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Seasonal exposures to triazine and other pesticides in surface waters in the western Highveld corn-production region in South Africa

The objective of this study was to characterize concentrations of atrazine, terbuthylazine, and other pesticides in amphibian habitats in surface waters of a corn-production area of the western Highveld region (North-West Province) of South Africa. The study was conducted from November 2001 to June 2002, coinciding with the corn-production season. Pesticide residues were measured at regular intervals in surface water from eight ponds, three in a non-corn-growing area (NCGA) and five within the corn-growing area (CGA). Measured atrazine concentrations differed significantly among sites and between samples. In the five CGA sites, the maximum atrazine concentrations measured during the study ranged from 1.2 to 9.3 ??g/L. Although no atrazine was recorded as being applied in the catchment of the three NCGA sites, maximum concentrations from 0.39 to 0.84 ??g/L were measured during the study, possibly as a result of atmospheric transport. Maximum measured concentrations of terbuthylazine ranged from 1.22 to 2.1 ??g/L in the NCGA sites and from 1.04 to 4.1 ??g/L in the CGA sites. The source of terbuthylazine in the NCGA sites may have been in use other than in corn. The triazine degradation products, deisopropylatrazine (DIA) and deethylatrazine (DEA) and diaminochlorotriazine (DACT) were also found in water from both the CGA and NCGA sites. Concentrations of DIA were ??? 1 ??g/L throughout the season, while DEA concentrations were mostly <0.5 ??g/L before planting but increased after planting and application of herbicides to concentrations > 2 ??g/L in some locations. Concentrations of DACT were highly variable (LOD to 8 ??g/L) both before and after planting and application, suggesting that they resulted from historical use of triazines in the area. Other herbicides such as simazine and acetochlor were only detected infrequently and pesticides such as S-metolachlor, cypermethrin, monocrotophos, and terbuphos, known to be used in the CGA, were not detected in any of the samples. Because of dilution by higher than normal rainfall in the study period, these concentrations may not be predictive of those in years of normal rainfall. ?? 2004 Elsevier Ltd. All rights reserved.

Environmental Pollution↗

Acid neutralization within limestone sand reactors receiving coal mine drainage

Pulsed bed treatment of acid mine drainage (AMD) uses CO2 to accelerate limestone dissolution and intermittent fluidization to abrade and carry away metal hydrolysis products. Tests conducted with a prototype of 60 L/min capacity showed effective removal of H+ acidity over the range 196-584 mg/L (CaCO3) while concurrently generating surplus acid neutralization capacity. Effluent alkalinity (mg/L CaCO3) rose with increases in CO2 (DC, mg/L) according to the model Alkalinity = 31.22 + 2.97(DC)0.5, where DC was varied from 11-726 mg/L. Altering fluidization and contraction periods from 30 s/30 s to 10 s/50 s did not influence alkalinity but did increase energy dissipation and bed expansion ratios. Field trials with three AMD sources demonstrated the process is capable of raising AMD pH above that required for hydrolysis and precipitation of Fe3+ and Al3+ but not Fe2+ and Mn2+. Numerical modeling showed CO2 requirements are reduced as AMD acidity increases and when DC is recycled from system effluent. ?? 2005 Elsevier Ltd. All rights reserved.

Environmental Pollution↗

Photodegradation of polyaromatic hydrocarbons in passive air samplers: Field testing different deployment chambers

Semi-permeable membrane devices (SPMDs) were loaded with deuterated anthracene and pyrene as performance reference compounds (PRCs) and deployed at a test site in four different chambers (open and closed box chamber, bowl chamber and cage chamber) for 29 days. The losses of PRCs and the uptake of polyaromatic hydrocarbons (PAHs) from the ambient air were quantified. UV-B levels measured in each deployment chamber indicated that SPMDs would be exposed to the most UV-B in the cage chamber and open box chamber. Significantly less PAHs were quantified in SPMDs deployed in the cage chamber and open box chamber compared to samplers from the other two chambers, suggesting that photodegradation of PAHs had occurred. The loss of PRCs confirmed these results but also showed that photodegradation was occurring in the closed box chamber. The bowl chamber appears to provide the best protection from the influence of direct photodegradation. ?? 2006 Elsevier Ltd. All rights reserved.

