Chromium speciation in river sediment pore water contaminated by tannery effluent

Cr(VI) is far more soluble and toxic than Cr(III). Sediment pore water was investigated in a river adjacent to the property of a large former tannery, into which Cr-contaminated effluent was discharged over a 55-year period, and where extremely high Cr concentrations have been found in the sediments. Dialysis cells, or peepers, were used to generate depth profiles of Cr concentration in sediment pore water. Samples were analyzed for total Cr using inductively coupled plasma-mass spectrometry (ICP-MS) and for Cr species using high performance liquid chromatography (HPLC)-ICP-MS. The results show an absence of Cr(VI) in all samples. Furthermore, incomplete recovery of Cr(VI) added to the samples collected at the locations with highest sediment Cr concentrations indicate strong reducing conditions at those locations, which are not conducive to the presence of Cr(VI).     

Response of phytoplankton communities to acidification and recovery in Killarney Park and the Experimental Lakes Area,Ontario

It has been widely speculated that controls of SO2 emissions would stimulate recovery of acidified freshwater lakes in Canada, the United States and Europe. Phytoplankton communities from 22 lakes near Killarney Park Ontario, covering a pH range from 4.5-7.7, were studied from 1998-2000 and compared to data from experimentally acidified (pH decreased 6.7 to 4.5) and recovered (pH increased to 6.0) Lake 302 South at the Experimental Lakes Area (ELA), northwestern Ontario to assess recovery from acidification. Based on historical data, pH levels have rebounded to above 6.0 in several lakes in the Killarney area that were previously acidified to pH 5.0-5.5. Phytoplankton biomass was not correlated to pH, but there was a highly significant relationship between species richness and pH. Recovery trajectories were observed in a subset of 6 lakes, combining species diversity data from the present study with historical data. Correspondence analysis indicated that several of the lakes that experienced increased pH have shifted towards phytoplankton assemblages typical of circumneutral environments.     

Development and validation of a method for analysis of "dioxin-like" PCBs in environmental samples from the steel industry

A method, previously used for determination of 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs), has been modified for quantitative analysis of "dioxin-like" polychlorobiphenyls (PCBs) in environmental samples from the steel industry. The existing sample clean-up procedure, involving liquid chromatography on multi-layered silica and Florisil columns, has been extended to include a third chromatography stage on a basic alumina stationary phase. The additional clean-up stage is required for PCB analysis in order to eliminate interferences from relatively large concentrations of saturated cyclic and aliphatic hydrocarbons. Samples were analysed for WHO-12 congeners using high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS) and standard solutions of the method US EPA 1668A. Replicate analysis of method blanks revealed background contamination for PCBs 118, 105 and 77, which are generally abundant in ambient air. These contaminants were taken into account using a subtraction method. The entire procedure was validated by replicate analysis (N = 3) of a certified reference sediment. The RSD for each WHO-12 congener was below 15%, 13C12-labelled PCB internal standard recoveries were in the range 70-95%. A waste dust sample collected in the electrostatic precipitator of a UK sinter plant was analysed for determination of PCDD/Fs and WHO-12 PCBs and exhibited a PCDD/F I-TEQ of 148.5 +/- 21.2 ngkg(-1) and a WHO-TEQ of 7.2 +/- 1.5 ngkg(-1). WHO-12 congeners contributed only 4.6% to the overall TEQ and PCB 126 was the major congener contributing to the WHO-TEQ (96%). The contribution to the overall TEQ of the waste dust sample was mainly attributed to PCDF followed by PCDD, which accounted for 86.6% and 8.7% to the overall TEQ, respectively.     

Laboratory leaching studies of oryzalin and diuron through three undisturbed vineyard soil columns

The leaching of diuron and oryzalin through undisturbed soil columns was studied in the laboratory using three vineyard soils from Vosne-Romanée (Burgundy): a rendosol, a calcosol and a vegetated calcosol. After 845 mm of simulated rainfall in 15 days, soil leachates contained higher amounts of diuron (3.2%, 11.8% and 18.8% of applied diuron, respectively) than oryzalin (0.2%, 4.9%, 3.7%, respectively). A greater proportion of soil extractable residues was obtained for diuron (42.5%, 26.8% and 32.2%, respectively) than for oryzalin (14.7%, 12% and 15.5%, respectively). The greater mobility of diuron might be related to its higher water solubility (36.4 mgl(-1) compared with 2.6 mgl(-1) for oryzalin) and smaller adsorption coefficient (400 lkg(-1), compared with 700-1100 lkg(-1) for oryzalin). The mobility of the two herbicides was greater in the two calcosols than in the rendosol, not only due to different organic carbon contents but also different soil textures and structures.     

Development of a regenerable system employing silica-titania composites for the recovery of mercury from end-box exhaust at a chlor-alkali facility

The release of mercury to the environment is of particular concern because of its volatility, persistence, and tendency to bioaccumulate. The recovery of mercury from end-box exhaust at chlor-alkali facilities is important to prevent release into the environment and reduce emissions as required by NESHAP (National Emission Standards for Hazardous Air Pollutants). A pilot-scale photocatalytic reactor packed with silica-titania composite (STC) pellets was tested at a chloralkali facility over a 3-month period. This pilot reactor treated up to 10 ft3/min (ACFM) of end-box exhaust and achieved 95% removal. The pilot reactor was able to maintain excellent removal efficiency even with large fluctuations in influent mercury concentration (400-1600 microg/ft3). The STC pellets were regenerated ex situ by regeneration with hydrochloric acid and performed similarly to virgin STC pellets when returned to service. On the basis of these promising results, two full-scale reactors with in situ regeneration capabilities were installed and operated. After optimization, these reactors performed similarly to the pilot reactor. A cost analysis was performed comparing the treatment costs (i.e., cost per pound of mercury removed) for sulfur-impregnated activated carbon and the STC system. The STC proved to be both technologically and economically feasible for this installation.     

