Hydroxylamine hydrochloride-acetic acid-soluble and -insoluble fractions of pelagic sediment: Readsorption revisited
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The sorption of hydrophobic organic chemicals (HOCs) to ??-Al2O3 was investigated with a headspace analysis method. The semiautomated headspace analyzer gave rapid, precise, and accurate results for a homologous series alkylbenzenes even at low percentages of solute mass sorbed (3-50%). Sorption experiments carried out with benzene alone indicated weak interactions with well-characterized aluminum oxide, and a solids concentration effect was observed. When the sorption coefficients for benzene alone obtained by headspace analysis were extrapolated up to the solids concentrations typically used in batch sorption experiments, the measured sorption coefficients agreed with reported sorption coefficients for HOCs and sediments of low fractional organic carbon content. Sorbed concentrations increased exponentially with aqueous concentration in isotherms with mixtures of alkylbenzenes, indicating solute-solute interactions at the mineral surface. Sorption was, however, greater than predicted for partitioning of a solute between its pure liquid phase and water, indicating additional influences of the surface and/or the structured liquid near the mineral surface. ?? 1993 American Chemical Society.
Concentrations of pesticides in the dissolved phase of surface water samples from the Yakima River basin, WA, were determined using preconcentration in the Goulden large-sample extractor (GLSE) and gas chromatography/mass spectrometry (GC/MS) analysis. Sample volumes ranging from 10 to 120 L were processed with the GLSE, and the results from the large-sample analyses were compared to those derived from 1-L continuous liquid-liquid extractions Few of the 40 target pesticides were detected in 1-L samples, whereas large-sample preconcentration in the GLSE provided detectable levels for many of the target pesticides. The number of pesticides detected in GLSE processed samples was usually directly proportional to sample volume, although the measured concentrations of the pesticides were generally lower at the larger sample volumes for the same water source. The GLSE can be used to provide lower detection levels relative to conventional liquid-liquid extraction in GC/MS analysis of pesticides in samples of surface water.
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The loss of the preemergent herbicide atrazine in surface runoff from experimental field plots growing corn (Zea mays L.) was significantly reduced using a starchencapsulated formulation versus a conventional powdered formulation. Field edge losses of starch-encapsulated atrazine were described as following a Rayleigh distribution totaling 1.8% of applied herbicide compared to exponential powdered atrazine losses of 2.9% applied - a 40% decrease. This has important implications for the reduction of nonpoint source contamination of surface water by agricultural chemicals. Unsaturated zone release of starchencapsulated atrazine was gradual, but comparable weed control was maintained. Deethylatrazine was a major dealkylated metabolite from each formulation, and deisopropylatrazine was a minor metabolite. The determination of soil partition coefficients for deethylatrazine and deisopropylatrazine (0.4 and 0.3, respectively), aqueous solubilities (3200 and 670 mg/L, respectively), and melting points (133 and 177 C, respectively) confirmed that the dealkylated metabolites should move more rapidly through the soil profile to groundwater than atrazine.
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Sorption of tetra- and pentachlorobenzene by sediment from a glacial outwash aquifer on Cape Cod, MA, was evaluated. Particle size and mineralogical fractions (separated based on paramagnetic susceptibility) were characterized with respect to sediment organic carbon (SOC), mineralogy, surface area, metal oxide coatings, and spatial variability. SOC increases by a factor of 10 as particle size decreases from 500-1000 to <63 um. Magnetic mineral abundance is a function of particle size and increases from 5 % in the 500-1000-xm fraction to > 25 % in the <63-um fraction, and SOC is preferentially associated with the magnetic minerals. Sorption increases with decreasing particle size (increasing SOC, magnetic minerals, surface area, and metal oxyhydroxides), and the magnetic mineral fraction has greater sorption than the bulk or nonmagnetic fractions. Removal of SOC decreases sorption proportional to the decrease in SOC and results in a nonlinear isotherm.
Linear alkylbenzenes (LABs), coprostanol and epi-coprostanol, were detected in sediment trap and bottom sediment samples at the Deep Water Dump Site 106 located 185 km off the coast of New Jersey, in water depths from 2400 to 2900 m. These findings clearly indicate that organic pollutants derived from dumped sludge are transported through the water column and have accumulated on the deep-sea floor. No significant difference in LABs isomeric composition was observed among sludge and samples, indicating little environmental biodegradation of these compounds. LABs and coprostanol have penetrated down to a depth of 6 cm in sediment, indicating the mixing of these compounds by biological and physical processes. Also, in artificially resuspended surface sediments, high concentrations of LABs and coprostanols were detected, implying that sewage-derived organic pollutants initially deposited on the deep-sea floor can be further dispersed by resuspension and transport processes. Small but significant amounts of coprostanol were detected in the sediment from a control site at which no LABs were detected. The coprostanol is probably derived from feces of marine mammals and sea birds and/or from microbial or geochemical transformations of cholesterol. Polcyclic aromatic hydrocarbons (PAHs) in sediment trap samples from the dump site were largely from the sewage sludge and had a mixed petroleum and pyrogenic composition. In contrast, PAHs in sediments in the dump site were mainly pyrogenic; contributed either from sewage sludge or from atmospheric transport to the overlying waters. & 1994 American Chemical Society.