Environmental Pollution↗

Dacthal and chlorophenoxy herbicides and chlorothalonil fungicide in eggs of osprey (Pandion haliaetus) from the Duwamish-Lake Washington-Puget Sound area of Washington state, USA

Current-use chlorophenoxy herbicides including 2,4-dichlorophenoxyacetic acid, dicamba, triclopyr, dicamba, dimethyl tetrachloroterephthalate (DCPA or dacthal), and the metabolite of pyrethroids, 3-phenoxybenzoic acid (3-PBA), and the fungicide, chlorothalonil, were investigated in the eggs of osprey (Pandion haliaetus) that were collected from 15 sites from five study areas Puget Sound/Seattle area of Washington State, USA. DCPA differs from acidic chlorophenoxy herbicides, and is not readily hydrolyzed to free acid or acid metabolites, and thus we developed a new method. Of the 12 chlorophenoxy herbicides and chlorothalonil analyzed only DCPA could be quantified at six of these sites (2.0 to 10.3 pg/g fresh weight). However, higher levels (6.9 to 85.5 pg/g fresh weight) of the unexpected DCPA structural isomer, dimethyl tetrachlorophthalate (diMe-TCP) were quantified in eggs from all sites. diMe-TCP concentrations tended to be higher in eggs from the Everett Harbor area. As diMe-TCP is not an industrial product, and not commercially available, the source of diMe-TCP is unclear. Regardless, these findings indicate that DCPA and diMe-TCP can be accumulated in the food chain of fish-eating osprey, and transferred in ovo to eggs, and thus may be of concern to the health of the developing chick and the general reproductive health of this osprey population. ?? 2006 Elsevier Ltd. All rights reserved.

Environmental Pollution↗

Seasonal and spatial patterns of metals at a restored copper mine site. I. Stream copper and zinc

Seasonal and spatial variations in metal concentrations and pH were found in a stream at a restored copper mine site located near a massive sulfide deposit in the Foothill copper-zinc belt of the Sierra Nevada, California. At the mouth of the stream, copper concentrations increased and pH decreased with increased streamflow after the onset of winter rain and, unexpectedly, reached extreme values 1 or 2 months after peaks in the seasonal hydrographs. In contrast, aqueous zinc and sulfate concentrations were highest during low-flow periods. Spatial variation was assessed in 400 m of reach encompassing an acidic, metal-laden seep. At this seep, pH remained low (2-3) throughout the year, and copper concentrations were highest. In contrast, the zinc concentrations increased with downstream distance. These spatial patterns were caused by immobilization of copper by hydrous ferric oxides in benthic sediments, coupled with increasing downstream supply of zinc from groundwater seepage.

Environmental Pollution↗

Metal accumulation in the earthworm Lumbricus rubellus. Model predictions compared to field data

The mechanistic bioaccumulation model OMEGA (Optimal Modeling for Ecotoxicological Applications) is used to estimate accumulation of zinc (Zn), copper (Cu), cadmium (Cd) and lead (Pb) in the earthworm Lumbricus rubellus. Our validation to field accumulation data shows that the model accurately predicts internal cadmium concentrations. In addition, our results show that internal metal concentrations in the earthworm are less than linearly (slope < 1) related to the total concentration in soil, while risk assessment procedures often assume the biota-soil accumulation factor (BSAF) to be constant. Although predicted internal concentrations of all metals are generally within a factor 5 compared to field data, incorporation of regulation in the model is necessary to improve predictability of the essential metals such as zinc and copper. ?? 2006 Elsevier Ltd. All rights reserved.

Environmental Pollution↗

Effects of Phos-Chek® G75-F and Silv-Ex® on red-winged blackbird ( Agelaius phoeniceus ) embryos

Effects of field application levels of wildfire control chemicals, Phos-Chek ® G75-F (PC) and Silv-Ex ® (SE), were examined on red-winged blackbird ( Agelaius phoeniceus ) embryos. Embryos were more sensitive to PC and SE when eggs were immersed for 10 s at an early developmental stage (days 3–5 of incubation) than at a later stage (days 6–9 of incubation). The LC 50 (concentration causing 50% mortality) for early stage embryos exposed to PC was 213.3 g/L (slope = 1.6; 95% confidence interval [CI] = 129.1–326.1). The no observed effect concentration (NOEC) was below 135 g PC/L, which caused a significant increase in embryonic mortality and represents the lowest field coverage level of 1 gal/100 feet 2 . The LC 50 for early stage embryos exposed to SE was 19.8 g/L (slope = 1.5; 95% CI = 11.7–52.2). Significant mortality was observed at 10 g SE/L and marginal at 7.5 g SE/L with an apparent NOEC around 5 g SE/L. Neither chemical resulted in apparent developmental malformations.

