Evaluations of combined zebrafish (Danio rerio) embryo and marine phytoplankton (Diacronema lutheri) toxicity of dissolved organic contaminants in the Ythan catchment,Scotland, UK

A wide variety of organic contaminants including pesticides, polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) have previously been detected in surface waters in the river Ythan catchment, North East Scotland UK. While the concentrations detected were below Water Framework Directive Environmental Quality Standards (WFD-EQSs) environmental exposures to the diverse mixtures of contaminants, known and unknown, may pose chronic and/or sublethal effects to non target organisms. The present study assessed the embryo and algal toxicity potential of freely dissolved organic contaminants from the Ythan catchment using silicone rubber passive sampling devices (SR-PSDs) and miniaturised bioassay techniques. Zebrafish (Danio rerio) embryos and marine phytoplankton species (Diacronema lutheri) were exposed to extracts from SR-PSDs deployed at different locations along the river Ythan and an undeployed procedural blank. Statistically significant developmental and algal toxicities were measured in all tests of extracts from deployed samples compared with the procedural blanks. This indicates environmental exposure to, and the combined toxicity potential of, freely dissolved organic contaminants in the catchment. The present and previous studies in the Ythan catchment, coupling SR-PSDs and bioassay techniques, have both helped to understand the interactions and combined effects of dissolved organic contaminants in the catchment. They have further revealed the need for improvement in the techniques currently used to assess environmental impact.     

Dissipation of chlorpyrifos,oxon, and 3,5,6‐trichloro‐2‐pyridinol in litter and elm forest soil

Abstract

After chlorpyrifos was applied to the basal 1 meter of elm tree trunks for control of elm bark beetles at two different application times and sites, initial chlorpyrifos residues in forest floor litter ranged from 120 to 916 μg/g depending on the application time. Residues dissipated by approximately 99% after 791 d with the DT₅₀ from 3.9 to 59 d and DT₉₀ from 55 to 310 d. The initial residues of chlorpyrifos in elm forest soil varied from 0.8 to 28 μg/g and were 1 to 2 μg/g at 791 d after application. The dissipation half‐lives of chlorpyrifos in fortified soil placed in the field ranged from 116 to 121 d.     

Pilot Study of Enclosed Thermal Soil Aeration for Removal of Volatile Organic Contamination

During the winter and spring of 1986 sandy soils contaminated with volatile organic chemicals were successfully treated during a pilot study of an enclosed thermal soil aeration process at the McKin Superfund site in Gray, Maine. Excavated soil containing up to 3310 ppm of trichloroethylene (TCE) was fed into a large rotating drum and mixed at 300°F. Aerated soil was then solidified with cement and water and returned to the on-site excavation location. Exhausted air from the enclosed aeration process was treated in a baghouse, a scrubber, and a vapor phase carbon bed prior to atmospheric release. Continuous air monitoring for organic vapors and particulates took place at the site perimeter and for organic vapors at onsite locations. Techniques to minimize uncontrolled volatilization of organic chemicals from the soil during excavation and aeration and to control dust emissions were implemented. Results of this pilot study indicate that concentrations of volatile organic contaminants routinely were reduced to nondetectable levels and achieved site-specific soil performance targets established by the U.S. Environmental Protection Agency. The pilot study was conducted by Canonie Environmental Services Corporation and funded by private companies under order from EPA.     

Description and evaluation of a sampling system for monitoring hydrocarbons in sediments