Spatial variability of carbonaceous aerosols and associated source tracers in two cites in the Midwestern United States

Semi-continuous and 24-h averaged measurements of fine carbonaceous aerosols were made concurrently at three sites within each of two U.S. Midwestern Cities; Detroit, Michigan and Cleveland, Ohio; during two, one-month intensive campaigns conducted in July of 2007 and January & February of 2008. A comparison of 24-h measurements revealed substantial intra-urban variability in carbonaceous aerosols consistent with the influence of local sources, and excesses in both PM_2.5 organic carbon (OC) and elemental carbon (EC) were identified at individual sites within each city. High time-resolved black carbon (BC) measurements indicated that elemental carbon concentrations were higher at sites adjacent to freeways and busy surface streets, and temporal patterns suggested that excess EC at sites adjacent to freeways was dominated by mobile source emissions while excesses in EC away from traffic corridors was dominated by point/area source emissions. The site-to-site variability in OC concentrations was approximately 7% within the neighborhood scale (0.5–4 km) and between 4 and 27% at the urban scale (4–100 km). In contrast, measurements of organic source tracers, in conjunction with a Chemical Mass Balance (CMB) source-apportionment model, indicated that the spatial variation in the contribution of both mobile and stationary sources to PM_2.5 OC often exceeded the variation in OC mass concentration by a factor of 3 or more. Markers for mobile sources, biomass smoke, natural gas, and coal combustion differed by as much as 60% within the neighborhood scale and by greater than 200% within the urban scale. The observations made during this study suggest that the urban excess of carbonaceous aerosols is much more complex than has been previously reported and that a more rigorous, source-oriented approach should be taken in order to assess the risk associated with exposure to carbonaceous aerosols within the industrialized environments of the Midwestern United States.     

The fate of estrogenic hormones in an engineered treatment wetland with dense macrophytes.

Recently, the estrogenic hormones 17beta-estradiol (E2) and 17alpha-ethinyl estradiol (EE2) have been detected in municipal wastewater effluent and surface waters at concentrations sufficient to cause feminization of male fish. To evaluate the fate of steroid hormones in an engineered treatment wetland, lithium chloride, E2, and EE2 were added to a treatment wetland test cell. Comparison of hormone and tracer data indicated that 36% of the E2 and 41% of the EE2 were removed during the cell's 84-h hydraulic retention time (HRT). The observed attenuation was most likely the result of sorption to hydrophobic surfaces in the wetland coupled with biotransformation. Sorption was indicated by the retardation of the hormones relative to the conservative tracer. Biotransformation was indicated by elevated concentrations of the E2 metabolite, estrone. It may be possible to improve the removal efficiency by increasing the HRT or the density of plant materials.     

A preliminary in vitro assessment of GroBiotic-A, brewer's yeast and fructooligosaccharide as prebiotics for the red drum Sciaenops ocellatus

This study examined the effects of brewers yeast, fructooligosaccharide (FOS), and GroBiotic-A, a mixture of partially autolyzed brewers yeast, dairy components and dried fermentation products, on the intestinal microbial community of red drum, Sciaenops ocellatus. Gastrointestinal (GI) tracts were aseptically removed from three sub-adult red drum previously maintained on a commercial diet and placed in an anaerobic chamber. Intestinal contents were removed, diluted and incubated in vitro in one of four liquid media: normal diet alone, diet + 2% (w/w) GroBiotic-A, diet + 2% brewers yeast, and diet + 2% FOS. After 24 and 48 h of incubation at 25 degrees C, supernatants were removed for volatile fatty acid (VFA) analysis and DNA was extracted for denaturing gradient gel electrophoresis (DGGE) analysis. Polymerase chain reaction (PCR) was performed on a highly conserved region of M 16S rDNA and the amplicons were subjected to DGGE. The microbial community (MC) fingerprint was used to distinguish microbial populations. The intestinal contents incubated with GroBiotic-A had significantly (P<0.05) higher acetate and total VFA concentrations at 48 h compared to the other treatments. DGGE analysis demonstrated that the microbial community was significantly altered by Grobiotic-A and brewers yeast.     

Hepatic monooxygenase (CYP1A and CYP3A) and UDPGT enzymatic activities as biomarkers for long-term carbofuran exposure in tench (Tinca tinca L)

The effect of a long-term exposure of tenchs to different concentrations (10 and 100 micro g/L) of the pesticide carbofuran has been evaluated. Microsomal hepatic cytochrome P450 subfamily 1A (CYP1A) and 3A (CYP3A) activities, as well as the phase II enzyme uridine diphospho-glucuronosyltransferase (UDPGT) activity were evaluated as adequate biomarkers of fish exposure to environmentally relevant concentrations of the pesticide carbofuran in freshwater ecosystems. A clear time-dependent inhibition of both CYP1A and UDPGT activities was observed in fish exposed to the highest dose of carbofuran with respect to controls, whereas in the case of CYP3A activity, values of exposed animals did not show a clear pattern of alteration during the experiment. The results of the present study demonstrated that hepatic CYP1A and UDPGT activities from tench could be considered as sensitive biomarkers for carbamate pesticides in polluted water, thus allowing future and ecologically relevant biomonitoring studies with this species.