Soil sorption of organic vapors and effects of humidity on sorptive mechanism and capacity
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This investigation assesses geographic variations in atmospheric deposition in Washington, Oregon, and California using snow cores from the Cascade-Sierra Nevada Mountains, collected from late February to mid-March 1983. A statistical analysis of the analytical and sampling precision was made. The snowpack in the higher Cascades and Sierra Nevada is not strongly influenced by anthropogenic activities at present. The pH of snow samples ranges from 5.11 to 5.88. Sulfate and nitrate correlate with H+ in some segments of the sample traverse. The SO4 data show apparent influence from major source areas in Washington and California; nitrate does not. An apparent decrease in NH4 in snow in Washington and California suggests atmospheric interactions resulting in the removal of NH4. The NH4 reduction raises questions about nutrient supply to the mountain vegetation. Heavy-metal correlations included Cd, Cu, and Fe with Pb, and Mn with K and DOC, among others. No correlation was found between constituents and snow-water content.
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Seven samples of commercial "humic acids", purchased from five different suppliers, were studied, and their characteristics were compared with humic and fulvic acids isolated from streams, soils, peat, leonardite, and a dopplerite sample. Cross-polarization and magic-angle spinning 13C NMR spectroscopy clearly shows pronounced differences between the commercial materials and all other samples. Elemental and infrared spectroscopic data do not show such clear-cut differences but can be used as supportive evidence, with the 13C NMR data, to substantiate the above distinctions. As a result of these differences and due to the general lack of information relating to the source, method of isolation, or other pretreatment of the commercial materials, these commercial products are not considered to be appropriate for use as analogues of true soil and water humic substances, in experiments designed to evaluate the nature and reactivity of humic substances in natural waters and soils.
No abstract available.
Gas-film coefficients for the volatilization of ethylene dibromide (EDB) and water were determined in the laboratory as a function of wind speed and temperature. The ratio of the coefficients was independent of wind speed and increased slightly with temperature. Use of this ratio with an environmentally determined gas-film coefficient for the evaporation of water permits determination of the gas-film coefficient for the volatilization of EDB from environmental waters.
A recently developed analytical method using liquid chromatography/mass spectrometry was used to investigate the occurrence of cyanazine and its degradates cyanazine acid (CAC), cyanazine amide (CAM), deethylcyanazine (DEC), and deethylcyanazine acid (DCAC) in groundwater. This research represents some of the earliest data on the occurrence of cyanazine degradates in groundwater. Although cyanazine was infrequently detected in the 64 wells across Iowa sampled in 1999, cyanazine degradates were commonly found during this study. The most frequently detected cyanazine compound was DCAC (32.8%) followed by CAC (29.7%), CAM (17.2%), DEC (3.1%), and cyanazine (3.1%). The frequency of detection for cyanazine or one or more of its degradates (CYTOT) was more than 12-fold over that of cyanazine alone (39.1% for CYTOT versus 3.1% for cyanazine). Of the total measured concentration of cyanazine, only 0.2% was derived from its parent compound - with DCAC (74.1%) and CAC (18.4%) comprising 92.5% of this total. Thus, although DCAC and CAC had similar frequencies of detection, DCAC was generally present in higher concentrations. No concentrations of cyanazine compounds for this study exceeded water-quality criteria for the protection of human health. Only cyanazine, however, has such a criteria established. Nevertheless, because these cyanazine degradates are still chlorinated, they may have similar toxicity as their parent compound - similar to what has been found with the chlorinated degradates of atrazine. Thus, the results of this study documented that data on the degradates for cyanazine are critical for understanding its fate and transport in the hydrologic system. Furthermore, the prevalence of the chlorinated degradates of cyanazine found in groundwater suggests that to accurately determine the overall effect on human health and the environment from cyanazine its degradates should also be considered. In addition, because CYTOT was found in 57.6% of the samples collected from alluvial aquifers, about 2-5 times more frequently than the other major aquifer types (glacial drift, bedrock/karst, bedrock/nonkarst) under investigation, this finding has long-term implications for the occurrence of CYTOT in streams. It is anticipated that low-level concentrations of CYTOT will continue to be detected in streams for years after the use of cyanazine has terminated (scheduled for the year 2000 in the United States), primarily through its movement from groundwater into streams during base-flow conditions.
