Atmospheric concentrations and dry and wet deposits of some herbicides currently used on the Canadian Prairies

High volume air sampling in the Canadian Prairies was used to characterize atmospheric concentrations for 10 herbicides (alachlor, atrazine, ethalfluralin, metolachlor, 2,4-D, dicamba, bromoxynil, MCPA, trifluralin, and triallate) along a 500-km north-south transect. Atmospheric concentration measurements at various altitudes identified that of the six herbicides present in the highest concentrations, triallate was strongly influenced by local sources, while 2,4-D, dicamba, bromoxynil, MCPA and trifluralin were dominated by regional atmospheric transport. Concentrations of the herbicides measured at various altitudes were compared with dry deposition rates measured using a dry/wet deposition sampler and used to calculate deposition velocities V(d). The primary atmospheric transport mechanism for MCPA and bromoxynil was shown to be adsorption to particles dispersed in the atmosphere, with the same mechanism also confirmed for 2,4-D and dicamba, while trifluralin was shown to be transported mainly in the gas phase. This method of calculation indicated that transportation of triallate was influenced by particle adsorption. Weekly maximum atmospheric loadings of the major herbicides present in the Prairies were estimated to range from 73 kg for trifluralin to 541 kg for 2,4-D.     

Comparison of micrometeorological and two-film estimates of air–water gas exchange for alpha-hexachlorocyclohexane in the Canadian archipelago

The air-sea gas exchange of alpha-hexachlorocyclohexane (α-HCH) in the Canadian Arctic was estimated using a micrometeorological approach and the commonly used Whitman two-film model. Concurrent shipboard measurements of α-HCH in air at two heights (1 and 15 m) and in surface seawater were conducted during the Circumpolar Flaw Lead study in 2008. Sampling was carried out during eight events in the early summer time when open water was encountered. The micrometeorological technique employed the vertical gradient in air concentration and the wind speed to estimate the flux; results were corrected for atmospheric stability using the Monin-Obukhov stability parameter. The Whitman two-film model used the concentrations of α-HCH in surface seawater, in bulk air at 1 and 15 m above the surface, and the Henry's law constant adjusted for temperature and salinity to derive the flux. Both approaches showed that the overall net flux of α-HCH was from water to air. Mean fluxes calculated using the micrometeorological technique ranged from -3.5 to 18 ng m(-2) day(-1) (mean 7.4), compared to 3.5 to 14 ng m(-2) day(-1) (mean 7.5) using the Whitman two-film model. Flux estimates for individual events agreed in direction and within a factor of two in magnitude for six of eight events. For two events, fluxes estimated by micrometeorology were zero or negative, while fluxes estimated with the two-film model were positive, and the reasons for these discrepancies are unclear. Improvements are needed to shorten air sampling times to ensure that stationarity of meteorological conditions is not compromised over the measurement periods. The micrometeorological technique could be particularly useful to estimate fluxes of organic chemicals over water in situations where no water samples are available.     

Persistent organic pollutants (PCB, DDT, HCH, HCB & BDE) in eels (Anguilla anguilla) in Scotland: Current levels and temporal trends

Eels are an ideal biomonitor for persistent organic pollutants (POPs) because of their high lipid content, longevity and tendency to remain within a defined range during their freshwater life phase. This study investigated concentrations of POPs in eels (Anguilla anguilla) from 30 sites across Scotland, including polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (BDEs), DDT (and metabolites), hexachlorocyclohexanes (α, β, γ-HCH), hexachlorobenzene (HCB), hexachlorobutadiene (HCBD) and pentachlorobenzene. Despite its EU-wide ban ∼30 years ago, DDT and its derivatives were detected in almost all samples. PCB 153 and 138 were the most widely detected PCB congeners, while BDE 47 was the dominant BDE. Pentachlorobenzene was not detected, while HCBD was detected once only. α-HCH, β-HCH and HCB concentrations were very low (generally <3 μg/kg or below detection). When compared with 1986 and 1995 data, the results revealed considerable decreases in p,p′-DDE concentrations. More drastic reductions were evident for γ-HCH, reflecting the tightening restrictions on pesticide use imposed over the previous decades.     

