Passive water sampling for polynuclear aromatic hydrocarbons using lipidcontaining semipermeable membrane devices (SPMDs): Application to contaminant residence times

Lipid-containing semipermeable membrane devices are applied to the quantitative determination of the persistence of polynuclear aromatic hydrocarbons (PAH) in an irrigation water canal, a representative waterway. The uniform and reproducible sampling of the USGS design of lipid-containing SPMDs is exploited to measure PAH half-lives without requiring calculation of water concentrations. The trend in calculated PAH half-lives agrees with that expected if volatilization is a significant mechanism for loss from the canal with more volatile PAHs having shorter half-lives. The higher persistence of phenanthrene compared to anthracene is consistent with the greater stability of phenanthrene and suggests, with other physicochemical evidence, that other (reactive) mechanisms may be involved. The results of this study demonstrate the feasibility of the SPMD method for the measurement of residence times in aquatic and other compartments. Such information is essential for quantifying contaminant behavior in the environment and providing insights into contaminant fate.     

Predictions by the Odor From Feedlots, Setback Estimation Tool (OFFSET) compared with observations by neighborhood monitors

A comparison between predicted and observed odor intensities at 20 neighborhood residences in the vicinity of seven various livestock farms in five different Minnesota counties was made to evaluate the Odor From Feedlots, Setback Estimation Tool (OFFSET) developed by the University of Minnesota. Observations by neighborhood monitors suggest that the OFFSET-predicted separation distances for annoyance-free frequencies of 99, 98, and 97% are large enough. The observations additionally indicate that predicted distances to obtain 94 and 91% annoyance-free frequencies may be large enough for some farms, but for other farms, greater distances may be needed. For two farms in the study, no significant difference between all of the observed and predicted intensities could be found. At four sites, a significant difference was found, and at three of these the difference was considerable. Odor emission rates used in the OFFSET model seem to describe the average emission fairly well for many odor sources, but improvement may be needed for some types of sources. Possible reasons for observations of annoying odor when not predicted include fluctuations in the odor emissions, wind speed fluctuations, topographic variation between sites, sensitivity differences by neighborhood monitors, and background emissions from other sources.     

Reduction of silver solubility by humic acid and thiol ligands during acanthite (beta-Ag2S) dissolution

Precipitation of highly insoluble metal sulfide minerals like acanthite (beta-Ag2S) or red cinnabar (HgS) is in principle an effective means to reduce metal availability and toxicity in contaminated soils. Unfortunately, experiments have shown that red cinnabar may be solubilized in the presence of dissolved organic matter or thiol ligands. To determine whether the same applies to acanthite, a laboratory synthesized beta-Ag2S mineral was incubated for up to 3 weeks in the presence of KNO3, dissolved humic acids, cysteine, methionine and thiosulfate. XPS analysis identified Ag2O (52%), Ag2SO4 (8%) and Ag2S (40%) on the particle surfaces. Ag was released into solution in the presence of KNO3 and methionine, presumably from mixed-oxidation surface layers. Contrary to earlier results with cinnabar, however, humic acids reduced Ag concentrations in solution by about 75%, and cysteine and thiosulfate, each containing a free -SH functional group, almost completely suppressed Ag release into solution.     

Groundwater conditions under a reconstructed prairie chronosequence

Chronosequences are useful to evaluate long-term changes in ecosystem services but assessing groundwater quality changes using this approach has rarely been done. In this study, groundwater level and quality comparisons were made in a watershed-scale reconstructed prairie chronosequence that extended back in time approximately 13 years at the Neal Smith National Wildlife Refuge (NSNWR) near Prairie City, Iowa. Our objectives were to determine whether groundwater conditions varied significantly across the chronosequence and quantify the rate of nitrate concentration reduction when row crop fields are replaced by prairie. We installed 19 groundwater wells at upland locations selected to provide similar soil type, landscape position and slope. Water samples were collected on five occasions in 2006 and 2007 and analyzed for field parameters, anions and NO₃-N, NH₄-N and PO₄-P. Significant groundwater changes were primarily associated with groundwater levels, and groundwater nitrate and chloride concentrations. The groundwater was deeper under the older prairie plantings but fluctuated similarly among all well sites. Groundwater nitrate and chloride concentrations decreased 0.58 and 0.52 mg/l per year over the 13-year chronosequence, respectively. Results are seen to provide some guidance to land managers regarding possible nitrate concentration reductions achievable from converting cropland to perennial land cover in similar geomorphic settings.     

