 18.6-m vertical transects of the same trunks showed that TCE concentrations decline by 30&minus;70% with trunk height. The ability of the tested trees to take up c DCE and TCE make tree coring a potentially cost-effective and simple approach to optimizing well placement at this site.

Environmental Science & Technology↗

Methylmercury content of eggs in yellow perch related to maternal exposure in four Wisconsin lakes

We examined the influence of maternal mercury and selected lacustrine variables on the mercury content of eggs from yellow perch ( Perca flavescens ). Total mercury, methylmercury, and inorganic mercury were determined in eggs and carcasses (less eggs) from three seepage lakes with a pH range of 6.1−7.0 and a fourth lake in which pH was experimentally increased from 5.5 to 6.8 by addition of alkaline groundwater. The concentration of total mercury in eggs was strongly correlated with that in the maternal carcass. Concentrations and burdens of mercury in eggs and carcasses were inversely correlated with lake water pH, acid-neutralizing capacity, calcium, and dissolved organic carbon. In eggs containing more than 30 ng/g dry weight (4.5 ng/g wet weight) of total mercury, methylmercury averaged 91% of total mercury and ranged from 85% to 96%. Mean burdens of total mercury in individual eggs varied greatly among lakes (range, 2.3−63 pg), and the egg mass averaged 1.9% of the whole-body burden. We conclude that exposure of the developing yellow perch embryo to methylmercury is strongly affected by maternal bioaccumulation, which can vary substantially among and within lakes; however, the toxicological significance of the observed exposure of embryos to methylmercury is unclear.

Wisconsin↗

Seasonal and annual load of herbicides from the Mississippi River Basin to the Gulf of Mexico

Water samples collected from rivers in the Mississippi River Basin were analyzed for selected herbicides to evaluate their discharge to the Gulf of Mexico and to identify their predominant source areas within the basin. Samples were collected from the Mississippi River at Baton Rouge, LA from 1991 to 1997 and from sites on the upper Mississippi, the Missouri, and the Ohio Rivers from 1996 to 1997. Atrazine, metolachlor, and alachlor ESA (an alachlor metabolite) were the most frequently detected herbicides in the Mississippi River at Baton Rouge, and, in general, were present in the largest concentrations. The peak annual herbicide load was in 1993 when about 640 metric tons of atrazine, 320 metric tons of cyanazine, 215 metric tons of metolachlor, 53 metric tons of simazine, and 50 metric tons of alachlor were discharged to the Gulf of Mexico. The annual load of atrazine and cyanazine was generally 1−3% of the amount annually applied in the Mississippi River drainage basin; the annual load of acetochlor, alachlor, and metolachlor was generally less than 1%. During 1996−1997 the Ohio River contributed about 50% of the discharge and 50% or more of the herbicide load to the Gulf of Mexico.

Environmental Science & Technology↗

Inhibition of precipitation and aggregation of metacinnabar (mercuric sulfide) by dissolved organic matter isolated from the Florida Everglades

Precipitation and aggregation of metacinnabar (black HgS) was inhibited in the presence of low concentrations (≥3 mg C/L) of humic fractions of dissolved organic matter (DOM) isolated from the Florida Everglades. At low Hg concentrations (≤5 × 10 - 8 M), DOM prevented the precipitation of metacinnabar. At moderate Hg concentrations (5 × 10 - 5 M), DOM inhibited the aggregation of colloidal metacinnabar (Hg passed through a 0.1 μm filter but was removed by centrifugation). At Hg concentrations greater than 5 × 10 - 4 M, mercury formed solid metacinnabar particles that were removed from solution by a 0.1 μm filter. Organic matter rich in aromatic moieties was preferentially removed with the solid. Hydrophobic organic acids (humic and fulvic acids) inhibited aggregation better than hydrophilic organic acids. The presence of chloride, acetate, salicylate, EDTA, and cysteine did not inhibit the precipitation or aggregation of metacinnabar. Calcium enhanced metacinnabar aggregation even in the presence of DOM, but the magnitude of the effect was dependent on the concentrations of DOM, Hg, and Ca. Inhibition of metacinnabar precipitation appears to be a result of strong DOM-Hg binding. Prevention of aggregation of colloidal particles appears to be caused by adsorption of DOM and electrostatic repulsion.