Duplicate sampling reproducibility of atmospheric residues of herbicides for paired pan and high-volume air samplers

The reproducibility of collection of atmospheric residues of the herbicides 2,4-D and triallate as bulk (wet plus dry) deposition samples by paired pan samplers and as particulate (filter) and vapour (PUF/XAD-2 resin cartridge) samples by paired high-volume air samplers was determined. Variability of herbicide concentrations in paired bulk deposition samples was within 25% for 65 and 80% of the samples for 2,4-D and triallate, respectively, with approximately 90% of the paired samples being within a factor of 2 for both herbicides. The vapour samples of 2,4-D and triallate showed similar reproducibilities. The highest reproducibility was observed for the filter samples with 92% of the paired data sets for 2,4-D being within 25% variability. No triallate was detected in the filter samples.     

Water–gas exchange of organochlorine pesticides at Lake Chaohu, a large Chinese lake

Organochlorine pesticides (OCPs), a potential threat to ecosystems and human health, are still widely residual in the environment. The residual levels of OCPs in the water and gas phase were monitored in Lake Chaohu, a large Chinese lake, from March 2010 to February 2011. Nineteen types of OCPs were detected in the water with a total concentration of 7.27?±?3.32 ng/l. Aldrin, DDTs and HCHs were the major OCPs in the water, accounting for 38.3 %, 28.9 % and 23.6 % of the total, respectively. The highest mean concentration (12.32 ng/l) in the water was found in September, while the lowest (1.74 ng/l) was found in November. Twenty types of gaseous OCPs were detected in the atmosphere with a total concentration of 542.0?±?636.5 pg/m³. Endosulfan, DDTs and chlordane were the major gaseous OCPs in the atmosphere, accounting for 48.9 %, 22.5 % and 14.4 % of the total, respectively. The mean concentration of gaseous OCPs was significantly higher in summer than in winter. o,p′-DDE was the main metabolite of DDT in both the water and gas phase. Of the HCHs, 52.3 % existed as β-HCH in the water, while α-HCH (37.9 %) and γ-HCH (30.9 %) were dominant isomers in the gas phase. The average fluxes were ?21.11, ?3.30, ?152.41, ?35.50 and ?1314.15 ng/(m²?day) for α-HCH, γ-HCH, HCB, DDT and DDE, respectively. The water–gas exchanges of the five types of OCPs indicate that water was the main potential source of gaseous OCPs in the atmosphere. A sensitivity analysis indicated that the water-gas flux of α-HCH, γ-HCH and DDT is more vulnerable than that of HCB and DDE to the variation of the parameters. The possible source of the HCHs in the water was from the historical usage of lindane; however, that in the air was mainly from the recent usage of lindane. The technical DDT and dicofol might be the source of DDTs in the water and air.     

Influence of usage and chemical–physical properties on the atmospheric transport and deposition of pesticides to agricultural regions of Manitoba,Canada

This study quantified the masses of 14 pesticides deposited as wet (precipitation) versus dry (gaseous and particle) atmospheric deposition at a research farm in southwestern Manitoba, Canada. The concentration in air of these pesticides was also measured. Total bulk deposition amounts (wet + dry) ranged from 0.009 to 2.3 μg m^?2 for the 12 pesticides detected, and for the six pesticides with both wet and dry deposition detections, dry deposition contributed 12–51% of the total deposition over the crop growing season. Although not applied at the site, eight herbicides registered for use in Canada, as well as lindane (γ-HCH), were all frequently detected (92–100%) in the 12 air samples analyzed during the crop growing season, with by-product isomer α-HCH (75%), clopyralid (50%) and atrazine (8%) detected to a lesser extent. The chemical’s physicochemical properties and the relative mean mass of each agricultural pesticide applied in the province of Manitoba and in a 13 km radius were significant parameters in explaining the trends in the concentrations of pesticides detected in our samples. The important contribution of dry deposition to total pesticide deposition warrants greater attention in arid and semi-arid areas such as the Prairie Region of Canada, also because under a changing climate this region is estimated to experience more severe droughts while the more favorable conditions predicted for pest infestations could lead to increased pesticide applications in agricultural and urban areas.     