A composite random sampling design was used to estimate the concentrations of hydrocarbons in sediments from two near-shore areas of Scotland (Firth of Clyde and Firth of Forth). The aim of this work was to estimate a mean value for each parameter in these areas, and to determine whether this can be done with more thorough coverage (better representation), better precision and less variance at lower analytical cost through a composite random sampling scheme rather than a simple random sampling scheme, and thereby contribute to the re-design of the UK National Marine Monitoring Programme (NMMP), re-named the UK Clean Seas Environmental Monitoring Programme (CSEMP) in 2006. Samples were collected using a simple random sampling design during 2005. All sediment samples were analysed for their particle size distribution and total organic carbon (TOC). All sediments were analysed for polycyclic aromatic hydrocarbons (PAHs) and n-alkanes. The concentrations of PAHs and n-alkanes in the study areas are described, and sources of PAHs were investigated through the PAH distributions and n-alkane profiles. Individual sediment samples from each area were combined to give a series of composite sub-samples, each comprised of 5 individual sediment samples. These composite samples were re-analysed for the same parameters as the individual samples. Mean total PAH (2- to 6-ring parent and branched) concentrations, based on the individual original sediment samples collected through simple random sampling, were 1858 microg kg(-1) dry weight (SE = 196 microg kg(-1) dry weight, n = 25) and 532.4 microg kg(-1) dry weight (SE = 59 microg kg(-1) dry weight, n = 25) in the Clyde and Forth, respectively. Mean total PAH concentrations of the composite samples were 1745 microg kg(-1) dry weight (SE = 121.0 microg kg(-1) dry weight, n = 5) in the Clyde and 511.6 microg kg(-1) dry weight (SE = 37.4 microg kg(-1) dry weight, n = 5) in the Forth. No significant differences were found between the mean PAH concentrations from the two sampling designs. This study demonstrated that the composite random sampling design gave a mean value with less variance than the simple random sampling design, at significantly reduced analytical effort (and cost).     

Halogenated persistent organic pollutants in deep water fish from waters to the west of Scotland

Halogenated persistent organic pollutants [polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs)] along with total lipid, were measured in the liver and muscle of three species of deep water fish (black scabbard, black dogfish (liver only) and roundnose grenadier) collected from the Rockall fishing area, to the west of Scotland, between 2006 and 2008. Both contaminant groups were detected in the muscle and liver, with concentrations of PCBs being higher than PBDEs. There were no significant differences in the PCB or PBDE concentrations between the three species, or different sampling locations in the Rockall fishing area. PCB concentrations (ΣICES (International Council for the Exploration of the Sea)7 PCBs) greater than 500 μg kg⁻¹ lipid weight were found in 26 of the 106 liver samples. PCB concentrations were compared to OSPAR assessment criteria, concentrations were above background but below Environmental Assessment Criteria. Estimated Toxic Equivalent (TEQ) concentrations, calculated using published models, in the fish muscle and liver indicated that consumption of deep water fish is unlikely to represent a risk to human health. The high squalene content in some of the black dogfish liver necessitated an additional clean-up step, involving gel permeation chromatography, when analyzing for PBDEs. Concentrations of PBDEs were low with many congeners being below detection limits, particularly in the muscle. There are currently no assessment criteria available for PBDEs. Furthermore, there is only very limited data on PBDEs in deep water fish. However, the concentrations observed in this study were similar to the concentrations recently reported in Mediterranean deep water fish.     

Water Quality Signals from Rural Land Use and Exurbanization in a Mountain Landscape: What's Clear and What's Confounded?

In mountainous landscapes with high climatic and geomorphic variability, how do rural land uses and exurbanization alter hydrology and water quality? We evaluated effects of rural land use and exurbanization on streamflows, suspended sediment concentrations and loads, specific conductance, and summer water temperatures in 12 streams and rivers within the Upper Little Tennessee River basin in the southern Appalachian Mountains. Eleven streams featured low levels of development (>61% forest cover) but differed in land use patterning, basin size, annual precipitation, and watershed morphology. One urban stream, located within the largest town in the basin, provided the high development comparative endpoint. Even low levels of rural development and exurbanization were associated with substantial increases in suspended sediment concentrations, sediment loads, and summer stream temperature daily maxima and diurnal variation. Observed summer temperature increases were much larger than would be expected due to global climate change over the next century. Specific conductance was idiosyncratic among the smaller streams. These water quality changes were not accompanied by streamflow changes that were discernible amid the high natural variation in precipitation and geomorphology. The water quality findings suggest the need for applying the best management practices, including riparian buffers, to even low levels of rural development.     

Estimating chemical biotransformation rates from food web concentrations

Biotransformation is widely recognized as the most important and most uncertain determinant of bioaccumulation. A step-wise method for estimating organism-specific biotransformation half-lives from field observations and using established food web modeling is developed. As a proof of concept, the method is applied to the case of nine polycyclic aromatic hydrocarbons (PAHs) in a well-studied food web in Bohai Bay, China. The estimated half-lives are in good agreement with the existing literature. The proposed biotransformation estimation method, through data mining, for sufficiently defined ecosystems, may greatly reduce the necessary animal testing involved in chemical assessments by providing useful guidance to experimentalists and regulators.     

