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At least 235 records · Page 13Linked to original sources
USGS2002

Strong-acid, carboxyl-group structures in fulvic acid from the Suwannee River, Georgia. 2. Major structures

Polycarboxylic acid structures that account for the strong-acid characteristics (pKa1 near 2.0) were examined for fulvic acid from the Suwannee River. Studies of model compounds demonstrated that pKa values near 2.0 occur only if the a-ether or a-ester groups were in cyclic structures with two to three additional electronegative functional groups (carboxyl, ester, ketone, aromatic groups) at adjacent positions on the ring. Ester linkage removal by alkaline hydrolysis and destruction of ether linkages through cleavage and reduction with hydriodic acid confirmed that the strong carboxyl acidity in fulvic acid was associated with polycarboxylic a-ether and a-ester structures. Studies of hypothetical structural models of fulvic acid indicated possible relation of these polycarboxylic structures with the amphiphilic and metal-binding properties of fulvic acid.

Environmental Science & Technology↗
USGS2002

Procedures for formation of composite samples from segmented populations

We used a simulation approach to investigate the implication of two methods of forming composite samples to characterize segmented populations. We illustrate the case where the weight of individual segments varies randomly, a situation common with fish samples. Composite samples from segments such as whole fish or muscle tissue should be formed by homogenizing each segment separately and combining equal-sized portions randomly drawn from each homogenate. This approach permits unbiased estimation of the mean concentration per fish. Estimates of mean contaminant concentration varied little with variation in the number of composite samples analyzed or with composite size (number of segments in a composite sample). However, for a fixed number of composite samples, the precision of the variance estimate increases as composite size increased. In addition, for a fixed number of composites, the estimate of the variance stabilized as more segments were included in the composite samples. Estimates of the variance among fish or other population segments can be recovered using appropriate compositing procedures and specially-designed studies.

Environmental Science & Technology↗
USGS2002

Oxidation of dimethylselenide by δMnO 2 : oxidation product and factors affecting oxidation rate

Volatile dimethylselenide (DMSe) was transformed to a nonvolatile Se compound in a ??-MnO2 suspension. The nonvolatile product was a single compound identified as dimethylselenoxide based on its mass spectra pattern. After 24 h, 100% of the DMSe added to a ??-MnO2 suspension was converted to nonpurgable Se as opposed to 20%, 18%, and 4% conversion for chromate, permanganate, and the filtrate from the suspension, respectively. Manganese was found in solution after reaction. These results imply that the reaction between manganese oxide and DMSe was a heterogeneous redox reaction involving solid phase ??-MnO2 and solution phase DMSe. Oxidation of DMSe to dimethylselenoxide [OSe(CH3)2] by a ??-MnO2 suspension appears to be first order with respect to ??-MnO2, to DMSe, and to hydrogen ion with an overall rate law of d[OSe(CH3)2 ]/dt = 95 M-2 min-1 [MnO2]1[DMSe]1[H+]1 for the MnO2 concentration range of 0.89 ?? 10-3 - 2.46 ?? 10-3 M, the DMSe concentration range of 3.9 ?? 10-7 - 15.5 ?? 10-7 M Se, and a hydrogen ion concentation range of 7.4 ?? 10-6 -9.5 ?? 10-8 M. A general surface site adsorption model is consistent with this rate equation if the uncharged |OMnOH is the surface adsorption site. DMSe acts as a Lewis base, and the manganese oxide surface acts as a Lewis acid. DMSe adsorption to |OMnOH can be viewed as a Lewis acid/ base complex between the largely p orbitals of the DMSe lone pair and the unoccupied eg orbitals on manganese oxide. For such a complex, frontier molecular orbital theory predicts electron transfer to occur via an inner-sphere complex between the DMSe and the manganese oxide. ?? 1995 American Chemical Society.

Environmental Science & Technology↗
USGS2002

Use of the semipermeable membrane device as an in situ sampler of waterborne bioavailable PCDD and PCDF residues at sub-parts-per-quadrillion concentrations

Semipermeable membrane devices (SPMDs) were used to passively sample aqueous polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in Bayou Meto, AR. The two sites were upstream and downstream from the confluence with a tributary that delivers PCDDs and PCDFs to the Bayou. Following dialysis, cleanup, and fractionation, four replicate 17-9 SPMD samples from each site were analyzed by GUMS, and four were evaluated by H411E bioassay. Traces of only OCDD and HpCDDs were detected in samples from the upstream site. The four samples from below the tributary contained averages of 1550 ± 80 pg of 2,3,7,8-TCDD, 1640 ± 80 pg of 2,3,7,8-TCDF, and lesser quantities of other congeners. The TCDD equivalents obtained by bioassay of replicate SPMD samples agreed well with results obtained by GC/MS. The quantities of 2,3,7,8- TCDD and 2,3,7,8-TCDF sequestered by SPMDs at the downstream site were used to estimate the aqueous concentrations for both compounds as 2 pg/L.

Environmental Science & Technology↗
USGS2002

Linear solvation energy relationships: "rule of thumb" for estimation of variable values

For the linear solvation energy relationship (LSER), values are listed for each of the variables (V i /100, π*, &beta m , α m ) for fundamental organic structures and functional groups. We give the guidelines to estimate LSER variable values quickly for a vast array of possible organic compounds such as those found in the environment. The difficulty in generating these variables has greatly discouraged the application of this quantitative structure-activity relationship (QSAR) method. This paper present the first compilation of molecular functional group values together with a utilitarian set of the LSER variable estimation rules. The availability of these variable values and rules should facilitate widespread application of LSER for hazard evaluation of environmental contaminants.

Environmental Science & Technology↗
USGS2002

Herbicides in surface waters of the midwestern United States: The effect of spring flush

Approximately three-fourths of all preemergent herbicides used in the United States are applied to row crops over a 12-state area, called the "corn belt" (I). The application of these compounds may cause widespread degradation of water quality (2). Because herbicides are water soluble, there is the potential for leaching into groundwater and surface water (3, 4), as well as aerial transport and Occurrence in precipitation (5). Monitoring studies in the Midwest have shown widespread detection of herbicides in groundwater and in surface water (3,4); however, little is known about the regional impact of herbicide application (6). The objective of our research was to assess the mag. nitude and persistence of herbicide runoff in the spring flush at the regional scale.

Environmental Science & Technology↗
USGS2002

Parameterizing the equilibrium distribution of chemicals between the dissolved, solid particulate matter, and colloidal matter compartments in aqueous systems

The manner in which a chemical material partitions among the dissolved (D), participate (P), and colloidal (C) phases affects both its chemical and physical behavior in the aquatic environment. The fractions of the chemical that are present in each of these three phases will be determined by the values of two simple parameters, KpSp/??w and KcSc/??w. The variables Kp and Kc are the particle/water and colloid/water partition constants (mL/g), respectively, Sp and Sc are the volume concentrations of particulate and colloidal material (mg/L), respectively, and ??w is the fractional volume of the system that is aqueous. This parameterization allows a rapid overview of how partitioning (1) changes as a function of chemical partitioning properties and water type, (2) affects apparent partition constants (i.e., Kpapp values) computed between the particulate phase and the remainder of the system, and (3) causes Kpapp values to become independent of chemical properties at high values of KcSc/??w. ?? 1991 American Chemical Society.

Environmental Science & Technology↗