Distributions, sources, and ecological risks of hexachlorocyclohexanes in the sediments from Haihe Plain, Northern China

The levels of hexachlorocyclohexanes (HCHs) in the sediments from Haihe Plain, China, were measured by a gas chromatograph with a ⁶³Ni microelectron capture detector. The spatial distributions, possible sources, and potential ecological risks of these compounds were analyzed. The residual level of total HCHs was 33.84?±?173.37 ng?g^?1 dry weight (d.w.) with ranges of 0.13?～?1,107.41 ng?g^?1 d.w. Much higher ΣHCH contents were found in the lower reaches of some rivers and in the mouth of the main stream receiving tributaries. The predominance of β-HCH (36 %) in the sediments was similar to that in the soils from Haihe Plain. The high percentages of γ-HCH (23–41 %) could be detected at 25 % of the sampling sites in the seven river systems. There were statistically significant positive relationships between the contents of HCHs and total organic carbon. Lindane was identified as the primary source of HCHs in the sediments, and it seemed that recent illegal lindane inputs still existed in some areas in Haihe Plain, as indicated by the α-/γ-HCH and β-/(α?+?γ)-HCH ratios. Severe potential ecological risks of γ-HCH to benthic organisms at some sampling sites were found based on the consensus-based sediment quality guidelines.     

Residues of organochlorine and organophosphorus pesticides in sugarcane crop soils and river water

The presence of residual organochlorine and organophosphorus pesticides was evaluated at different periods of sugarcane cultivation in agricultural soil and water samples from the town of Tlaltizapan, which is located in the state of Morelos in Mexico, to determine the presence and persistence of these compounds and their possible effects on the region. The compounds p,p′-DDE, p,p′-DDD (metabolites of p,p′-DDT), γ-HCH and heptachlor were found in more of 95% of the sampling zones in the three monitoring periods performed along 2 years. The highest concentration detected (129.6 μg/kg _{dry soil}) was for α-HCH, but its frequency of detection was ～5%. The low detection frequency of α-HCH and the high concentration values of γ-HCH indicate the repeated use of technical-grade HCH and Lindane (γ-HCH) in the region. Among the organophosphorus pesticides, ethyl parathion was the compound with the highest soil concentration, at ～2000 μg/kg_{dry soil}, during the initial monitoring. However, this compound was detected in the second monitoring with a concentration of ～4 μg/kg_{dry soil}, but it was not detected in the third, indicating that is was not accumulated in the environment. The heptachlor was the compound most commonly found in all water samples, within a range of 0.45–1.25 ng/L. The presence of this organochlorine compound in the water samples indicated a possible migration from the soil to water bodies due to soil erosion. The presence of organophosphorus compounds was not detected in the water samples, which could be attributed to the moderate persistence of these compounds and their consequent degradation before arriving at the water bodies.     

Comparative study of the effects of MCPA, butylate, atrazine, and cyanazine on Selenastrum capricornutum

The herbicides MCPA, butylate, atrazine and cyanazine are extensively used in Canadian agriculture and information regarding their effects on indigenous biota is scarce. Phytotoxicity assessments were conducted in the laboratory on the common green alga Selenastrum capricornutum using both the active ingredient of the herbicides and their formulated products (for MCPA and butylate). Endpoints determined after the 96 h exposure included algal population growth inhibition (IC50-cell counts), percent lethality (LC50-flow cytometry derived) and photosynthetic electron transport inhibition (EC50-fluorescence induction). Pesticide formulations had greater toxic effects than the active ingredient alone. The 96 h IC50 (50% Inhibition Concentration) and LOEC (Lowest Observable Effects Concentration) using cell counts of S. capricornutum were 18.4 and 8.9 mg l(-1) respectively for MCPA-active ingredient and for MCPA-formulated, these were 0.62 and 0.0062 mg l(-1) respectively. Those for butylateactive ingredient were 61.0 and 8.3 mg l(-1) and for butylate-formulated 1.46 and 0.17 mg l(-1), respectively. The triazines active ingredient, which are photosynthetic inhibitors, had greater effects than either the MCPA or butylate. The IC50 for cyanazine and atrazine were 0.059 and 0.026 mg l(-1), respectively. By comparing the IC50 and LC50 values for the tested active ingredients, it was found that the effects of atrazine were algicidal, whereas those of cyanazine, butylate and MCPA were algistatic.     