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The number- and weight-averaged molecular weights of a number of aquatic fulvic acids, a commercial humic acid, and unfractionated organic matter from four natural water samples were measured by high-pressure size exclusion chromatography (HPSEC). Molecular weights determined in this manner compared favorably with those values reported in the literature. Both recent literature values and our data indicate that these substances are smaller and less polydisperse than previously believed. Moreover, the molecular weights of the organic matter from three of the four natural water samples compared favorably to the fulvic acid samples extracted from similar environments. Bulk spectroscopic properties of the fulvic substances such as molar absorptivity at 280 nm and the E4/E6 ratio were also measured. A strong correlation was observed between molar absorptivity, total aromaticity, and the weight average molecular weights of all the humic substances. This observation suggests that bulk spectroscopic properties can be used to quickly estimate the size of humic substances and their aromatic contents. Both parameters are important with respect to understanding humic substance mobility and their propensity to react with both organic and inorganic pollutants.
Experiments in St. Kevin Gulch, an acid mine drainage stream, examined the coupling of hydrologic transport to chemical reactions affecting metal concentrations. Injection of LiCl as a conservative tracer was used to determine discharge and residence time along a 1497-m reach. Transport of metals downstream from inflows of acidic, metal-rich water was evaluated based on synoptic samples of metal concentrations and the hydrologic characteristics of the stream. Transport of SO 4 and Mn was generally conservative, but in the subreaches most affected by acidic inflows, transport was reactive. Both 0.1-um filtered and particulate Fe were reactive over most of the stream reach. Filtered Al partitioned to the particulate phase in response to high instream concentrations. Simulations that accounted for the removal of SO 4 , Mn, Fe, and Al with first-order reactions reproduced the steady-state profiles. The calculated rate constants for net removal used in the simulations embody several processes that occur on a stream-reach scale. The comparison between rates of hydrologie transport and chemical reactions indicates that reactions are only important over short distances in the stream near the acidic inflows, where reactions occur on a comparable time scale with hydrologic transport and thus affect metal concentrations.
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The reductive dehalogenation of hexachloroethane (C2Cl6), carbon tetrachloride (CCl4), and bromoform (CHBr3) was examined at 50??C in aqueous solutions containing either (1) 500 ??M of 2,6-anthrahydroquinone disulfonate (AHQDS), (2) 250 ??M Fe2+, or (3) 250 ??M HS-. The pH ranged from 4.5 to 11.5 for AHQDS solutions and was 7.2 in the Fe2+ solutions and 7.8 in the HS- solutions. The observed disappearance of C2Cl6 in the presence of AHQDS was pseudo-first-order and fit k??ccl4 = k0[A(OH)2] + k1[A(OH)O-] + k2[A(O)22-] where A(OH)2, A(OH)O-, and A(O)22- represent the concentrations of the three forms of the AHQDS in solution. The values of k0, k1, and k2 were ???0,0.031, and 0.24 M-1 s-1, respectively. The addition of 25 mg of C/L of humic acid or organic matter extracted from Borden aquifer solids to aqueous solutions containing 250 ??M HS- or Fe2+ increased the reduction rate by factors of up to 10. The logarithms of the rate constants for the disappearance of C2Cl6 and CCl4 in seven different experimental systems were significantly correlated; log k???ccl4 = 0-64 log k??? c2cl6 - 0.83 with r2 = 0.80. The observed trend in reaction rates of C2Cl6 > CCl4 > CHBr3 is consistent with a decreasing trend in one-electron reduction potentials. ?? 1994 American Chemical Society.
Differences between field and laboratory pH values reported by the National Atmospheric Deposition Program/National Trends Network (NADP/NTN) monitoring program from 1984 through 1986 are investigated. Median differences in hydrogen ion concentration between laboratory and field pH determinations at sites averaged -4.6 μ equiv/L in natural precipitation samples on an annual basis. The median difference found in external quality assurance samples analyzed during the same time period was -11 μ equiv/L. The results suggest a systematic bias in pH values reported by the NADP/NTN network. The bias appears to have a fixed component of approximately -7 μ equiv/L, which can be attributed to the sampling bucket and lid, and a seasonal and regional component that ranges from +4 to -22 μ equiv/L at the 10th and 90th percentiles. Differences were found to be independent of sample pH and sample volume. The magnitude of the bias has implications for the interpretation of previously published pH and hydrogen ion concentration and deposition values in the western United States.