Current and historical deposition of PBDEs, pesticides, PCBs, and PAHs to Rocky Mountain National Park

An analytical method was developed for the trace analysis of 98 semivolatile organic compounds (SOCs) in remote, high-elevation lake sediment. Sediment cores from Lone Pine Lake (west of the Continental Divide) and Mills Lake (east of the Continental Divide) in Rocky Mountain National Park, CO, were dated using 210Pb and 137Cs and analyzed for polybrominated diphenyl ethers (PBDEs), organochlorine pesticides, phosphorothioate pesticides, thiocarbamate pesticides, amide herbicides, triazine herbicides, polychlorinated biphenyls (PCBs), and polycyclic aromatic hydrocarbons (PAHs) using this method. SOC deposition profiles were reconstructed, and deposition half-lives and doubling times were calculated, for U.S. historic-use pesticides (HUPs) and current-use pesticides (CUPs) as well as PBDEs, PCBs, and PAHs. Sediment records indicate that the deposition of CUPs has increased in recent years, while the deposition of HUPs has decreased since U.S. restriction, but has not been eliminated. This is likely due to the revolatilization of HUPs from regional soils, atmospheric transport, and deposition. Differences in the magnitude of SOC sediment fluxes, flux profiles, time trends within those profiles, and isomeric ratios suggest that SOC deposition in high-elevation ecosystems is dependent on regional upslope wind directions and site location with respect to regional sources and topographic barriers.     

Distribution of organochlorine pesticides in the northern South China Sea: implications for land outflow and air-sea exchange

The South China Sea (SCS) is surrounded by developing countries in Southeast Asia, where persistent organic pollutants (POPs), such as organochlorine pesticides (OCPs), are still used legally or illegally, and are of concern. Yet little is known about the distribution of OCPs in the water and atmosphere over SCS, as well as their air-sea equilibrium status and time trends. In this study, ship-board air samples and surface seawater collected in the northern SCS between September 6 and 22, 2005 were analyzed for selected OCPs. The measured OCP concentrations in the atmosphere over the northern SCS were influenced by proximity to source regions and air mass origins. The highest atmospheric OCP concentrations were found at sampling sites adjacent to continental South China. OCPs in surface seawater showed significant spatial variations, with the highest concentration observed in a water sample from off Vietnam. The coastal currents were suggested to play a key role in the delivery of waterborne OCPs in the northern SCS. Time trend, land outflow, and air-sea exchange of selected OCPs in the SCS were investigated, by comparison of this dataset with historical data.     

Organochlorine pesticides in the soils and atmosphere of Costa Rica

A survey of the contamination of the physical environment of Costa Rica with banned organochlorine pesticides (OCPs) relied on sampling air and soil at 23 stations acrossthe country in 2004. Average annual air concentrations, determined with XAD-based passive samplers, and surface soil concentrations were generally low when compared to values reported for North and Central America, which is consistent with relatively low historical domestic use and little atmospheric inflow from neighboring countries. Statistical analysis and concentration maps reveal three types of spatial distribution: alpha-hexachlorocyclohexane and p,p'-DDD had a relatively uniform distribution across the country; other DDT-related species were greatly elevated over the national average at Manuel Antonio, a National Park on the Pacific coast; and dieldrin, lindane, and chlordane-related species had higher concentrations in Costa Rica's populated Central Valley. An altitudinal transect of stations in the Central Valley shows declining air-soil concentration ratios with elevation for lindane, likely driven by atmospheric inversions and soil organic carbon content. Enantiomeric composition of chiral OCPs in air and soil was close to racemic, with slight depletion of (-)-alpha-HCH, (-)-cis-chlordane, and (+)-trans-chlordane. Estimated air-soil fugacity fractions are highly uncertain but indicate equilibrium conditions for most OCPs, net volatilization of lindane at some sites, and net deposition for p,p'-DDE. The study demonstrates an approach for quickly evaluating the spatial distribution of OCPs in an understudied area, identifying regionally important contaminants and areas of elevated concentrations.     