Microorganisms indigenous to stream and lake bed sediments, collected from 11 sites throughout the United States, demonstrated significant mineralization of the fuel oxygenate, methyl-tert-butyl ether (MTBE). Mineralization of [U-14C]MTBE to 14CO2 ranged from 15 to 66% over 50 days and did not differ significantly between sediments collected from MTBE contaminated sites and from sites with no history of MTBE exposure. This result suggests that even the microbial communities indigenous to newly contaminated surface water systems will exhibit some innate ability to attenuate MTBE under aerobic conditions. The magnitude of MTBE mineralization was related to the sediment grain size distribution. A pronounced, inverse correlation (p < 0.001; r2 = 0.73) was observed between the final recovery of 14CO2 and the percentage content of silt and clay sized grains (grain diameter < 0.125 mm). The results of this study indicate that the microorganisms that inhabit the bed sediments of streams and lakes can degrade MTBE efficiently and that this capability is widespread in the environment. Thus aerobic bed sediment microbial processes may provide a significant environmental sink for MTBE in surface water systems throughout the United States and may contribute to the reported transience of MTBE in some surface waters.
Overall mass-transfer coefficients for the volatilization of ethylene dibromide from water were measured simultaneously with the oxygen absorption coefficient in a laboratory stirred tank. Coefficients were measured as a function of mixing conditions in the water for two windspeeds. The ethylene dibromide mass-transfer coefficient depended on windspeed; the ethylene dibromide liquid-film coefficient did not, in agreement with theory. A constant relation existed between the liquid-film coefficients for ethylene dibromide and oxygen.
Acid mine drainage has acidified large volumes of water and added high concentrations of dissolved heavy metals to West Squaw Creek, a California stream draining igneous rocks of low acid-neutralizing capacity. During mixing of the acid sulfate stream waters in the South Fork of West Squaw Creek with an almost equal volume of dilute uncontaminated water, Cu, Zn, Mn, and Al remained in solution rather than precipitating or adsorbing on solid phases. Changes in the concentration of these generally conservative metals could be used to determine relative flow volumes of acid tributaries and the main stream. An amorphous orange precipitate (probably ferric hydroxides or a mixture of ferric hydroxides and jarosite) was ubiquitous in the acid stream beds and was intimately associated with algae at the most acid sites. Relative sorption of cations decreased with decreasing water pH. However, arsenic was almost completely scavenged from solution within a short distance from the sulfide sources.
The biota - sediment accumulation factor (BSAF) model has been suggested as a simple tool to predict bioaccumulation of hydrophobic organic compounds (HOCs)in fish and other aquatic biota from measured concentrations in sediment based on equilibrium partitioning between the sediment organic carbon and biotic lipid pools. Currently, evaluation of this model as a predictive tool has been limited to laboratory studies and small-scale field studies, using a limited number of biotic species. This study evaluates the model, from field data, for a suite of organochlorine HOCs from paired fluvial sediment and biota (fish and bivalves) samples throughout the United States and over a large range of biotic species. These data represent a real-world, worst-case scenario of the model because environmental variables are not controlled. Median BSAF values for fish (3.3) and bivalves (2.8) were not statistically different but are higher than theoretically predicted values (1-2). BSAF values varied significantly in a few species. Differences in chemical-specific BSAF values were not observed in bivalves but were statistically significant in fish. The HOCs with differing BSAF values were those known to be biotransformed. Sediment organic carbon content and biota lipid content had no effect on BSAF values in fish and only a weak effect in bivalves. This study suggests that the BSAF model could be useful under in situ riverine conditions as a first-level screening tool for predicting bioaccumulation; however, variability in BSAF values may impose limits on its utility.
No abstract available.
Oxalic acid retards the alteration of Mn3O4 to γ-MnOOH during aging at pH 7.4 ?? 0.2 in well-aerated, abiotic suspensions that contain 4.4 ?? 10-3 M total Mn. In solutions of 1.25 ?? 10-3 M oxalate and greater, about 15% of the initial Mn3O4 altered to ??-MnOOH by day 10, and in solutions of 6.7 ?? 10-4 M oxalate, about 45% altered to ??-MnOOH by day 67. Although precipitation continued through day 365, the degree of conversion remained the same as at day 10 and day 67, respectively. In oxalate-free suspensions, the conversion was about 80% complete by day 67 and 100% by day 109. Oxalate complexed most of the dissolved divalent Mn, lowered the free Mn(II) and MnSO40 concentrations, but increased the total dissolved Mn. Steric hindrance of surface reactions by a suggested manganese oxalate layer on the Mn3O4 surface may explain the blockage of the oxidation cycle.
No abstract available.