Effects of Riparian Vegetation and Watershed Urbanization on Fishes in Streams of the Mid‐Atlantic Piedmont (USA)1

Abstract: The joint influences of riparian vegetation and urbanization on fish assemblages were analyzed by depletion sampling in paired forested and nonforested reaches of 25 small streams along an urbanization gradient. Nonforested reaches were narrower than their forested counterparts, so densities based on surface area differ from linear densities (based on reach length). Linear densities (based on number or biomass of fish) of American eel, white sucker and tesselated darter, and the proportion of biomass of benthic invertivores were significantly higher in nonforested reaches, while linear densities of margined madtom and the number of pool species were significantly higher in forested reaches. Observed riparian effects may reflect differences in habitat and algal productivity between forested and nonforested reaches. These results suggest that relatively small‐scale riparian restoration projects can affect local geomorphology and the abundance of fish. Dense vegetative cover in riparian zones and similar or analogous habitats in both forested and nonforested reaches, the relatively small scale of the nonforested reaches, and the low statistical power to detect differences in abundance of rare species may have limited the observed differences between forested and nonforested reaches. There was a strong urbanization gradient, with reductions of intolerant species and increases of tolerant species and omnivores with increasing urbanization. Interactions between riparian vegetation type and urbanization were found for blacknose dace, creek chub, tesselated darter, and the proportion of biomass of lithophilic spawners. The study did not provide consistent support for the hypotheses that responses of fish to riparian vegetation would be overwhelmed by urban degradation or insignificant at low urbanization.     

Effects of Flow Augmentations in the Snake River Basin on Farms Profitability1

Abstract: For over 10 years, several species of salmon have been identified as either threatened or endangered in the Snake River Basin of Idaho. The United States Bureau of Reclamation, in cooperation with the National Marine Fisheries Service, has proposed a variety of plans to increase stream flows in the Snake River Basin to facilitate movement by juvenile salmon smolts to the ocean. This research examines two of the flow augmentation plans proposed by the Bureau of Reclamation as well as two alternative plans, one founded purely on existing priority‐based water rights and another geared toward minimizing the effects of flow augmentations on farms profitability. Results from a basin‐wide model of agricultural production in the Snake River Basin, the Snake River Agricultural Model, present evidence that (1) older water rights are used towards production of less valuable crops, (2) flow augmentation scenarios have unequal effects on farms profitability across agricultural regions within the basin, and (3) irrigation water is valued from US$4 to US$59 an acre‐foot.     

Characterizing Storm Hydrograph Rise and Fall Dynamics With Stream Stage Data1

Abstract: Storm‐flow transients (i.e., hydrograph rise and fall dynamics) may represent an important aspect of understanding streamflow dynamics. However, little is known about how temporal resolution of transient data and climate variability may color these potential indicators of hydrologic pattern or condition. Warm‐season stream stage and rainfall were monitored continuously (5 min) during the 2002 water year in eight tributaries of the Little Miami River (Ohio), which drain 17‐58 km² catchments. Rise rates generated using 5‐min data were different than those generated with mean daily data [calculated with the Indicators of Hydrologic Alteration (IHA) software], though fall rates were similar for fine and coarse temporal data. This result suggests that data with low temporal resolution may not be adequate to fully represent the dynamics of storm rise rates. Conversely, fall rates based on daily stage data (via IHA) were similar to those based on the 5‐min data, and so daily mean data may be appropriate for characterizing fall rates. We next analyzed the possible correlations between rainfall variability and storm‐flow stage dynamics. We derived rise and recession rates from storm stage hydrographs by assuming exponential rise and decay of a runoff peak. We found that raw rise rates (R_raw) were correlated with both the maximum rainfall rate and the time to the centroid of a rain event. We subsequently removed the trend based on these rainfall characteristics, which yielded new representations of rise rates abbreviated as R_rate and R_tcent, respectively, and that had lower variability than the uncorrected (raw) data. Fall rates were found to be independent of rainfall characteristics. Due to the predominant influence of stream hydrology upon aquatic biota and nutrient fluxes, our work suggests that these stage data analysis protocols can refine or otherwise reduce variability in these indices by accounting for relevant factors such as rainfall forcing. These protocols for derivation of transient indices should be tested for their potential to improve correlations between stream hydrology and temporally aligned biotic data and dissolved nutrient fluxes in streams.     