Atmospheric distribution and long-range transport behavior of organochlorine pesticides in North America

Annually averaged concentrations and enantiomeric compositions of organochlorine pesticides (OCPs) in air were determined in 2000/2001 at 40 stations across North America using XAD-based passive samplers. Absolute concentration differences acrossthe continent, the skewness and kurtosis of the concentration distribution, the relative abundance of parent compound and metabolites, and the chiral signatures can identify regional sources of OCP to the atmosphere. Specifically, air samples collected in the southeastern United States had elevated concentrations of chlordane-related compounds, higher ratios of trans- to cis-chlordane and heptachlor to heptachlor epoxide, as well as higher enantiomeric fractions of trans-chlordane as compared to other regions, suggesting continued release of microbially unprocessed chlordane to the regional atmosphere. Similarly, greatly elevated concentrations of p,p'-DDT, low relative abundance of the metabolite DDE, and a racemic composition of o,p'-DDT in samples from southern Mexico and Belize indicate recent use of DDT in these regions. Belize is also a potential source region for dieldrin. Reflecting its continued use in North America, endosulfan is now one of the most abundant and ubiquitous OCPs in the continental atmosphere. In contrast to these OCPs, air concentrations of penta- and hexachlorobenzene vary only by factors of 2-4 across the continent, reflecting a long atmospheric residence time and few primary sources. Atmospheric levels of the chlorobenzenes, alpha-endosulfan, and p,p'-DDE increase with elevation in the Canadian Rocky Mountains. Empirical travel distances for the OCPs derived from latitudinal concentration profiles are in good agreementwith model-derived indicators of long-range transport potential and, in particular, lead to a similar categorization of the OCPs. Large-scale passive air sampling networks are suitable for monitoring compliance with, and effectiveness of, regulatory control measures and for establishing experimentally the atmospheric long-range transport behavior of organic air pollutants.     

Fate of brominated flame retardants and organochlorine pesticides in urban soil: volatility and degradation

As the uses of polybrominated diphenyl ethers (BDEs) are being phased out in many countries, soils could become a secondary emission source to the atmosphere. It is also anticipated that the demand for alternative brominated flame retardants (BFRs) will grow, but little is known about their environmental fate in soils. In this study, the volatility and degradation of BFRs and organochlorine pesticides (OCPs) in soil was investigated. A low organic carbon (5.6%) urban soil was spiked with a suite of BFRs and OCPs, followed by incubation under laboratory condition for 360 days. These included BDE- 17, -28, -47, -99; α- and β-1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH), β-1,2,5,6-tetrabromocyclooctane (TBCO), and 2,3-dibromopropyl-2,4,6-tribromophenyl ether (DPTE), OCPs: α-hexachlorocyclohexane (α-HCH) and (13)C(6)-α-HCH, trans-chlordane (TC), and (13)C(10)-TC. The volatility of spiked chemicals was investigated using a fugacity meter to measure the soil-air partition coefficient (K(SA)). K(SA) of some spiked BFRs and OCPs increased from Day 10 to 60 or 90 and leveled off afterward. This suggests that the volatility of BFRs and OCPs decreases over time as the chemicals become more strongly bound to the soil. Degradation of alternative BFRs (α- and β-TBECH, β-TBCO, DPTE), BDE-17, and α-HCH ((13)C-labeled and nonlabeled) was evident in soils over 360 days, but no degradation was observed for the BDE-28, -47, -99, and TC ((13)C-labeled and nonlabeled). A method to separate the enantiomers of α-TBECH and β-TBCO was developed and their degradation, along with α-HCH ((13)C-labeled and nonlabeled) was enantioselective. This is the first study which reports the enantioselective degradation of chiral BFRs in soils. Discrepancies between the enantiomer fraction (EF) of chemicals extracted from the soil by dichloromethane (DCM) and air were found. It is suggested that DCM removes both the sequestered and loosely bound fractions of chemicals in soil, whereas air accesses only the loosely bound fraction, and these two pools are subject to different degrees of enantioselective degradation. This calls for caution when interpreting EFs obtained from DCM extraction of soil with EFs in ambient air.     