Herbicide incorporation by irrigation and tillage impact on runoff loss

Runoff from farm fields is a common source of herbicide residues in surface waters. Incorporation by irrigation has the potential to reduce herbicide runoff risks. To assess impacts, rainfall was simulated on plots located in a peanut (Arachis hypogaea L.) field in Georgia's Atlantic Coastal Plain region after pre-emergence application of metolachlor (2-chloro-N-(2-ethyl-6-methylphenyl)-N-[(1S)-2-methoxy-1-methylethyl]-acetamide) and pendimethalin (N-(1-ethylpropyl)-3,4-dimethyl-2,6-dinitro-benzenamine). Runoff, sediment, and herbicide loss as function of strip tillage (ST) versus conventional tillage (CT) were compared with and without irrigation (12.5 mm) after application of an herbicide tank mixture. For the CT system, metolachlor runoff was reduced 2x and pendimethalin 1.2x when compared with the non-irrigated treatment. The difference in irrigated and non-irrigated metolachlor means was significant (P = 0.05). Irrigation reduced metolachlor runoff by 1.3x in the ST system, but there was a 1.4x increase for pendimethalin. Overall results indicated that irrigation incorporation reduces herbicide runoff with the greatest impact when CT is practiced and products like metolachlor, which have relatively low K(oc) and high water solubility, are used. The lower ST system response was likely due to a combination of spray interception and retention by the ST system cover crop mulch and higher ST soil organic carbon content and less total runoff. During the study, the measured K(oc) of both herbicides on runoff sediment was found to vary with tillage and irrigation after herbicide application. Generally, K(oc) was higher for ST sediment and when irrigation incorporation was used with the CT system. These results have significant implications for simulation model parametization.     

Propanil in a Manitoba soil: an interactive spreadsheet model based on conventional chemical kinetics

An interactive spreadsheet model has been created for quantitative predictions of propanil sorption and reaction in a slurried Manitoba clay soil. Based on experimental values for the numbers of empty and filled sorption sites as reactants and products, the reaction mechanism has been described with conventional chemical kinetics. The on line HPLC μ extraction method revealed labile sorption, intraparticle diffusion, and a chemical reaction. Laidler's integral rate law for second order kinetics describes the labile sorption. Desorption, intraparticle diffusion, and the chemical reaction are all described by first order kinetics. The time dependent effects of initial concentration and amount of slurried soil can be predicted for sorption, intraparticle diffusion, and the amount of reaction product. Suggested applications include storm runoff and inputs for fate and transport hydrology models.     

Critical factors in assessing exposure to PBDEs via house dust

Assessment of indoor exposure to polybrominated diphenyl ethers (PBDEs) requires a critical examination of methods that may influence exposure estimates and comparisons between studies. We measured PBDEs in residential dust collected from 20 homes in Boston, MA, to examine 5 key questions: 1) Does the choice of dust exposure metric-e.g., concentration (ng/g) or dust loading (ng/m2)-affect analysis and results? 2) To what degree do dust concentrations change over time? 3) Do dust concentrations vary between rooms? 4) Is the home vacuum bag an acceptable surrogate for researcher-collected dust? 5) Are air and dust concentrations correlated for the same room? We used linear mixed-effects models to analyze the data while accounting for within-home and within-room correlations. We found that PBDE dust concentration and surface loading were highly correlated (r=0.86-0.95, p<0.001). Average dust concentrations did not significantly differ over an 8-month period, possibly because home furnishings changed little over this time. We observed significant differences between rooms in the same home: PBDE concentrations in the main living area were 97% higher than the bedroom for decaBDE (p=0.02) and 72% higher for pentaBDE (p=0.05). Home vacuum bag dust concentrations were significantly lower than researcher-collected dust and not strongly correlated. Air (vapor and particulate phase) and dust concentrations were correlated for pentaBDE (p=0.62, p<0.01), but not for decaBDE (p=0.25). In addition, potential markers of BDE 209 debromination (BDE 202 and the BDE197:BDE201 ratio) were also observed in household dust samples. One vacuum bag sample contained the highest concentrations of BDE 209 (527,000 ng/g) and total PBDEs (544,000 ng/g) that have been reported in house dust.