Toxic Tire Wear Compounds (6PPD-Q and 4-ADPA) Detected in Airborne Particulate Matter Along a Highway in Mississippi, USA.

Tire wear particles (TWPs) are a major category of microplastic pollution produced by friction between tires and road surfaces. This non-exhaust particulate matter (PM) containing leachable toxic compounds is transported through the air and with stormwater runoff, leading to environmental pollution and human health concerns. In the present study, we collected airborne PM at varying distances (5, 15 and 30 m) along US Highway 278 in Oxford, Mississippi, USA, for ten consecutive days using Sigma-2 passive samplers. Particles (~ 1-80 µm) were passively collected directly into small (60 mL) wide-mouth separatory funnels placed inside the samplers. Particles were subsequently subjected to solvent extraction, and extracts were analyzed for TWP compounds by high resolution orbitrap mass spectrometry. This pilot study was focused solely on qualitative analyses to determine whether TWP compounds were present in this fraction of airborne PM. The abundance of airborne TWPs increased with proximity to the road with deposition rates (TWPs cm-2 day-1) of 23, 47, and 63 at 30 m, 15 m, and 5 m from the highway, respectively. Two common TWP compounds (6PPD-Q and 4-ADPA) were detected in all samples, except the field blank, at levels above their limits of detection, estimated at 2.90 and 1.14 ng L-1, respectively. Overall, this work suggests airborne TWPs may be a potential inhalation hazard, particularly for individuals and wildlife who spend extended periods outdoors along busy roadways. Research on the bioavailability of TWP compounds from inhaled TWPs is needed to address exposure risk.

The changing face of BECT: a citation analysis covering 1966-2009.

A citation analysis was completed on articles published in Bulletin of Environmental Contamination and Toxicology over the period of 1966-2009. Articles were grouped into 5 year intervals and the top 50 most-cited papers in each year interval were categorized according to research theme. Over the journal's history, articles in the toxicity research theme dominated top-cited articles published by the journal followed by articles in the environmental concentration theme and the mechanistic theme. The geographic area of submission of top-cited articles has shown large changes with time, initially being dominated by papers from North American and now dominated by papers from Asia. An examination of the citation history for the highest cited paper in each year interval indicated that the average time to achieve 90 % of total citations is 25 years.

Novel control and steady-state correction method for standard 28-day bioaccumulation tests using Nereis virens.

Evaluation of dredged material for aquatic placement requires assessment of bioaccumulation potentials for benthic organisms using standardized laboratory bioaccumulation tests. Critical to the interpretation of these data is the assessment of steady state for bioaccumulated residues needed to generate biota sediment accumulation factors (BSAFs) and to address control correction of day 0 contaminant residues measured in bioassay organisms. This study applied a novel performance reference compound approach with a pulse-chase experimental design to investigate elimination of a series of isotopically labeled polychlorinated biphenyl ((13)C-PCBs) in the polychaete worm Nereis virens while simultaneously evaluating native PCB bioaccumulation from field-collected sediments. Results demonstrated that all (13)C-PCBs, with the exception of (13)C-PCB209 (> 80%), were eliminated by more than 90% after 28 d. The three sediment types yielded similar (13)C-PCB whole-body elimination rate constants (k(tot)) producing the following predictive equation: log k(tot) = - 0.09 × log K(OW) - 0.45. The rapid loss of (13)C-PCBs from worms over the bioassay period indicated that control correction, by subtracting day 0 residues, would result in underestimates of bioavailable sediment residues. Significant uptake of native PCBs was observed only in the most contaminated sediment and proceeded according to kinetic model predictions with steady-state BSAFs ranging from 1 to 3 and peaking for congeners of log K(OW) between 6.2 and 6.5. The performance reference compound approach can provide novel information about chemical toxicokinetics and also serve as a quality check for the physiological performance of the bioassay organism during standardized bioaccumulation testing.

Variable vitellogenin response of Japanese medaka (Oryzias latipes) to weekly estrogen exposure.

Japanese medaka (Oryzias latipes) is a valuable model organism in reproductive and developmental toxicity testing. The purpose of this experiment is to assess the response of medaka to aquatic estrogen exposure over the course of 1 year. Each week, three pairs of adult male medaka were exposed separately for 4 days (100% static renewal daily) to 17beta-estradiol at a nominal level of 25 microg/l, with a fourth pair of fish exposed separately to an ethanol control. Vitellogenin (VTG) induction was observed each week, with hepatic and plasma VTG levels significantly higher (P < 0.001) than reported for ethanol control specimens. A significant (P < 0.001) increasing trend was observed for plasma VTG results over the duration of the study, whereas a decreasing trend (P = 0.030) of hepatic VTG was evident. A Durbin-Watson test, however, did not demonstrate any serial autocorrelation of hepatic (d = 1.180) or plasma (d = 1.311) VTG levels over the duration of the study. Time-series transformations of the hepatic and plasma VTG data did not reveal any significant seasonal or behavioral patterns. However, significant intermittent peaks in VTG production were observed in both tissue types during the study. These data indicate that some consideration must be taken to time long-term medaka exposures (>20 weeks) in order to eliminate any influence of cyclic changes on plasma VTG response. Alternatively, hepatic cytosolic measurement of VTG appears to show a more sensitive response to aquatic estrogen exposure.

