Temporal variation of trace metal geochemistry in floodplain lake sediment subject to dynamic hydrological conditions

Climate change and land use may significantly influence metal cycling in dynamic river systems. We studied temporal variation of sediment characteristics in a floodplain lake, including concentrations of dissolved organic carbon, acid volatile sulfide and trace metals. The sampling period included a severe winter inundation and a dramatic water level drop during summer. Temporal changes were interpreted using multivariate analysis and chemical equilibrium calculations. Metal concentrations in sediment increased with depth, indicating a gradual improvement of sediment quality. In contrast, dissolved metal concentrations were highest in top layers due to mobilization from oxyhydroxides and precipitation with sulfides in deeper layers. Inundation had a mobilizing effect as it stimulated resuspension and oxygenation of sediment top layers. Water table lowering combined with organic matter decomposition led to immobilization due to sulfide formation. The chemistry of the sediments was consistent with model calculations, especially for macro-elements. The results illustrate the importance of seasonality for metal risk assessment.     

Modeling mercury fluxes and concentrations in a Georgia watershed receiving atmospheric deposition load from direct and indirect sources

This paper presents a modeling analysis of airborne mercury (Hg) deposited on the Ochlockonee River watershed located in Georgia. Atmospheric deposition monitoring and source attribution data were used along with simulation models to calculate Hg buildup in the subwatershed soils, its subsequent runoff loading and delivery through the tributaries, and its ultimate fate in the mainstem river. The terrestrial model calculated annual watershed yields for total Hg ranging from 0.7 to 1.1 microg/m2. Results suggest that approximately two-thirds of the atmospherically deposited Hg to the watershed is returned to the atmosphere, 10% is delivered to the river, and the rest is retained in the watershed. A check of the aquatic model results against survey data showed a reasonable agreement. Comparing observed and simulated total and methylmercury concentrations gave root mean square error values of 0.26 and 0.10 ng/L, respectively, in the water column, and 5.9 and 1 ng/g, respectively, in the upper sediment layer. Sensitivity analysis results imply that mercury in the Ochlockonee River is dominated by watershed runoff inputs and not by direct atmospheric deposition, and that methylmercury concentrations in the river are determined mainly by net methylation rates in the watershed, presumably in wetted soils and in the wetlands feeding the river.     

Organochlorine residues in odontocete species from the southeast coast of India

Blubber from bottle-nose dolphins, spinner dolphins, humpback dolphin (Tursiops truncatus, Stenella longirostris and Sousa chinensis) were collected from the Bay of Bengal (southeast coast of India) and analyzed for the organochlorine pesticides hexachlorocyclohexane (HCHs), p,p'-dichlorodiphenyl trichloroethane (DDTs), and polychlorinated biphenyls (PCBs). All nine specimens analyzed contained considerable levels of all the three chemical classes where DDT was in the range of 3330-23330 ng/g; HCHs in the range of 95-765 ng/g; and PCBs in the range of 210-1220 ng/g (wet weight basis). The reasons for this and the variations in the isomer pattern of HCHs and DDT and its metabolites in marine mammal tissues are discussed.     

Photo-Fenton-assisted ozonation of p-Coumaric acid in aqueous solution

The degradation of p-Coumaric acid present in olive oil mill wastewater was investigated as a pretreatment stage to obtain more easily biodegradable molecules, with lower toxicity that facilitates subsequent anaerobic digestion. Thus, photo-Fenton-assisted ozonation has been studied and compared with ozonation at alkaline pH and conventional single ultraviolet (UV) and acid ozonation treatments. In the combined process, the overall kinetic rate constant was split into various components: direct oxidation by UV light, direct oxidation by ozone and oxidation by hydroxyl radicals. Molecular and/or radical ozone reaction was studied by conducting the reaction in the presence and absence of tert-butylalcohol at pHs 2, 7 and 9. Ozone oxidation rate increases with pH or by the addition of Fenton reagent and/or UV radiation due to generation of hydroxyl radicals, *OH. Hydrogen peroxide and ferrous ion play a double role during oxidation since at low concentrations they act as initiators of hydroxyl radicals but at high concentrations they act as radical scavengers. Finally, the additional levels of degradation by formation of hydroxyl radicals have been quantified in comparison to the conventional single processes and an equation is proposed for the reaction rate as a function of studied operating variables.     

The impact of pumped water from a de-watered Magnesian limestone quarry on an adjacent wetland: Thrislington, County Durham, UK

Although quarrying is often cited as a potential threat to wetland systems, there is a lack of relevant, quantitative case studies in the literature. The impact of pumped groundwater discharged from a quarry into a wetland area was assessed relative to reference conditions in an adjacent fen wetland that receives only natural runoff. Analysis of vegetation patterns at the quarry wetland site, using Detrended Correspondence Analysis and the species indicator values of Ellenberg, revealed a clear disparity between community transitions in the quarry wetland and the reference site. Limited establishment of moisture-sensitive taxa, the preferential proliferation of robust wetland species and an overall shift towards lower species diversity in the quarry wetland were explicable primarily by the physico-chemical environment created by quarry dewatering. This encompassed high pH (up to 12.8), sediment-rich effluent creating a nutrient-poor substrate with poor moisture retention in the quarry wetland, and large fluctuations in water levels.     