Herbicide levels in rivers draining two prairie agricultural watersheds (1984)

A monitoring survey was conducted during 1984 on the Ochre and Turtle Rivers, which flow into Dauphin Lake in western Manitoba, Canada, to determine levels of the herbicides MCPA, diclofop-methyl, dicamba, bromoxynil, 2,4-D, triallate and trifluralin which were widely used in each watershed. Triallate concentrations exceeded 4 ng/L in 50% and 10% of the 21 samples taken from each of the Turtle and Ochre River, respectively, during the period March to October 1984. Trifluralin concentrations exceeded 3 ng/L in 14% and 10% of the samples from the respective rivers. Maximum concentrations did not exceed 25 ng/L and were unrelated to changes in river flow. Bromoxynil and diclofop were detected in the Turtle River, at concentrations of 113 and 476 ng/L, respectively, following a major high water event in late June, but were undetectable (less than 2 and 12 ng/L, respectively) at other sampling times. Dicamba and 2,4-D were detectable throughout most of the sampling period in both rivers at low levels (less than 100 ng/L). High levels of dicamba and 2,4-D (5476 and 2568 ng/L respectively) were found in water from the Turtle River prior to the high water event event possibly caused by spraying of ditches or rights-of-way near the river. Discharges (grams/year) of all seven herbicides monitored in the study represented less than 0.1% of the amounts estimated to be used in each watershed. Unit loadings (mg/ha/year) of 2,4-D and dicamba were similar to those reported for Southern Ontario streams in the mid-1970's. The results indicate that herbicide contamination of Manitoba streams draining agricultural areas is generally low except when major runoff occurs during the application period in May and June.     

Evaluation of polyurethane foam as a trapping medium for herbicide vapor in air monitoring and worker inhalation studies

Polyurethane foam was an efficient adsorbent for trapping vapors of butyl esters of 2,4-D (2,4-dichlorophenoxyacetic acid) and triallate (S-(2,3,3-trichloroallyl)diisopropylthiocarbamate) in high volume air monitoring studies and of butyl esters of 2,4-D, iso-octyl ester of 2,4-D, n-butyl ester of 2,4,5-T (2,4,5-trichlorophenoxyacetic acid), bromoxynil octanoate (2,5-dibromo-4-hydroxybenzonitrile), triallate, and trifluralin (alpha, alpha, alpha-trifluoro-2,6-dinitro-N-N-dipropyl-p-toluidine) in short-term, low volume, worker inhalation exposure studies. The collected herbicide vapor was readily desorbed under soxhlet extraction with n-hexane and subsequently analyzed with electron-capture GLC. The overall efficiencies, for both trapping and extraction, were over 90%, using a single plug, for all herbicides, except triallate. In the case of triallate, two plugs in series were required for efficient trapping under the high volume air monitoring situation.     

A modeling assessment of association between East Asian summer monsoon and fate/outflow of α-HCH in Northeast Asia

Using a dynamic numerical atmospheric transport model for organochlorine pesticides (OCPs), the relationship between the East Asian summer monsoon and the fate of α-hexachlorocyclohexane (α-HCH), a banned OCP, in the atmosphere over Northeast Asia was investigated and assessed. The modeled temporal and spatial patterns and variability of α-HCH air concentrations during the summer months of 2005 revealed a strong link between this chemical in the atmosphere over Northeast Asia and the East Asian summer monsoon. At lower atmospheric levels, easterly and southeasterly winds blowing from relatively cold ocean surface convey α-HCH air concentration from southeast China to northeast China. A monsoon front extending from southeast China to Japan, characterized by a strong wind convergence, carried the air concentration to a high elevation of the atmosphere where it was delivered by southerly monsoon flow to northern China and North Pacific Ocean. This summer monsoon associated northward atmospheric transport caused a reversal of the soil/air exchange from outgassing to net deposition during spring–summer period. The modeled wet deposition fluxes of α-HCH agreed well with the changes in the typical summer monsoon rain bands, designated as Meiyu in China, Changma in Korea, and Baiu in Japan. The major wet deposition flux paralleled with the monsoon front as well as the monsoon rain bands. The temporal change in the fluxes exhibits abrupt northward advances, which is associated with a stepwise northward and northeastward advance of the East Asian summer monsoon. The modeled α-HCH outflow in the atmosphere from China occurs mostly in the summer months and through northeast China, featured strongly by the evolution of the summer month. This study suggests that the East Asian summer monsoon provides a major atmospheric pathway and summer outflows to α-HCH over East Asia.     