Predicting physical properties of emerging compounds with limited physical and chemical data: QSAR model uncertainty and applicability to military munitions.

Reliable, up-front information on physical and biological properties of emerging materials is essential before making a decision and investment to formulate, synthesize, scale-up, test, and manufacture a new material for use in both military and civilian applications. Multiple quantitative structure-activity relationships (QSARs) software tools are available for predicting a material's physical/chemical properties and environmental effects. Even though information on emerging materials is often limited, QSAR software output is treated without sufficient uncertainty analysis. We hypothesize that uncertainty and variability in material properties and uncertainty in model prediction can be too large to provide meaningful results. To test this hypothesis, we predicted octanol water partitioning coefficients (logP) for multiple, similar compounds with limited physical-chemical properties using six different commercial logP calculators (KOWWIN, MarvinSketch, ACD/Labs, ALogP, CLogP, SPARC). Analysis was done for materials with largely uncertain properties that were similar, based on molecular formula, to military compounds (RDX, BTTN, TNT) and pharmaceuticals (Carbamazepine, Gemfibrizol). We have also compared QSAR modeling results for a well-studied pesticide and pesticide breakdown product (Atrazine, DDE). Our analysis shows variability due to structural variations of the emerging chemicals may be several orders of magnitude. The model uncertainty across six software packages was very high (10 orders of magnitude) for emerging materials while it was low for traditional chemicals (e.g. Atrazine). Thus the use of QSAR models for emerging materials screening requires extensive model validation and coupling QSAR output with available empirical data and other relevant information.

Seasonality effects on pharmaceuticals and s-triazine herbicides in wastewater effluent and surface water from the Canadian side of the upper Detroit River.

The influence of seasonal changes in water conditions and parameters on several major pharmacologically active compounds (PhACs) and s-triazine herbicides was assessed in the wastewater and sewage treatment plant (WSTP) effluent as well as the downstream surface water from sites on the Canadian side of the upper Detroit River, between the Little River WSTP and near the water intake of a major drinking water treatment facility for the City of Windsor (ON, Canada). The assessed PhACs were of neutral (carbamazepine, cotinine, caffeine, cyclophosphamide, fluoxetine, norfluoxetine, pentoxifylline, and trimethoprim) and acidic (ibuprofen, bezafibrate, clofibric acid, diclofenac, fenoprofen, gemfibrozil, indomethacin, naproxen, and ketoprofen) varieties. The major assessed s-triazine herbicides were atrazine, simazine, propazine, prometon, ametryn, prometryn, and terbutryn. At sampling times from September 2002 to June 2003, 15 PhACs were detected in the WSTP effluent at concentrations ranging from 1.7 to 1244 ng/L. The PhAC concentrations decreased by as much 92 to 100% at the Little River/Detroit River confluence because of the river dilution effect, with further continual decreases at sites downstream from the WSTP. The only quantifiable s-triazine in WSTP effluent, atrazine, ranged from 6.7 to 200 ng/L and was higher in Detroit River surface waters than in WSTP effluent. Only carbamazepine, cotinine, and atrazine were detectable at the low-nanogram and subnanogram levels in surface waters near a drinking water intake site. Unlike the PhACs, atrazine in the Detroit River is not attributable to point sources, and it is heavily influenced by seasonal agricultural usage and runoff. Detroit River surface water concentrations of carbamazepine, cotinine, and atrazine may present a health concern to aquatic wildlife and to humans via the consumption of drinking water.

Ozone treatment and the depletion of detectable pharmaceuticals and atrazine herbicide in drinking water sourced from the upper Detroit River, Ontario, Canada.