Parental exposure to pesticides and poor clutch viability in American alligators

In central Florida, alligators (Alligator mississippiensis) inhabiting lakes contaminated with organochlorine pesticides (OCPs) produce eggs that have high OCP concentrations and low clutch viability (proportion of eggs in a clutch that yield a live hatchling) compared to those from less contaminated lakes (reference lakes). However, a clear dose-response relationship has not been established between OCPs and poor clutch viability. In order to better elucidate a cause and effect relationship between OCP exposure and clutch viability, we conducted concurrent field and laboratory studies. Our field study reaffirmed that eggs of wild alligators from OCP-contaminated lakes and wetlands continue to have lower clutch viability and higher OCP burdens than eggs from reference lakes. Our field study also demonstrated that OCP egg burdens were strongly correlated with clutch viability for some of the OCP-contaminated sites, but not all. To better test causal relationships, a parental exposure study was conducted using captive adult alligators. Our laboratory study demonstrated that dietary exposure of captive alligators to an ecologically relevant OCP mixture caused alligators to produce eggs with higher OCP burdens and reduced clutch viability, as compared to the captive-control population. The experimentally induced egg burdens and clutch viability reductions were similar to those of wild alligators from OCP-contaminated sites. Our field and laboratory results suggest parental OCP exposure may be contributing to low clutch viability in wild alligators inhabiting OCP-contaminated habitats, raising some concern for endangered crocodilians living in OCP-contaminated habitats.     

Using passive air samplers to assess urban-rural trends for persistent organic pollutants. 1. Polychlorinated biphenyls and organochlorine pesticides

Passive air samplers were used to investigate urban-rural differences of polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) over an integrated time period. Samplers consisting of polyurethane foam (PUF) disks and semi-permeable membrane devices (SPMDs) were housed in protective chambers and deployed at six sites for a 4 month duration in the summer of 2000. The sampling transect originated in downtown Toronto and extended approximately 75 km northward into a rural region. Results for the two types of samplers agreed well with one another. Higher blank levels were encountered for the SPMDs, especially for the OCPs, whereas blanks were very low for the PUF disks. Passive sampler-derived air concentrations were consistent with previous measurements of PCBs and OCPs in the region. The largest urban-rural gradient was observed for PCBs (approximately 5-10 times). Chlordanes also showed an urban-rural gradient, possibly reflecting past usage of chlordane on residential lawns and emissions from treated house foundations. Other OCPs exhibited a rural-urban gradient (dieldrin, endosulfan 1, and DDT isomers), which was attributed either to off-gassing from previously treated agricultural soils (dieldrin and DDTs) or to continued usage in agriculture (endosulfan 1). The results of this study demonstrated the feasibility of using such devices to determine air concentrations of persistent organic pollutants (POPs) and to assess their spatial distribution for time-integrated samples. Data such as this is essential for: model validation and for process research and addressing international monitoring strategies on POPs.     

Measurement of DDT fluxes from a historically treated agricultural soil in Canada

Organocohlorine pesticide (OCP) residues in agricultural soils are of concern due to the uptake of these compounds by crops, accumulation in the foodchain, and reemission from soils to the atmosphere. Although it has been about three decades since DDT was banned for agricultural uses in Canada, residues persist in soils of some agricultural areas. Emission of DDT compounds to the atmosphere from a historically treated field in southern Ontario was determined in fall 2004 and spring 2005. The sigmaDDTs concentration in the high organic matter (71%) soil was 19 +/- 4 microg g(-1) dry weight. Concentration gradients in the air were measured at 5, 20, 72, and 200 cm above soil using glass fiber filter-polyurethane foam cartridges. Air concentrations of sigmaDDTs averaged 5.7 +/- 5.1 ng m(-3) at 5 cm and decreased to 1.3 +/- 0.8 ng m(-3) at 200 cm and were 60-300 times higher than levels measured at a background site 30 km away. Soil-air fugacity fractions, fs/(fs + fa), of p,p'-DDE, p,p'-DDD, and p,p'-DDT ranged from 0.42 to 0.91 using air concentrations measured above the soil and > or = 0.99 using background air concentrations, indicating that the soil was a net source to the background air. Fractionation of DDT compounds during volatilization was predicted using either liquid-phase vapor pressures (PL) or octanol-air partition coefficients (KOA). Relative emissions of p,p'-DDE and p,p'-DDT were better described by PL than KOA, whereas either PL or KOA successfully accounted for the fractionation of p,p'-DDT and o,p'-DDT. Soil-to-air fluxes were calculated from air concentration gradients and turbulent exchange coefficients determined from micrometeorological measurements. Average fluxes of sigmaDDTs were 90 +/- 24 ng m(-2) h(-1) in fall and 660 +/- 370 ng m(-2) h(-1) in spring. Higher soil temperatures in spring accounted for the higher fluxes. A volatilization half-life of approximately 200 y was estimated for sigmaDDT in the upper 5 cm of the soil column, assuming the average flux rate for 12 h d-(1) over 8 months of the year. Thus, in the absence of other dissipation processes, the soil will continue to be a source of atmospheric contamination for a very long time.     