Bioconversion of olive-mill dry residue by Fusarium lateritium and subsequent impact on its phytotoxicity

The present study investigated the ability of the non-pathogenic fungus Fusarium lateritium to either degrade or modify aromatic substances in olive-mill dry residue (DOR) and to reduce its phytotoxicity. The 80% reduction of ethylacetate extractable phenols in DOR colonized by the fungus for 20 weeks appeared to be due to polymerization reactions of phenol molecules as suggested by mass-balance ultrafiltration and size-exclusion chromatography experiments. Several lignin-modifying oxidases, including laccase, Mn-peroxidase and Mn-inhibited peroxidase were detected in F. lateritium solid-state cultures. Tests performed with tomato seedlings in soils containing 6% (w/w) sterilized non-inoculated DOR showed that the waste was highly phytotoxic. By contract, F. lateritium growth on DOR for 20 weeks led to a complete removal of the waste toxicity and to a higher shoot dry weight of tomato plants than that obtained in the absence of DOR.     

Degradation of 2,4,6-trinitrotoluene by selected helophytes

Four emergent plants (helophytes, synonyms emersion macrophytes, marsh plants, etc.) Phragmites australis, Juncus glaucus, Carex gracillis and Typha latifolia were successfully used for degradation of TNT (2,4,6-trinitrotoluene) under in vitro conditions. The plants took up and transformed more than 90% of TNT from the medium within ten days of cultivation. The most efficient species was Ph. australis which took up 98% of TNT within ten days. The first stable degradation products 4-amino-2,6-dinitrotoluene (4-ADNT) and 2-amino-4,6-dinitrotoluene (2-ADNT) were identified and analysed during the cultivation period. [14C] TNT was used for the detection of TNT degradation products and their compartmentalization in plant tissues after two weeks of cultivation. Forty one percent of 14C was detected as insoluble or bound in cell structures: 34% in roots and 8% in the aerial parts. These results open the perspective of using the above-mentioned plants for the remediation of TNT contaminated waters.     

Tylosin sorption to silty clay loam soils, swine manure, and sand

The objectives of this study were to assess sorption and desorption of tylosin, a macrolide antimicrobial chemical used in swine, cattle, and poultry production, in three silty clay loam soils of South Dakota and compare soil sorption to sand and manure sorption. The silty clay loam soils, from a toposequence in eastern South Dakota, standardized sand samples, and swine manure were used in 24-h batch sorption studies with tylosin concentrations ranging from 25 to 232 micro mole/L. Desorption from soil was conducted over a four-day period. Partition coefficients, based on the Freundlich isotherm (K(f)) or K(d) values, were calculated. K(f) values for the silty clay loams were similar, not influenced by landscape position, and averaged 1,350 with isotherm slopes ranging from 0.85 to 0.93. K(f) values for sand were dependent on solution/sand ratios and pH, ranging from 1.4 to 25.1. K(d) values of manure were dependent on the solution type and ranged from 840 L/kg with urine to about 175 L/kg when sorbed from water. Desorption of tylosin from each soil over the four-day period was < 0.2% of the amount added. The soils' high K(f) values and low desorption amounts suggest that once tylosin is in these soils, leaching to lower depths may not occur. However, this does not preclude runoff with soil eroded particles. If tylosin reaches a sand aquifer, through bypass flow or other mechanism(s), movement in the aquifer most likely would occur.     

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.     

Inter- and intra-species variation in acute zinc tolerance of field-collected cladoceran populations

Acute zinc toxicity was assessed for 10 freshwater cladoceran species collected in six different ecosystems across Europe and for two standard laboratory-reared species (Daphnia magna and Ceriodaphnia dubia). The collected organisms belonged to five different genera: Daphnia (subgenus Daphnia and Ctenodaphnia), Ceriodaphnia, Simocephalus, Acroperus and Chydorus. The 48-h EC50 of the field-collected organisms tested in standard laboratory water ranged from 375+/-141 to 4314+/-1513 microg Znl(-1). The laboratory clone of D. magna was less sensitive than the majority of the field-collected species, while our laboratory Ceriodaphnia dubia was the second most sensitive. Considerable inter-species variation was found within the genus of Ceriodaphnia (factor 6) and within the genus Daphnia (factor 8). Among the different (sub)genera tested, Chydorus and Ctenodaphnia were significantly more tolerant than the others (up to a factor 3 difference). A significant positive relationship (r2=0.67, p<0.05) between the mean cladoceran 48-h EC50 and the ambient zinc concentration of the different aquatic systems was demonstrated, suggesting a role of acclimation and/or adaptation. No significant correlation between the acute zinc tolerance and the length of the organisms was found.