Soil sensitivity to acidification in Asia: status and prospects

Exceedance of steady-state critical loads for soil acidification is consistently found in southern China and parts of SE Asia, but there is no evidence of impacts outside of China. This study describes a methodology for calculating the time to effects for soils sensitive to acidic deposition in Asia under potential future sulfur (S), nitrogen (N), and calcium (Ca) emission scenarios. The calculations are matched to data availability in Asia to produce regional-scale maps that provide estimates of the time (y) it will take for soil base saturation to reach a critical limit of 20% in response to acidic inputs. The results show that sensitive soil types in areas of South, Southeast, and East Asia, including parts of southern China, Burma, Hainan, Laos, Thailand, Vietnam, and the Western Ghats of India, may acidify to a significant degree on a 0-50 y timescale, depending on individual site management and abiotic and biotic characteristics. To make a clearer assessment of risk, site-specific data are required for soil chemistry and deposition (especially base cation deposition); S and N retention in soils and ecosystems; and biomass harvesting and weathering rates from sites across Asia representative of different soil and vegetation types and management regimes. National and regional assessments of soils using the simple methods described in this paper can provide an appreciation of the time dimension of soil acidification-related impacts and should be useful in planning further studies and, possibly, implementing measures to reduce risks of acidification.     

Ozonation of oil sands process water removes naphthenic acids and toxicity

Naphthenic acids are naturally-occurring, aliphatic or alicyclic carboxylic acids found in petroleum. Water used to extract bitumen from the Athabasca oil sands becomes toxic to various organisms due to the presence of naphthenic acids released from the bitumen. Natural biodegradation was expected to be the most cost-effective method for reducing the toxicity of the oil sands process water (OSPW). However, naphthenic acids are poorly biodegraded in the holding ponds located on properties leased by the oil sands companies. In the present study, chemical oxidation using ozone was investigated as an option for mitigation of this toxicity. Ozonation of sediment-free OSPW was conducted using proprietary technology manufactured by Seair Diffusion Systems Inc. Ozonation for 50min generated a non-toxic effluent (based on the Microtox bioassay) and decreased the naphthenic acids concentration by approximately 70%. After 130min of ozonation, the residual naphthenic acids concentration was 2mgl(-1): <5% of the initial concentration in the filtered OSPW. Total organic carbon did not change with 130min of ozonation, whereas chemical oxygen demand decreased by approximately 50% and 5-d biochemical oxygen demand increased from an initial value of 2mgl(-1) to a final value of 15mgl(-1). GC-MS analysis showed that ozonation resulted in an overall decrease in the proportion of high molecular weight naphthenic acids (n> or = 22).     

Synthesis and analytical follow-up of the mineralization of a new fluorosurfactant prototype

Fluorinated surfactants have become essential in numerous technical applications due to their unparalleled effectiveness and efficiency. The environmental persistence of the non-biodegradable perfluorinated alkyl moiety has become a matter of concern. Therefore, it was searched for new molecules with chemically stable fluorinated end groups which can be microbially transformed into labile fluorinated substances. One prototype substance, 10-(trifluoromethoxy)decane-1-sulfonate, has shown biomineralization. Monitoring the formation of metabolites over time elucidated the mechanism of biotransformation. Analysis was performed utilizing liquid chromatography-single quadrupole mass spectrometry (LC-MS) and quadrupole-time of flight tandem mass spectrometry (QqTOF-MS). It was possible to distinguish between two major degradation pathways of the fluorinated alkylsulfonate derivative: (i) a desulfonation and subsequent oxidation and degradation of the alkyl chain being predominant and (ii) an insertion of oxygen with a subsequent cleavage and degradation of the molecule. The utilized trifluoromethoxy-endgroup resulted in instable trifluoromethanol after degradation of the alkyl chain, which led to a high degree of mineralization of the molecule.     