Environmental Science & Technology↗

Adsorption of bacteriophages on clay minerals

The ability to predict the fate of microorganisms in soil is dependent on an understanding of the process of their sorption on soil and subsurface materials. Presently, we have focused on studying the thermodynamics of sorption of bacteriophages (T-2, MS-2, and φX-174) on clays (hectorite, saponite, kaolinite, and clay fraction of samples collected from a landfill site). The thermodynamic study not only determines the feasibility of the process but also provides information on the relative magnitudes of the different forces under a particular set of conditions. The total free energy of interaction during sorption of bacteriophages on clays (Δ G ) has been assumed to be the summation of Δ G H (Δ G due to hydrophobic interactions) and Δ G EL (Δ G due to electrostatic interactions). The magnitude of Δ G H was determined from the different interfacial tensions (γ) present in the system, while Δ G EL was calculated from ζ-potentials of the colloidal particles. Calculated results show that surface hydrophobicities of the selected sorbents and sorbates dictate sorption. Among the selected bacteriophages, maximum sorption was observed with T-2, while hectorite has the maximum sorption capacity. Experimental results obtained from the batch adsorption studies also corroborated those obtained from the theoretical study.

Environmental Science & Technology↗

Biophysical mechanisms of trichloroethene uptake and loss in baldcypress growing in shallow contaminated groundwater

Wetland vegetation may be useful in the remediation of shallow contaminated aquifers. Mesocosm experiments were conducted to describe the regulatory mechanisms affecting trichloroethene (TCE) removal rates from groundwater by flood-adapted wetland trees at a contaminated site. TCE flux through baldcypress [Taxodium distichum (L) Rich] seedlings grown in glass- carboys decreased from day to night and from August to December. The diel fluctuation coincided with changes in leaf-level physiology, as the daytime flux was significantly correlated with net photosynthesis but not with respiration at night. A decrease in seedling water use from summer to winter explained the large seasonal difference in TCE flux. A simple model that simulates gas-phase diffusion through aerenchyma tested the importance of diffusion of TCE vapor from roots to the stem. The modeled diffusive flux was within 64% of the observed value during the winter but could only explain 8% of the summer flux. Seedling water use was a good estimator of flux during the summer. Hence, evapotranspiration (ET) in the summer may serve as a good predictor for the potential of TCE removal by baldcypress trees, while diffusive flux may better approximate potential contaminant loss in the winter.Wetland vegetation may be useful in the remediation of shallow contaminated aquifers. Mesocosm experiments were conducted to describe the regulatory mechanisms affecting trichloroethene (TCE) removal rates from groundwater by flood-adapted wetland trees at a contaminated site. TCE flux through baldcypress [Taxodium distichum (L) Rich] seedlings grown in glass-carboys decreased from day to night and from August to December. The diel fluctuation coincided with changes in leaf-level physiology, as the daytime flux was significantly correlated with net photosynthesis but not with respiration at night. A decrease in seedling water use from summer to winter explained the large seasonal difference in TCE flux. A simple model that simulates gas-phase diffusion through aerenchyma tested the importance of diffusion of TCE vapor from roots to the stem. The modeled diffusive flux was within 64% of the observed value during the winter but could only explain 8% of the summer flux. Seedling water use was a good estimator of flux during the summer. Hence, evapotranspiration (ET) in the summer may serve as a good predictor for the potential of TCE removal by baldcypress trees, while diffusive flux may better approximate potential contaminant loss in the winter.

Environmental Science & Technology↗

Metolachlor and its metabolites in tile drain and stream runoff in the canajoharie creek watershed

Water samples collected during April−November 1997 from tile drains beneath cultivated fields in central New York indicate that two metabolites of the herbicide metolachlor metolachlor ESA (ethanesulfonic acid) and OA (oxanilic acid) can persist in agricultural soils for 4 or more years after application and that fine-grained soils favor the transport of metolachlor ESA over metolachlor and metolachlor OA. Concentrations of metolachlor ESA from the tile drains ranged from 3.27 to 23.4 μg/L (200−1800 times higher than those of metolachlor), metolachlor OA concentrations ranged from 1.14 to 13.5 μg/L, and metolachlor concentrations ranged from less than 0.01 to 0.1 μg/L. In the receiving stream, concentrations of metolachlor ESA were always below 0.6 μg/L except during a November storm, when concentrations reached 0.85 μg/L. Concentrations of metolachlor ESA in the stream were 2−45 times higher than those of metolachlor, reflecting the greater relative concentrations of metolachlor in surface water runoff than in tile drain runoff. These results are consistent with findings in other studies that acetanilide herbicide degredates are found in much higher concentrations than parent compounds in both surface water and groundwater.