Accumulation of organochlorine pesticides from water using triolein embedded cellulose acetate membranes

A new type of composite membrane, triolein embedded cellulose acetate membrane (TECAM), was produced by embedding triolein drops in the matrix of cellulose acetate polymers. The distribution of six organochlorine pesticides (OCPs) between water and TECAM was investigated in a static water system. Its field application was tested in Taihu Lake (China). Results from both laboratory and field experiments indicate that TECAM quickly and efficiently accumulated hydrophobic OCPs from water. Under laboratory conditions, uptake equilibrium was achieved within 24 h for all of the six OCPs. Significant correlations were obtained between log Kp TECAM (TECAM-water partition coefficient) and log Kow (octanol-water partition coefficient); between log Ktw (triolein-water partition coefficient, triolein in TECAM) and log Kow; and between log Ktw and log BCF (bioconcentration factor in rainbow trout calculated from literatures). Triolein in TECAM significantly increased the accumulation of strongly hydrophobic OCPs when compared to the use of cellulose acetate polymers alone. Temperature had only slight effects on the Kp TECAM values of the strongly hydrophobic OCPs. The partition coefficient obtained by measuring OCP concentrations in TECAM under field conditions could be successfully applied to estimate OCPs concentrations in surface water.     

Chiral organochlorine pesticide signatures in global background soils

Chiral pesticides frequently undergo enantioselective degradation in soils. Prior studies to characterize chiral signatures have focused on treated agricultural soils, rather than background (untreated) soils, and tracking signatures in the atmosphere for source apportionment purposes. In this study, we investigated the chiral signatures in 65 background soils collected from different locations across the world. The soils were taken from different ecosystems (e.g., grasslands, forests), and the enantiomeric fractions (EFs) of chiral chlordanes, alpha-hexachlorocyclohexane (alpha-HCH), and o,p'-DDT were determined. Chlordanes in most of the soils showed the usual pattern of enantioselective degradation seen in agricultural soils, depletion of (+)-trans-chlordane (TC) and (-)-cis-chlordane (CC). However, some samples showed opposite enantiomer degradation patterns for TC, CC, and chlordane compound MC5. Correlations were tested between the deviation of EFs from racemic (DEVrac = absolute value of 0.500 - EF), the percent soil organic matter (% SOM), annual mean temperature, and the ratio of TC to the more stable compound trans-nonachlor (TN). Significant positive correlations were found between DEVrac and % SOM for TC and CC (p = 0.0022 and 0.0031), but not for the other OCPs. No significant correlations were found between DEVrac and annual mean temperature for any of the OCPs. DEVrac for TC was negatively correlated with the TC/TN ratio, but the regression was driven by two points with high ratios of TC/CC. Removing these two points resulted in a nonsignificant regression. The range of EFs for TC, CC, and alpha-HCH in soils was greater than in ambient air, providing evidence of in situ degradation after atmospheric deposition in some cases. Variable EFs in soil suggest that caution is needed when considering the enantiomer signatures in air as a marker of volatilization of weathered soil-derived organochlorines.     

Hexachlorocyclohexanes and endosulfans in urban, rural, and high altitude air samples in the Fraser Valley, British Columbia: evidence for trans-Pacific transport

High-volume air samples collected over the period Aug. 14-30, 2001, in the Lower Fraser Valley, BC, Canada, were used to assess urban/rural differences of organochlorine pesticides (OCPs) for ground level samples and to attempt to directly measure events of trans-Pacific inputs through the mid-troposphere. Hexachlorocyclohexanes (alpha- and gamma-isomers; 2-25 pg m(-3)) and endosulfan1 and -2 (5-150 pg m(-3)) were detected in all ground level samples. Seven air samples were collected during mid-troposphere flights (approximately 4400 m altitude) over the Lower Fraser Valley. These flights occurred concurrently with ground level sampling. Trajectory analysis identified three events of substantial mid-troposphere, trans-Pacific flow where 10-day back trajectories stemmed from potential source regions in Asia. These events were also characterized by higher air concentrations of alpha-HCH at 4400 m as compared to the ground level stations. This represents the first event-based, aircraft measurement of advection inputs of OCPs in the mid-troposphere of the west coast of North America.     