Toxicity assessment of 2,4-D and MCPA herbicides in primary culture of fish hepatic cells

In this study, we used primary cultures of fish hepatic cells as a tool for evaluating the effects of environmental contamination. Primary hepatic cell cultures derived from the subtropical fish Metynnis roosevelti were exposed to different concentrations (0.275, 2.75 and 27.5 μg L^?1) of the herbicides 2,4-dichlorophenoxyacetic acid (2,4-D) and 4-chloro-2-methylphenoxyacetic acid (MCPA). Cellular respiratory activity was evaluated by polarography using three substrates: 0.5 M glucose, 0.5 M succinate and 0.5 M α-ketoglutarate. Significant changes were observed in cellular oxygen consumption with 0.5 M α-ketoglutarate. Even at low concentrations, 2,4-D and MCPA were potent uncouplers of oxidative phosphorylation. Primary cultures of M. roosevelti liver cells may provide a useful tool for the evaluation of environmental contaminant effects. A review of regulations regarding permitted concentrations of these herbicides is needed.     

Occurrence of boscalid and other selected fungicides in surface water and groundwater in three targeted use areas in the United States

Although the use of the insecticide γ-hexachlorocyclohexane (HCH) is now prohibited in many countries because of its hazardousness, stockpiles of γ-HCH still exist. In this study, we subjected γ-HCH to mechanochemical (MC) treatment with a planetary ball mill in the presence of CaO to investigate the feasibility of using this method for the treatment of γ-HCH stockpiles. We confirmed the degradation of γ-HCH and investigated the degradation mechanism. The major intermediates were identified to be 1,3,4,5,6-pentachlorocyclohexene (γ-PCCH) and chlorobenzenes (CBzs). Analysis of the steric structure of γ-HCH and identification of the degradation intermediates suggested that successive dehydrochlorination led to the formation of trichlorobenzenes. Products of further degradation (dichlorobenzenes, monochlorobenzene, and benzene) were also detected. Surprisingly, methane and ethane were also detected, which suggests cleavage of the C-C bonds of the cyclohexane ring and hydrogenation. All of the chlorine atoms in the γ-HCH could be transformed into inorganic chloride compounds by the MC treatment with CaO. Our results indicate that γ-HCH can be completely dechlorinated by MC treatment.     

Release of hexachlorocyclohexanes from historically and freshly contaminated soils in China: implications for fate and regulation

Hexachlorocyclohexanes (HCHs) were produced and used in large quantity worldwide and are common soil pollutants. In this study, desorption of α-HCH and γ-HCH from two soil samples collected from a historical pesticide plant in Tianjin, China, was examined. As a comparison, desorption of freshly sorbed γ-HCH was examined, using five typical Chinese soils. Strong resistant desorption was observed for both historically contaminated and freshly contaminated soils, and desorption results were well modeled with a biphasic desorption isotherm. The unique thermodynamic characteristics associated with the desorption-resistant fraction indicated that physical constraint within soil organic matrices was likely the predominant mechanism controlling resistant desorption. Resistant desorption could have significant effects on fate and exposure of HCHs in soil environment. More accurate biphasic desorption models that take into account of the resistant desorption can be used to facilitate regulating, management and remediation of HCH-contaminated sites.     

Sorption and desorption of glyphosate,MCPA and tetracycline and their mixtures in soil as influenced by phosphate

Phosphate fertilizers and herbicides such as glyphosate and MCPA are commonly applied to agricultural land, and antibiotics such as tetracycline have been detected in soils following the application of livestock manures and biosolids to agricultural land. Utilizing a range of batch equilibrium experiments, this research examined the competitive sorption interactions of these chemicals in soil. Soil samples (0-15 cm) collected from long-term experimental plots contained Olsen P concentrations in the typical (13 to 20 mg kg^?1) and elevated (81 to 99 mg kg^?1) range of build-up phosphate in agricultural soils. The elevated Olsen P concentrations in field soils significantly reduced glyphosate sorption up to 50%, but had no significant impact on MCPA and tetracycline sorption. Fresh phosphate additions in the laboratory, introduced to soil prior to, or at the same time with the other chemical applications, had a greater impact on reducing glyphosate sorption (up to 45%) than on reducing tetracycline (up to 13%) and MCPA (up to 8%) sorption. The impact of fresh phosphate additions on the desorption of these three chemicals was also statistically significant, but numerically very small namely < 1% for glyphosate and tetracycline and 3% for MCPA. The presence of MCPA significantly reduced sorption and increased desorption of glyphosate, but only when MCPA was present at concentrations much greater than environmentally relevant and there was no phosphate added to the MCPA solution. Tetracycline addition had no significant effect on glyphosate sorption and desorption in soil. For the four chemicals studied, we conclude that when mixtures of phosphate, herbicides and antibiotics are present in soil, the greatest influence of their competitive interactions is phosphate decreasing glyphosate sorption and the presence of phosphate in solution lessens the potential impact of MCPA on glyphosate sorption. The presence of chemical mixtures in soil solution has an overall greater impact on the sorption than desorption of individual organic chemicals in soil.     