Environmental Pollution↗

Comparative toxicity of chlorpyrifos, diazinon, malathion and their oxon derivatives to larval Rana boylii

Organophosphorus pesticides (OPs) are ubiquitous in the environment and are highly toxic to amphibians. They deactivate cholinesterase, resulting in neurological dysfunction. Most chemicals in this group require oxidative desulfuration to achieve their greatest cholinesterase-inhibiting potencies. Oxon derivatives are formed within liver cells but also by bacterial decay of parental pesticides. This study examines the toxicity of chlorpyrifos, malathion and diazinon and their oxons on the foothill yellow-legged frog (Rana boylii). R. boylii is exposed to agricultural pesticides in the California Central Valley. Median lethal concentrations of the parental forms during a 96 h exposure were 3.00 mg/L (24 h) for chlorpyrifos, 2.14 mg/L for malathion and 7.49 mg/L for diazinon. Corresponding oxons were 10 to 100 times more toxic than their parental forms. We conclude that environmental concentrations of these pesticides can be harmful to R. boylii populations. ?? 2006 Elsevier Ltd. All rights reserved.

Environmental Pollution↗

Influence of fipronil compounds and rice-cultivation land-use intensity on macroinvertebrate communities in streams of southwestern Louisiana, USA

Laboratory tests of fipronil and its degradation products have revealed acute lethal toxicity at very low concentrations (LC50) of <0.5 ??g/L to selected aquatic macroinvertebrates. In streams draining basins with intensive rice cultivation in southwestern Louisiana, USA, concentrations of fipronil compounds were an order of magnitude larger than the LC50. The abundance (?? = -0.64; p = 0.015) and taxa richness (r2 = 0.515, p < 0.005) of macroinvertebrate communities declined significantly with increases in concentrations of fipronil compounds and rice-cultivation land-use intensity. Macroinvertebrate community tolerance scores increased linearly (r2 = 0.442, p < 0.005) with increases in the percentage of rice cultivation in the basins, indicating increasingly degraded stream conditions. Similarly, macroinvertebrate community-tolerance scores increased rapidly as fipronil concentrations approached about 1 ??g/L. Pesticide toxicity index determinations indicated that aquatic macroinvertebrates respond to a gradient of fipronil compounds in water although stream size and habitat cannot be ruled out as contributing influences.

Environmental Pollution↗

Influence of variable chemical conditions on EDTA-enhanced transport of metal ions in mildly acidic groundwater

Adsorption of Ni and Pb on aquifer sediments from Cape Cod, Massachusetts, USA increased with increasing pH and metal-ion concentration. Adsorption could be described quantitatively using a semi-mechanistic surface complexation model (SCM), in which adsorption is described using chemical reactions between metal ions and adsorption sites. Equilibrium reactive transport simulations incorporating the SCMs, formation of metal-ion-EDTA complexes, and either Fe(III)-oxyhydroxide solubility or Zn desorption from sediments identified important factors responsible for trends observed during transport experiments conducted with EDTA complexes of Ni, Zn, and Pb in the Cape Cod aquifer. Dissociation of Pb-EDTA by Fe(III) is more favorable than Ni-EDTA because of differences in Ni- and Pb-adsorption to the sediments. Dissociation of Ni-EDTA becomes more favorable with decreasing Ni-EDTA concentration and decreasing pH. In contrast to Ni, Pb-EDTA can be dissociated by Zn desorbed from the aquifer sediments. Variability in adsorbed Zn concentrations has a large impact on Pb-EDTA dissociation.

Environmental Pollution↗

Mercury and other element exposure to tree swallows (Tachycineta bicolor) nesting on Lostwood National Wildlife Refuge, North Dakota

Elevated mercury concentrations in water were reported in the prairie wetlands at Lostwood National Wildlife Refuge, ND. In order to determine whether wildlife associated with these wetlands was exposed to and then accumulated higher mercury concentrations than wildlife living near more permanent wetlands (e.g. lakes), tree swallow (Tachycineta bicolor) eggs and nestlings were collected from nests near seasonal wetlands, semi-permanent wetlands, and lakes. Mercury concentrations in eggs collected near seasonal wetlands were higher than those collected near semi-permanent wetlands or lakes. In contrast, mercury concentrations in nestling livers did not differ among wetland types. Mercury and other element concentrations in tree swallow eggs and nestlings collected from all wetlands were low. As suspected from these low concentrations, mercury concentrations in sample eggs were not a significant factor explaining the hatching success of the remaining eggs in each clutch.