New York↗

Exploring factors controlling the variability of pesticide concentrations in the Willamette River Basin using tree-based models

We analyzed available concentration data of five commonly used herbicides and three pesticides collected from small streams in the Willamette River Basin in Oregon to identify factors that affect the variation of their concentrations in the area. The emphasis of this paper is the innovative use of classification and regression tree models for exploratory data analysis as well as analyzing data with a substantial amount of left-censored values. Among variables included in this analysis, land-use pattern in the watershed is the most important for all but one (simazine) of the eight pesticides studied, followed by geographic location, intensity of agriculture activities in the watershed (represented by nutrient concentrations in the stream), and the size of the watershed. The significant difference between urban sites and agriculture sites is the variability of stream concentrations. While all 16 nonurban watersheds have significantly higher variation than urban sites, the same is not necessarily true for the mean concentrations. Seasonal variation accounts for only a small fraction of the total variance in all eight pesticides.We analyzed available concentration data of five commonly used herbicides and three pesticides collected from small streams in the Willamette River Basin in Oregon to identify factors that affect the variation of their concentrations in the area. The emphasis of this paper is the innovative use of classification and regression tree models for exploratory data analysis as well as analyzing data with a substantial amount of left-censored values. Among variables included in this analysis, land-use pattern in the watershed is the most important for all but one (simazine) of the eight pesticides studied, followed by geographic location, intensity of agriculture activities in the watershed (represented by nutrient concentrations in the stream), and the size of the watershed. The significant difference between urban sites and agriculture sites is the variability of stream concentrations. While all 16 nonurban watersheds have significantly higher variation than urban sites, the same is not necessarily true for the mean concentrations. Seasonal variation accounts for only a small fraction of the total variance in all eight pesticides.

Environmental Science & Technology↗

Geochemical influences on assimilation of sediment-bound metals in clams and mussels

A series of experiments was performed to evaluate the extent to which Cd, Co, Ag, Se, Cr, and Zn bound to sediments with different geochemical properties could be assimilated by the mussel Mytilus edulis and the clam Macoma balthica. Oxidized and reduced radiolabeled sediments were fed to suspension-feeding animals, the depuration patterns of the individuals were followed by ??-spectrometry, and the assimilation efficiencies (AEs) of ingested metals were determined. AEs from geochemically diverse sediments typically varied less than 2-fold and ranged from 1% for Cr to 42% for Zn. Metals were assimilated from anoxic sediment by both animals; Ag, Cd, and Co AEs in M. balthica were 9-16%, 2-fold lower than from oxic sediment, but in M. edulis AEs were about two times greater from anoxic sediment for all metals but Ag. For oxic sediment, Cd and Co AEs in M. edulis decreased 3-4-fold with increased sediment exposure time to the metals with smaller but significant effects also noted for Zn and Se but not Ag. A less pronounced decrease in AE for M. balthica was evident only after 6 months exposure time. Sequential extractions of the oxidized sediments showed a transfer of metals into more resistant sediment components over time, but the rate did not correlate with a decrease in metal AEs. Comparing the two bivalves, TOC concentrations had an inconsistent effect on metal AEs. AEs of metals from bacteria-coated glass beads were slightly higher than from humic acid-coated beads, which were comparable with whole-sediment AEs. There was correspondence of AE with desorption of Ag, Cd, Co, and Se (but not Zn) from sediments into pH 5 seawater, measured to simulate the gut pH of these bivalves. The results imply that metals associated with sulfides and anoxic sediments are bioavailable, that the bioavailability of metals from sediments decreases over exposure time, that organic carbon content generally has a small effect on AEs, and that AEs of sediment-bound metals differ among species.

Environmental Science & Technology↗