Residues and chiral signatures of organochlorine pesticides in sediments from Xiangshan Bay, East China Sea

Residual levels and enantiomeric signatures of hexachlorocyclohexanes (HCHs) and dichlorodiphenyltrichloroethanes (DDTs) in surface sediments from Xiangshan Bay, East China Sea were investigated. The concentrations of ∑HCHs (sums of α-, β-, γ-, and δ-HCH) and ∑DDTs (sums of p, p'-DDT, p, p'-DDD,p, p'-DDE, o, p'-DDT, and o, p'-DDD) ranged from 0.14 to 0.67 ng g?1 and 0.61 to 22.38 ng g?1, respectively. A slight potential health risk to the organism was then indicated for the residual levels of DDTs according to the ERL/ERM guidelines. Moreover, the predominant β-HCH implied that the technical HCH contamination was mainly due to the historical usage. But the high ratio of DDT/∑DDTs depicted a cocktail input pattern of fresh and weathered DDTs. The enantiomeric fractions (EFs) of α-HCH, o, p'-DDT, and o, p'-DDD were also determined. The degradation of α-HCH was enantioselective in all sediments samples, resulting in an enrichment of (-)-enantiomers. However, the racemic residues of o, p'-DDT and o, p'-DDD were observed in all sediments samples.     

Modeling redistribution of α-HCH in Chinese soil induced by environment factors

This study explores long-term environmental fate of α-HCH in China from 1952 to 2007 using ChnGPERM (Chinese Gridded Pesticide Emission and Residue Model). The model captures well the temporal and spatial variations of α-HCH concentration in Chinese soils by comparing with a number of measured data across China in different periods. The results demonstrate α-HCH grasshopping effect in Eastern China and reveal several important features of the chemical in Northeast and Southeast China. It is found that Northeast China is a prominent sink region of α-HCH emitted from Chinese sources and α-HCH contamination in Southwest China is largely attributed to foreign sources. Southeast China is shown to be a major source contributing to α-HCH contamination in Northeast China, incurred by several environmental factors including temperature, soil organic carbon content, wind field and precipitation.     

Organochlorine pesticides and polychlorinated biphenyls in air and soil across Azerbaijan

Concentrations of selected organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) are reported in air and surface soil in an extensive spatial survey across Azerbaijan, a country bordering the Caspian Sea with a history of OCP production and extensive use. Polyurethane foam disc passive air samplers (PAS) were deployed during October-November 2008 with soil samples collected in July 2009. Levels of Σ(7)PCB in ambient air were generally low (mean of 0.046 ng m(-3), n?=?13) and comparable to concentrations reported in countries within Eastern Europe and similar to or lower than concentrations reported in urban air in the UK and other western countries. Surprisingly, PCB concentrations in rural/background soil fell below the method detection limits at most sites, although concentrations were 0.209 and 0.071 ng Σ(7)PCB g(-1) dry weight (dw) for two urban sites, again comparable to PCB levels measured at background sites in Europe. Levels of α-HCH, β-HCH, γ-HCH and p,p'-DDT/E were elevated in ambient air across Azerbaijan in comparison to PAS-derived concentrations reported elsewhere, with concentrations of α-HCH in air ranging from 0.085 to 2.699 ng m(-3) and p,p'-DDE, 0.037-2.290 ng m(-3). High concentrations of OCPs occurred at several of the urban sites and at sites in proximity to old pesticide storage facilities with concentrations in soil >0.1 μg g(-1) dw for p,p'-DDE and p,p'-DDT at several sites. The ratio of p,p'-DDT/p,p'-DDE was close to unity in the soil at these sites, but elsewhere, the ratio was <1, indicating a weathered DDT pattern, which was also reflected in the air at all sites. A fugacity approach revealed the strong likelihood of net soil-to-air transfer at the majority of sites for all OCPs. The calculated annual fluxes or loading to the atmosphere from a rural/agricultural area (representing land as vineyards and cotton cultivation) were estimated to be on the order of ≈10-100 kg year(-1) for the HCH isomers (including the β -isomer) and p,p'-DDE. The high levels of OCPs in soils, particularly in the vicinity of obsolete-pesticide storage facilities and at select urban sites are of concern and warrant regular monitoring activities and the development of containment or mitigation strategies.