Environmental Pollution↗

Influence of natural dissolved organic carbon on the bioavailability of mercury to a freshwater alga

Bioavailability of mercury (Hg) to Selenastrum capricornutum was assessed in bioassays containing field-collected freshwater of varying dissolved organic carbon (DOC) concentrations. Bioconcentration factor (BCF) was measured using stable isotopes of methylmercury (MeHg) and inorganic Hg(II). BCFs for MeHg in low-DOC lake water were significantly larger than those in mixtures of lake water and high-DOC river water. The BCF for MeHg in rainwater (lowest DOC) was the largest of any treatment. Rainwater and lake water also had larger BCFs for Hg(II) than river water. Moreover, in freshwater collected from several US and Canadian field sites, BCFs for Hg(II) and MeHg were low when DOC concentrations were >5 mg L-1. These results suggest high concentrations of DOC inhibit bioavailability, while low concentrations may provide optimal conditions for algal uptake of Hg. However, variability of BCFs at low DOC indicates that DOC composition or other ligands may determine site-specific bioavailability of Hg.

Environmental Pollution↗

Wetlands as principal zones of methylmercury production in southern Louisiana and the Gulf of Mexico region

It is widely recognized that wetlands, especially those rich in organic matter and receiving appreciable atmospheric mercury (Hg) inputs, are important sites of methylmercury (MeHg) production. Extensive wetlands in the southeastern United States have many ecosystem attributes ideal for promoting high MeHg production rates; however, relatively few mercury cycling studies have been conducted in these environments. We conducted a landscape scale study examining Hg cycling in coastal Louisiana (USA) including four field trips conducted between August 2003 and May 2005. Sites were chosen to represent different ecosystem types, including: a large shallow eutrophic estuarine lake (Lake Pontchartrain), three rivers draining into the lake, a cypress-tupelo dominated freshwater swamp, and six emergent marshes ranging from a freshwater marsh dominated by Panicum hemitomon to a Spartina alterniflora dominated salt marsh close to the Gulf of Mexico. We measured MeHg and total Hg (THg) concentrations, and ancillary chemical characteristics, in whole and filtered surface water, and filtered porewater. Overall, MeHg concentrations were greatest in surface water of freshwater wetlands and lowest in the profundal (non-vegetated) regions of the lake and river mainstems. Concentrations of THg and MeHg in filtered surface water were positively correlated with the highly reactive, aromatic (hydrophobic organic acid) fraction of dissolved organic carbon (DOC). These results suggest that DOC plays an important role in promoting the mobility, transport and bioavailability of inorganic Hg in these environments. Further, elevated porewater concentrations in marine and brackish wetlands suggest coastal wetlands along the Gulf Coast are key sites for MeHg production and may be a principal source of MeHg to foodwebs in the Gulf of Mexico. Examining the relationships among MeHg, THg, and DOC across these multiple landscape types is a first step in evaluating possible links between key zones for Hg(II)-methylation and the bioaccumulation of mercury in the biota inhabiting the Gulf of Mexico region

Environmental Pollution↗

Comparison of total mercury and methylmercury cycling at five sites using the small watershed approach

The small watershed approach is well-suited but underutilized in mercury research. We applied the small watershed approach to investigate total mercury (THg) and methylmercury (MeHg) dynamics in streamwater at the five diverse forested headwater catchments of the US Geological Survey Water, Energy, and Biogeochemical Budgets (WEBB) program. At all sites, baseflow THg was generally less than 1 ng L −1 and MeHg was less than 0.2 ng L −1 . THg and MeHg concentrations increased with streamflow, so export was primarily episodic. At three sites, THg and MeHg concentration and export were dominated by the particulate fraction in association with POC at high flows, with maximum THg (MeHg) concentrations of 94 (2.56) ng L −1 at Sleepers River, Vermont; 112 (0.75) ng L −1 at Rio Icacos, Puerto Rico; and 55 (0.80) ng L −1 at Panola Mt., Georgia. Filtered (<0.7 μm) THg increased more modestly with flow in association with the hydrophobic acid fraction (HPOA) of DOC, with maximum filtered THg concentrations near 5 ng L −1 at both Sleepers and Icacos. At Andrews Creek, Colorado, THg export was also episodic but was dominated by filtered THg, as POC concentrations were low. MeHg typically tracked THg so that each site had a fairly constant MeHg/THg ratio, which ranged from near zero at Andrews to 15% at the low-relief, groundwater-dominated Allequash Creek, Wisconsin. Allequash was the only site with filtered MeHg consistently above detection, and the filtered fraction dominated both THg and MeHg. Relative to inputs in wet deposition, watershed retention of THg (minus any subsequent volatilization) was 96.6% at Allequash, 60% at Sleepers, and 83% at Andrews. Icacos had a net export of THg, possibly due to historic gold mining or frequent disturbance from landslides. Quantification and interpretation of Hg dynamics was facilitated by the small watershed approach with emphasis on event sampling.