Predicting bioavailability and accumulation of organochlorine pesticides by Japanese medaka in the presence of humic acid and natural organic matter using passive sampling membranes

Adsorption to dissolved organic matter (DOM) may significantly decrease the freely dissolved concentration of many hydrophobic organic compounds and, hence, result in reduced bioavailability to aquatic organisms. Here, the suitability of using triolein-embedded cellulose acetate membrane (TECAM) as a biomimetic surrogate to assess the bioavailability of organochlorine pesticides (OCPs) in water in the presence of DOM was explored. The accumulation of OCPs was measured in TECAM and pelagic Japanese medaka (Oryzias latipes) in the laboratory after 12 h exposure to water containing different levels of Aldrich humic acid. Further, OCP uptake by TECAM and medaka in real aqueous environments was evaluated after 30 d exposures in two sites. Laboratory results showed that OCP uptake by medaka consistently decreased with increasing levels of humic acid in the range of 0-15 mg C/L in sample solutions. This tendency was closely mimicked by OCP accumulation in TECAM under the same conditions. Field results showed that TECAM accumulated similar OCP patterns as medaka (r2 = 0.92 for site 1 and r2 = 0.94 for site 2), although comparison of the in-field eight OCP concentrations in TECAM to those in medaka yielded approximately a factor of 3 (on a wet weight basis). These results suggest that the TECAM method can be used as a simple and useful tool to predict the bioavailability and bioaccumulation potential of poorly biotransformed organic compounds in pelagic fish in aqueous environment.     

Three-year atmospheric monitoring of organochlorine pesticides and polychlorinated biphenyls in polar regions and the South Pacific

XAD-2 resin based passive air samplers (PAS) were deployed for three one-year periods at the Korean polar and South Pacific research stations at Ny-?lesund (2005-2009), King George Island (2005-2007), and Chuuk (2006-2009) to investigate long-range transport, local sources, and temporal trends of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs). The highest hexachlocyclohexane (HCH) concentration (35.2-78.9 pg·m(-3)) over the entire sampling period was detected at Ny-?lesund, in the Arctic. α-HCH was the dominant OCP (31.1-67.1 pg·m(-3)), contributing about 50% of the total OCP load. Additionally, a high and consistent α/γ-HCH ratio was observed at Ny-?lesund. HCHs might reach Arctic sites more easily than other OCPs from surrounding countries through long-range atmospheric transport (LRAT). Interestingly, high levels of the current-use OCP endosulfan-particularly endosulfan-I--were detected at almost all sampling sites, including in Antarctica, ranging 12.2-88.5, 17.7-130, and ND-59.7 pg·m(-3) at King George Island, Ny-?lesund, and Chuuk, respectively. Specific OCP and PCB patterns, such as low trans/cis-chlordane ratios and a prevalence of lighter PCB congeners, were observed in all three regions (excepting one site at Ny-?lesund and one site in the South Pacific affected by local sources) during all sampling periods. This indicates that these Polar and remote South Pacific sites are mainly influenced by LRAT. Over the entire sampling period, a decreasing trend of HCHs (α- and γ-HCH) and an increasing trend of endosulfan-I were observed at the Ny-?lesund sites.     

Pesticides in the atmosphere across Canadian agricultural regions

The Canadian Atmospheric Network for Currently Used Pesticides (CANCUP) was the first comprehensive, nationwide air surveillance study of pesticides in Canada. This paper presentsthe atmospheric occurrence and distribution of pesticides including organochlorine pesticides (OCPs), organophosphate pesticides (OPPs), acid herbicides (AHs), and neutral herbicides (NHs) during the spring to summer of 2004 and 2005 across agricultural regions in Canada. Atmospheric concentrations of pesticides varied within years and time periods, and regional characteristics were observed including the following: (i) highest air concentrations of several herbicides (e.g., mecoprop, triallate, and ethalfluralin) were found at Bratt's Lake, SK, a site in the Canadian Prairies; (ii) the west-coast site at Abbotsford, BC, had the maximum concentrations of diazinon; (iii) the fruit and vegetable growing region in Vineland, ON, showed highest levels for several insecticides including chlorpyrifos, endosulfan, and azinphos-methyl; (iv) high concentrations of atrazine and metolachlor were measured at St. Anicet, QC, a corn-growing region; (v) the Kensington site in PEI, Canada's largest potato-producing province, exhibited highest level of dimethoate. Analysis of particle- and gas-phase fractions of air samples revealed that most pesticides including OCPs, OPPs, and NHs exist mainly in the gas phase, while AHs exhibit more diversity in particle-gas partitioning behavior. This study also demonstrated that stirred up soil dust does not account for pesticides that are detected in the particle phase. The estimated dry and wet deposition fluxes indicate considerable atmospheric inputs for some current-use pesticides (CUPs). This data set represents the first measurements for many pesticides in the atmosphere, precipitation, and soil for given agricultural regions across Canada.     