The depletion and degradation of pharmacologically active compounds (PhACs) and pesticides as a function of ozonation in drinking water treatment processes is not well studied. The A.H. Weeks drinking water treatment plant (DWTP) serves the City of Windsor, Ontario Canada, and incorporates ozone treatment into the production of drinking water. This DWTP also operates a real-time, scaled down pilot plant, which has two parallel streams, conventional and ozone plus conventional treatments. In this study water samples were collected from key points in the two streams of the pilot plant system to determine the depletion and influence of seasonal changes in water processing parameters on eighteen major PhACs (and metabolites) and seven s-triazines herbicides. However, only carbamazepine (antiepileptic), caffeine (stimulant), cotinine (metabolite of nicotine) and atrazine were consistently detectable in the raw water intake (low to sub-ng/L level). Regardless of the seasonality, the flocculation-coagulation and dual media filtration steps without ozone treatment resulted in no decrease in analyte concentrations, while decreases of 66-100% (undetectable, method detection limits 0.05-1 ng/L) of the analyte concentrations were observed when ozone treatment was part of the water processing. These findings demonstrate that ozone treatment is highly effective in depleting carbamazepine, caffeine, cotinine, and atrazine, and thus is highly influential in the fate of these compounds in drinking water treatment regardless of the seasonal time frame. Currently very few Canadian DWTPs incorporate ozonation into conventional treatment, which suggests that human exposure to these compounds via drinking water consumption may be an issue in affected communities.

Vegetated agricultural drainage ditches for the mitigation of pyrethroid-associated runoff.

Drainage ditches are indispensable components of the agricultural production landscape. A benefit of these ditches is contaminant mitigation of agricultural storm runoff. This study determined bifenthrin and lambda-cyhalothrin (two pyrethroid insecticides) partitioning and retention in ditch water, sediment, and plant material as well as estimated necessary ditch length required for effective mitigation. A controlled-release runoff simulation was conducted on a 650-m vegetated drainage ditch in the Mississippi Delta, USA. Bifenthrin and lambda-cyhalothrin were released into the ditch in a water-sediment slurry. Samples of water, sediment, and plants were collected and analyzed for pyrethroid concentrations. Three hours following runoff initiation, inlet bifenthrin and lambda-cyhalothrin water concentrations ranged from 666 and 374 microg/L, respectively, to 7.24 and 5.23 microg/L at 200 m downstream. No chemical residues were detected at the 400-m sampling site. A similar trend was observed throughout the first 7 d of the study where water concentrations were elevated at the front end of the ditch (0-25 m) and greatly reduced by the 400-m sampling site. Regression formulas predicted that bifenthrin and lambda-cyhalothrin concentrations in ditch water were reduced to 0.1% of the initial value within 280 m. Mass balance calculations determined that ditch plants were the major sink and/or sorption site responsible for the rapid aqueous pyrethroid dissipation. By incorporating vegetated drainage ditches into a watershed management program, agriculture can continue to decrease potential non-point source threats to downstream aquatic receiving systems. Overall results of this study illustrate that aquatic macrophytes play an important role in the retention and distribution of pyrethroids in vegetated agricultural drainage ditches.

Triclosan in waste and surface waters from the upper Detroit River by liquid chromatography-electrospray-tandem quadrupole mass spectrometry.

Triclosan (5-chloro-2-(2,4-dichlorophenoxy)phenol) is an antimicroibial disinfectant agent used in a wide array of consumer products. An analytical method based on solid-phase extraction (SPE) followed by reverse phase, liquid chromatography coupled with electrospray ionization (negative)-tandem quadrupole mass spectrometry (LC-ESI(-)-MS/MS; in the multiple reaction monitoring (MRM) mode) was developed, optimized and validated for the determination of triclosan in wastewater/sewage treatment plant (WSTP) effluent and surface waters from the upper Detroit River (Canada). The mean recoveries (+/-%RSD) of triclosan and the internal standard 2'-HO-tribromodiphenyl ether (2'-HO-BDE-28) spiked to surface water and WSTP effluent samples ranged similarly from 104+/-8% and 91+/-10%, respectively, and method limits of quantification were in the low ppb/high ppt range. However, ESI(-) enhancement was found for both analytes due to sample matrix effects, as indicated by % process efficiencies (a measure of ESI(-) enhancement/suppression), which were in the 111-128% range. We report the first known assessment of triclosan in the Detroit River watershed of the Great Lakes, which preliminarily examined the presence and UV-treatment effects on triclosan in effluent from the major WSTP serving the City of Windsor, Ontario, Canada, and fate in surface waters of the upper Detroit River. Triclosan in WSTP effluent decreased 22% after final UV treatment to a mean concentration of 63 ng/L. Concentrations were further reduced to 4 and 8 ng/L (a >90% reduction) in surface water samples from sites downstream on the Canadian shoreline of the Detroit River, which was due to dilution. Two hydroxylated tribrominated diphenyl ethers, which are structurally similar to triclosan, were also detected in WSTP effluent and surface water samples.

Obtaining quantitative vapor emissions estimates of polychlorinated biphenyls and other semivolatile organic compounds from contaminated sites.