Identification and quantification of the hydrological impacts of imperviousness in urban catchments: a review

Urbanisation produces numerous changes in the natural environments it replaces. The impacts include habitat fragmentation and changes to both the quality and quantity of the stormwater runoff, and result in changes to hydrological systems. This review integrates research in relatively diverse areas to examine how the impacts of urban imperviousness on hydrological systems can be quantified and modelled. It examines the nature of reported impacts of urbanisation on hydrological systems over four decades, including the effects of changes in imperviousness within catchments, and some inconsistencies in studies of the impacts of urbanisation. The distribution of imperviousness within urban areas is important in understanding the impacts of urbanisation and quantification requires detailed characterisation of urban areas. As a result most mapping of urban areas uses remote sensing techniques and this review examines a range of techniques using medium and high resolution imagery, including spectral unmixing. The third section examines the ways in which scientists and hydrological and environmental engineers model and quantify water flows in urban areas, the nature of hydrological models and methods for their calibration. The final section examines additional factors which influence the impact of impervious surfaces and some uncertainties that exist in current knowledge.     

Grazers, producer stoichiometry, and the light : nutrient hypothesis revisited

The stoichiometric light:nutrient hypothesis (LNH) links the relative supplies of key resources with the nutrient content of tissues of producers. This resource-driven variation in producer stoichiometry, in turn, can mediate the efficiency of grazing. Typically, discussions of the LNH attribute this resource-stoichiometry link to bottom-up effects of light and phosphorus, which are mediated through producer physiology. Emphasis on bottom-up effects implies that grazers must consume food of quality solely determined by resource supply to ecosystems (i.e., they eat what they are served). Here, we expand upon this largely bottom-up interpretation with evidence from pond surveys, a mesocosm experiment, and a model. Data from shallow ponds showed the "LNH pattern" (positive correlation of an index of light : phosphorus supply with algal carbon : phosphorus content). However, algal carbon : phosphorus content also declined as zooplankton biomass increased in the ponds. The experiment and model confirmed that this latter correlation was partially caused by the various bottom-up and top-down roles of grazers: the LNH pattern emerged only in treatments with crustacean grazers, not those without them. Furthermore, model and experiment clarified that another bottom-up factor, natural covariation of nitrogen : phosphorus ratios with light : phosphorus supply (as seen in ponds), does not likely contribute to the LNH pattern. Finally, the experiment produced correlations between shifts in species composition of algae, partially driven by grazing effects of crustaceans, and algal stoichiometry. These shifts in species composition might shape stoichiometric response of producer assemblages to resource supply and grazing, but their consequences remain largely unexplored. Thus, this study accentuated the importance of grazing for the LNH; de-emphasized a potentially confounding, bottom-up factor (covarying nitrogen : phosphorus supply); and highlighted an avenue for future research for the LNH (grazer-mediated shifts in producer composition).     

Evaluation of ogawa passive sampling devices as an alternative measurement method for the nitrogen dioxide annual standard in El Paso, Texas

Nitrogen Dioxide (NO₂) is a common urban air pollutant that results from the combustion of fossil fuels. It causes serious human health effects, is a precursor to the formation of ground level ozone, another serious air pollutant, and is one of the six criteria air pollutants established by the United States (U.S.) Clean Air Act (CAA). Ogawa Passive Sampling Devices (PSDs) for NO₂ were collocated and operated at six NO₂ Federal Reference Method (FRM) monitor locations in the El Paso, Texas area for the 2004 calendar year. Passive samples were taken at 2-week, 3-week, and 4-week intervals and compared against the continuously operating FRM monitors. Results showed that the collective NO₂ annual arithmetic mean for all passive monitors was identical to the NO₂ mean for all FRM monitors. Of the individual locations, three passive annual NO₂ means were identical to their corresponding FRM means, and three passive annual NO₂ means differed from their corresponding FRM means by only one part per billion (ppb). Linear correlation analysis between all readings of the individual NO₂ PSDs and FRM values showed an average absolute difference of 1.2 ppb with an r ² of 0.95. Paired comparison between high and low concentration annual NO₂ sites, seasonal considerations, and interlab quality control comparisons all showed excellent results. The ease of deployment, reliability, and the cost-savings that can be realized with NO₂ PSDs could make them an attractive alternative to FRM monitors for screening purposes, and even possibly an equivalent method for annual NO₂ monitoring. More tests of the Ogawa NO₂ PSD are recommended for different ecosystem and climate regimes.