Relating soil solution Zn concentration to diffusive gradients in thin films measurements in contaminated soils

The technique of diffusive gradients in thin films (DGT) has been suggested to sample an available fraction of metals in soil. The objectives of this study were to compare DGT measurements with commonly measured fractions of Zn in soil, viz, the soil solution concentration and the total Zn concentration. The DGT technique was used to measure fluxes and interfacial concentrations of Zn in three series of field-contaminated soils collected in transects toward galvanized electricity pylons and in 15 soils amended with ZnCl2 at six rates. The ratio of DGT-measured concentration to pore water concentration of Zn, R, varied between 0.02 and 1.52 (mean 0.29). This ratio decreased with decreasing distribution coefficient, Kd, of Zn in the soil, which is in agreement with the predictions of the DGT-induced fluxes in soils (DIFS) model. The R values predicted with the DIFS model were generally larger than the observed values in the ZnCl2-amended soils at the higher Zn rates. A modification of the DIFS model indicated that saturation of the resin gel was approached in these soils, despite the short deployment times used (2 h). The saturation of the resin with Zn did not occur in the control soils (no Zn salt added) or the field-contaminated soils. Pore water concentration of Zn in these soils was predicted from the DGT-measured concentration and the total Zn content. Predicted values and observations were generally in good agreement. The pore water concentration was more than 5 times underpredicted for the most acid soil (pH = 3) and for six other soils, for which the underprediction was attributed to the presence of colloidal Zn in the soil solution.     

Metal distributions in New Orleans following hurricanes Katrina and Rita: A continuation study

In late October 2005, twenty-seven metals were determined in soils and sediment layers deposited by floodwaters (flood sediments) within New Orleans, Louisiana. Samples originated from 43 sites along four transects, at an industrial canal, and near the Superdome. The sampling design encompassed flooded and nonflooded areas as well as differing economic strata within the city. Results from this effort confirmed findings of our previous study designed to quantify contaminant profiles in the aftermath of Hurricane Katrina. The expanded sampling from this most recent investigation revealed that arsenic (As) and lead (Pb) concentrations exceeded United States Environmental Protection Agency (USEPA) soil screening criteria indiscriminately throughout the city. However, As and Pb concentrations were lower along St. Charles Avenue, an area largely unaffected by hurricane related flooding. Toxicant concentrations did not exceed soil screening criteria values for lead within any flood sediments or for 32 of 37 soil samples, but arsenic concentrations in 40 of 43 samples exceeded screening criteria.     

Reduction of oxamyl and related pesticides by FeII: influence of organic ligands and natural organic matter

The reduction of oxamyl and related oxime carbamate pesticides (OCPs; methomyl and aldicarb) by FeII is an important pathway for the degradation of these compounds in soil and groundwater. A series of batch kinetic experiments was carried out to assess the effects that selected carboxylate and aminocarboxylate ligands have on these reactions. In the absence of FeII, no OCP reduction by the ligands is observed. In the presence of FeII, the rate of OCP reduction varies by several orders of magnitude and can be described by the expression k(red) = [FeII]sigma(i)k(i)alpha(i) where k(red) is the observed pseudo-first-order rate constant for OCP reduction, [FeII] is the total FeII concentration, alpha(i) is the fraction of each FeII species in solution, and k(i) is the second-order rate constant for OCP reduction by each FeII species. The reactivity of individual FeII species is dependent upon the standard one-electron reduction potential of the corresponding FeIII/FeII redox couple (E(H)o) and the availability of inner-sphere FeII coordination sites for bonding with Lewis base donor groups within the OCP structure. A linear free energy relationship is proposed. Kinetic measurements demonstrate that natural organic matter from the Great Dismal Swamp facilitates OCP reduction by FeII in the same manner as the individual organic ligands. Results from this study improve our understanding of the pathways and rates of pesticide degradation in reducing subsurface environments, especially those rich in organic matter.     