Soils contaminated with polychlorinated biphenyls (PCBs) and other semivolatile organic compounds (SVOCs) represent a potentially major, ongoing source of these compounds to the environment, especially during warmer temperatures. A great deal of work has been devoted to understanding the mechanisms that govern the vaporization of SVOCs from soil, but to date, few quantitative estimates have been published regarding emissions from contaminated sites. The present paper describes methods for obtaining quantitative estimates of SVOCs from soils based on flux chamber measurements, modeling, and ambient air measurements. On wet (i.e., H2O) soils, SVOCs at very low chemical loading levels on the adsorption sites (the so-called critical chemical concentration, critical loading, or saturation concentration) will behave, for volatilization purposes, as the pure-liquid substance would. For one soil, the PCB critical concentration was determined to be 775 ppm (95% confidence interval, 5.40E+02). Flux chamber-measured emissions from two contaminated sites were used and compared to model estimated values. The results agree reasonably well and indicate that the modeling approach used provided a conservative upper bound on the emissions. These approaches can be used to develop emissions estimates for SVOC-contaminated sites and inputs to air dispersion models.

Fate and effects of azinphos-methyl in a flow through wetland in South Africa.

Our knowledge about the effectiveness of constructed wetlands in retaining agricultural nonpoint-source pesticide pollution is limited. A 0.44-ha vegetated wetland built along a tributary of the Lourens River, Western Cape, South Africa, was studied to ascertain the retention, fate, and effects of spray drift-borne azinphos-methyl (AZP). Composite water samples taken at the inlet and outlet during five spray drift trials in summer 2000 and 2001 revealed an overall reduction of AZP levels by 90 +/- 1% and a retention of AZP mass by 61 +/- 5%. Samples were collected at the inlet outlet, and four platforms within the wetland to determine the fate and effect of AZP in the wetland after direct spray drift deposition in the tributary 200 m upstream of the inlet. Peak concentrations of AZP decreased, and the duration of exposure increased from inlet (0.73 microg/L; 9 h) via platforms 1 and 4 to outlet (0.08 microg/L; 16 h). AZP sorbed to plants or plant surfaces, leading to a peak concentration of 6.8 microg/kg dw. The living plant biomass accounted for 10.5% of the AZP mass initially retained in the wetland, indicating processes such as volatilization, photolysis, hydrolysis, or metabolic degradation as being very important AZP was not detected in sediments. Water samples taken along two 10-m transects situated perpendicular to the shore indicated a homogeneous horizontal distribution of the pesticide: 0.23 +/- 0.02 and 0.14 +/- 0.04 microg/L (n = 5), respectively. Both Copepoda (p = 0.019) and Cladocere (p = 0.027) decreased significantly 6 h postdeposition and remained at reduced densities for at least 7 d. In parallel, the chlorophyll a concentration showed an increase, although not significant, within 6 h of spray deposition. The study highlights the potential of constructed wetlands as a risk-mitigation strategy for spray drift-related pesticide pollution.

Methyl parathion toxicity in vegetated and nonvegetated wetland mesocosms.

Methyl parathion (MeP) was introduced into constructed wetlands for the purpose of assessing the influence of emergent vegetation on transport and toxicity of the pesticide. Two vegetated (90% cover, mainly Juncus effusus) and two nonvegetated wetland cells (each with a water body of 50 x 5.5 x 0.2 m) were each dosed with 6.5 m3 of water containing active ingredient of MeP at 6.6 mg/L associated with suspended soil at 400 mg/L to simulate a storm runoff event. Acute toxicity was assessed by sampling benthic macroinvertebrates at 5, 10, 20, and 40 m from the inlet before and 96 h after contamination and by in situ exposure of Chironomus tentans (Diptera) up to 24 h after contamination. Methyl parathion was detected throughout the nonvegetated wetland cells (70 microg/L at 20 m, 8 microg/L at 40 m), whereas the pesticide was not transported through the vegetated wetland cells (20 microg/L at 20 m, < 0.1 microg/L at 40 m). A three-way analysis of variance using contamination (repeated measure variable), location, and vegetation indicated significant negative effects of contamination on various insect taxa, such as mayfly nymphs and caddisfly larvae. Seven out of the total of 15 species revealed a significant contamination x vegetation effect, with individuals in the vegetated wetlands being less affected. Four species showed a significant contamination x location effect, confirming a higher toxicity in the inlet area of the wetlands. A significant three-way interaction of contamination x vegetation x location was detected in Chironomus sp., which was most strongly affected at the inlet area of the nonvegetated wetland cells. The in situ bioassay employing C. tentans confirmed the positive effect of wetland vegetation on MeP toxicity. These results demonstrate the importance of vegetation for pesticide mitigation in constructed wetlands.