Effects of pig manure compost and nonionic-surfactant Tween 80 on phenanthrene and pyrene removal from soil vegetated with Agropyron elongatum

This paper evaluates the effects of pig manure compost (PMC) and Tween 80 on the removal of phenanthrene (PHE) and pyrene (PYR) from soil cultivated with Agropyron elongatum. Soils spiked with about 300mgkg(-1) of PHE and PYR were individually amended with 0%, 2.5%, 5% and 7.5% (dry wt) of PMC or 0, 20 and 100mgkg(-1) of Tween 80. Unplanted and sterile microcosms were prepared as the controls. PAH concentration, total organic matter (TOM), dissolved organic carbon (DOC), total heterotrophic and PAH degrading microbial populations in soil were quantified before and after 60d period. The results indicated that A. elongatum could significantly enhance PYR removal (from 46% to 61%) but had less impact on PHE removal (from 96% to 97%). Plant uptake of the PAHs was insignificant. Biodegradation was the key mechanism of PAH removals (<3% losses in the sterile control). Increase in PMC or Tween 80 levels increased the removal of PYR but not of PHE. Maximal PYR removal of 79% and 92% were observed in vegetated soil receiving 100mgkg(-1) Tween 80 and 7.5% PMC, respectively. Enhanced PYR removal in soil receiving PMC could be explained by the elevated levels of DOC, TOM and microbial populations as suggested by Pearson correlation test. While the positive effect of Tween 80 on PYR removal could probably due to its capacities to enhance PYR bioavailability in soil. This paper suggests that the addition of either PMC or nonionic-surfactant Tween 80 could facilitate phytoremediation of PAH contaminated soil.     

Regio- and stereoselective isomerization of hexabromocyclododecanes (HBCDs): kinetics and mechanism of gamma- to alpha-HBCD isomerization

Hexabromocyclododecanes (HBCDs) are high production volume chemicals (>20000 ty(-1)) used as flame retardants for plastics and textiles. Lately, we reported on the stereoselective isomerization of beta-HBCDs. Herein we present insights into the mechanism and kinetics of (+)gamma- to (+)alpha- and of (-)gamma- to (-)alpha-HBCD isomerization. Only two of the six bromine atoms migrated, indicating that rearrangements of gamma- to alpha-HBCDs are regio- and stereoselective as well. The apparent first-order isomerization rate constants increased from 0.0013 to 0.0031 to 0.0070 min(-1) at 120, 130, and 140 degrees C, respectively, corresponding to half-lives of 540, 230, and 99 min. Thus, a thermal treatment of materials containing gamma-HBCDs at temperatures >100 degrees C may induce the formation of alpha-HBCDs and, hence, may alter the diastereomeric ratio of a HBCD mixture. The inversion of vicinal dibromides in like-configurations (RR/SS) prevailed, whereas unlike-configurations (RS/SR) were not affected. An intramolecular, stereoselective migration of neighboring bromine atoms via a four-center transition state would explain the observed stereoisomer pattern and first-order kinetics. Despite the fact that vicinal dibromides in HBCDs prefer synclinal (gauche) conformations, antiperiplanar (staggered) conformations are assumed to facilitate concerted 1.2-shifts of both bromine atoms. A conformation analysis revealed that under kinetic control, only those bromine atoms in the more flexible part of the molecules are migrating, whereas those in the conserved triple-turn motive were not affected. Thus, this structural motive, common to all alpha-, beta-, and gamma-HBCDs, is more rigid and less reactive than the flexible part, containing the reacting dibromides in like-configurations.     

NMR study of the humification process during sewage sludge treatment

Humic acids, extracted from sludge at the biologic-mechanical sewage treatment plant in Jastrzebie Zdroj, have been investigated by means of (1)H, (13)C and (31)P NMR spectroscopy. Sludge samples for studies were taken from the primary settling tank, the nitrification chamber, the digestion chamber and the sludge drying beds. The (1)H NMR analysis of humic acid extracted from sludge at various stages of sewage treatment confirmed the presence of the functional groups that are characteristic for humic substances, and the analysis showed changes in their relative intensities. The (13)C NMR indicated that the aromatisation of the humic acid increased during sewage treatment. Moreover, the analysis of the (31)P NMR spectra allowed us to observe the changes in the phosphorus groups of the studied humic acids.     

Solubility of toluene, benzene and TCE in high-microbial concentration systems

We report measurements of solubility limits for benzene, toluene, and TCE in systems that contain varying levels of biomass up to 0.13 g mL⁻¹ for TCE and 0.25 g mL⁻¹ for benzene and toluene. The solubility limit increased from 21 to 48 mM when biomass (in the form of yeast) was added to aqueous batch systems containing benzene. The toluene solubility limit increased from 4.9 to greater than 20 mM. For TCE, the solubility increased from 8 mM to more than 1000 mM. Solubility for TCE (trichloroethylene) was most heavily impacted by biomass levels, changing by two orders of magnitude as the microbial concentrations approach those in biofilms.