Environmental Pollution↗

Distribution of toxic trace elements in soil/sediment in post-Katrina New Orleans and the Louisiana Delta

This study provided a comprehensive assessment of seven toxic trace elements (As, Pb, V, Cr, Cd, Cu, and Hg) in the soil/sediment of Katrina affected greater New Orleans region 1 month after the recession of flood water. Results indicated significant contamination of As and V and non-significant contamination of Cd, Cr, Cu, Hg and Pb at most sampling sites. Compared to the reported EPA Region 6 soil background inorganic levels, except As, the concentrations of other six elements had greatly increased throughout the studied area; St. Bernard Parish and Plaquemines Parish showed greater contamination than other regions. Comparison between pre- and post-Katrina data in similar areas, and data for surface, shallow, and deep samples indicated that the trace element distribution in post-Katrina New Orleans was not obviously attributed to the flooding. This study suggests that more detailed study of As and V contamination at identified locations is needed. ?? 2008 Elsevier Ltd.

Environmental Pollution↗

Effects of methylmercury exposure on glutathione metabolism, oxidative stress, and chromosomal damage in captive-reared common loon (Gavia immer) chicks

We quantified the level of dietary mercury (Hg), delivered as methylmercury chloride (CH3HgCl), associated with negative effects on organ and plasma biochemistries related to glutathione (GSH) metabolism and oxidative stress, and chromosomal damage in captive-reared common loon (Gavia immer) chicks reared from hatch to 105 days. Mercury-associated effects related to oxidative stress and altered glutathione metabolism occurred at 1.2 :g Hg/g and 0.4 :g Hg/g, an ecologically relevant dietary mercury level, but not at 0.08 :g Hg/g. Among the variables that contributed most to dissimilarities in tissue chemistries between control and treatment groups were increased levels of oxidized glutathione (GSSG), GSH peroxidase, and the ratio of GSSG to GSH in brain tissue; increased levels of hepatic GSH; and decreased levels of hepatic glucose-6-phosphate dehydrogenase (G-6-PDH). Our results also suggest that chronic exposure to environmentally relevant dietary Hg levels did not result in statistically significant somatic chromosomal damage in common loon chicks. Oxidative stress and altered glutathione metabolism were evident in common loon chicks exposed to >0.4 :g Hg as CH3HgCl per gram wet food intake.

Environmental Pollution↗

Persistence of organochlorine chemical residues in fish from the Tombigbee River (Alabama, USA): Continuing risk to wildlife from a former DDT manufacturing facility

Organochlorine pesticide and total polychlorinated biphenyl (PCB) concentrations were measured in largemouth bass from the Tombigbee River near a former DDT manufacturing facility at McIntosh, Alabama. Evaluation of mean p,p???- and o,p???-DDT isomer concentrations and o,p???- versus p,p???-isomer proportions in McIntosh bass indicated that DDT is moving off site from the facility and into the Tombigbee River. Concentrations of p,p???-DDT isomers in McIntosh bass remained unchanged from 1974 to 2004 and were four times greater than contemporary concentrations from a national program. Total DDT in McIntosh bass exceeded dietary effect concentrations developed for bald eagle and osprey. Hexachlorobenzene, PCBs, and toxaphene concentrations in bass from McIntosh also exceeded thresholds to protect fish and piscivorous wildlife. Whereas concentrations of DDT and most other organochlorine chemicals in fish have generally declined in the U.S. since their ban, concentrations of DDT in fish from McIntosh remain elevated and represent a threat to wildlife.

Environmental Pollution↗

Relationships between hepatic trace element concentrations, reproductive status, and body condition of female greater scaup

We collected female greater scaup ( Aythya marila ) on the Yukon–Kuskokwim Delta, Alaska during two breeding seasons to determine if concentrations of 18 trace elements in livers and eggs were elevated and if hepatic concentrations correlated with body condition or affected reproductive status. Fifty-six percent, 5%, and 42% of females, respectively, had elevated hepatic cadmium (Cd: >3 μg g −1 dry weight [dw]), mercury (Hg: >3 μg g −1 dw), and selenium (Se: >10 μg g −1 dw). Somatic protein and lipid reserves were not correlated with hepatic Cd or Hg, but there was a weak negative correlation between protein and Se. Hepatic Cd, Hg, and Se were similar in females that had and had not initiated egg production. In a sample of six eggs, 33% and 100%, respectively, contained Se and Hg, but concentrations were below embryotoxicity thresholds. We conclude that trace element concentrations documented likely were not adversely impacting this study population.

Environmental Pollution↗