Organochlorine pesticide residues in bamboo shoot

BACKGROUND: Xenobiotic organochlorine pesticides (OCPs) are a major environmental problem because of their historic widespread use, pronounced persistence against chemical and biological degradation, and bioaccumulation in the food chain. Pesticide use is prevalent in the production of edible bamboo shoots, which are exported widely from China. To evaluate the quality of Chinese bamboo shoots we determined the residual content of some OCPs in shoot samples. RESULTS: Three types of OCPs—hexachlorocyclohexane (HCH), 1,1,1‐trichlor‐2,2‐bis(p‐chlorophenyl)ethane (DDT) and pentachloronitrobenzene (PCNB)—were detected in bamboo shoots from Zhejiang province, China. Detection rates were 100%, 100% and 75% for HCH, DDT and PCNB, respectively. However, the average residue concentration did not exceed the maximum residue limit for pesticides detected in food in China (50 µg kg^?1). In terms of residue concentrations of the pesticides, 82.14% of the bamboo shoot samples could be classified as safe. CONCLUSION: While all sampled bamboo shoots contained OCP, most (82.14%) were safe for consumption. Copyright © 2010 Society of Chemical Industry     

Using passive air samplers to assess urban-rural trends for persistent organic pollutants and polycyclic aromatic hydrocarbons. 2. Seasonal trends for PAHs, PCBs, and organochlorine pesticides

This is the second of two papers demonstrating the feasibility of using passive air samplers to investigate persistent organic pollutants along an urban-rural transect in Toronto. The first paper investigated spatial trends for polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs). This second paper investigates the seasonality of air concentrations for polycyclic aromatic hydrocarbons (PAHs), PCBs, and OCPs along this transect. Air samplers, consisting of polyurethane foam (PUF) disks housed in stainless steel domed chambers, were deployed for three 4-month integration periods from June 2000 to July 2001. The seasonal variations of derived air concentrations for PAHs, PCBs, and OCPs reflected the different source characteristics for these compounds. PAHs showed a strong urban-rural gradient with maximum concentrations at urban sites during the summer period (July-October). These high summer values in Toronto were attributed to increases in evaporative emissions from petroleum products such as asphalt. PCBs also exhibited a strong urban-rural gradient with maximum air concentrations (approximately 2-3 times higher) during the spring period (April-June). This was attributed to increased surface-air exchange of PCBs that had accumulated in the surface layer over the winter. alpha-HCH was fairly uniformly distributed, spatially and temporally, as expected. This pattern and the derived air concentration of approximately 35 to approximately 100 pg m(-3) agreed well with high volume air data from this region, adding confidence to the operation of the passive samplers and showing that site-to-site differences in sampling rates was not an issue. For other OCPs, highest concentrations were observed during the spring period. This was associated with either (i) their local and/or regional application (gamma-HCH, endosulfan) and (ii) their revolatilization (chlordanes, DDT isomers, dieldrin, and toxaphene). Principal component analysis resulted in clusters for the different target chemicals according to their chemical class/source type. The results of this study demonstrate how such a simple sampling technique can provide both spatial and seasonal information. These data, integrated over seasons, can be used to evaluate contaminant trends and the potential role of large urban centers as sources of some semivolatile compounds to the regional environment, including the Great Lakes ecosystem.     

Has the burden and distribution of PCBs and PBDEs changed in European background soils between 1998 and 2008? Implications for sources and processes

Background soils were collected from 70 locations on a latitudinal transect in the United Kingdom and Norway in 2008, ten years after they had first been sampled in 1998. The soils were analyzed for polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and organochlorine pesticides (OCs), to see whether there had been any change in the loadings or distributions of these persistent organic pollutants (POPs). The same transect has also been used to sample air between the mid-1990s and the present, so the air and soil spatial and temporal trends provide information on air-soil transfers, source-receptor relationships, long-range atmospheric transport (LRAT), and recycling phenomena. Comparisons of the 2008 and 1998 data sets show a general decline for PBDEs in surface soil, and a smaller averaged net decline of PCBs. Changes between the years were observed for total POP concentrations in soil and also for correlations with site and sample characteristics assumed to affect those concentrations. POP concentrations were correlated to distance and strength of possible sources, a relationship that became weaker in the 2008 data. Fractionation, a commonly discussed process for the global cycling of POPs was also lost in the 2008 data. As in 1998, soil organic matter content continues to have a strong influence on the loadings of POPs in surface soils, but changes in the PCB loads were noted. These factors indicate an approach to air-surface soil equilibrium and a lessening of the influence of primary sources on POP concentrations in soil between 1998 and 2008.