Atmospheric Hydroxyl Radical Reaction Rate Coefficient and Total Environmental Lifetime of α-Endosulfan.

Endosulfan is a persistent organochlorine pesticide that was globally distributed before it was banned and continues to cycle in the Earth system. The chemical kinetics of the gas-phase reaction of α-endosulfan with the hydroxyl radical (OH) was studied by means of pulsed vacuum UV flash photolysis and time-resolved resonance fluorescence (FP-RF) as a function of temperature in the range of 348-395 K and led to a second-order rate coefficient kOH = 5.8 × 10-11 exp(-1960K/T) cm3 s-1 with an uncertainty range of 7 × 10-12 exp(-1210K/T) to 4 × 10-10 exp(-2710K/T) cm3 s-1. This corresponds to an estimated photochemical atmospheric half-life in the range of 3-12 months, which is much longer than previously assumed (days to weeks). Comparing the atmospheric concentrations observed after the global ban of endosulfan with environmental multimedia model predictions, we find that photochemical degradation in the atmosphere is slower than the model-estimated biodegradation in soil or water and that the latter limits the total environmental lifetime of endosulfan. We conclude that the lifetimes typically assumed for soil and aquatic systems are likely underestimated and should be revisited, in particular, for temperate and warm climates.

Selected Persistent Organic Pollutants in Ambient Air in Turkey: Regional Sources and Controlling Factors.

As a result of its unique location, Turkey receives air masses from Europe, Russia, Middle East, and Africa, making it an important place in terms of long-range atmospheric transport (LRT) of contaminants. Atmospheric levels of 22 organochlorine pesticides (OCPs), 45 polychlorinated biphenyls (PCBs), and 14 polybrominated diphenyl ethers (PBDEs) were measured in two metropolitan cities, Istanbul and Izmir, on a weekly basis from May 2014 to May 2015. Dichlorodiphenyltrichloroethane (DDT) and its derivatives were dominant OCP species, followed by isomers of hexachlorocyclohexane (HCH) at both sites. The annual mean concentration of ∑DDX (sum of o,p'-DDT, p,p'-DDT, o,p'-DDD, p,p'-DDD, o,p'-DDE, and p,p'-DDE) was 82 pg/m3 for Istanbul and 89 pg/m3 for Izmir, while these levels were about 46 pg/m3 for ∑HCHs (sum of α-, ß-, γ-, and δ-HCH) at both of the sites. At both stations, tri- and tetra-PCBs and tetra- and penta-PBDEs were dominant congeners. The temperature dependence indicates that both LRT and local contaminated areas contribute to the elevated levels. A Lagrangian particle dispersion model (FLEXPART) showed a few potential source regions in northern Africa and Middle East, southern-southwestern and eastern Europe including Russia, as well as from local domestic metropolitan areas.

Modeling the Formation, Degradation, and Spatiotemporal Distribution of 2-Nitrofluoranthene and 2-Nitropyrene in the Global Atmosphere.

Polycyclic aromatic hydrocarbons (PAHs) are common atmospheric pollutants and known to cause adverse health effects. Nitrated PAHs (NPAHs) are formed in combustion activities and by nitration of PAHs in the atmosphere and may be equally or more toxic, but their spatial and temporal distribution in the atmosphere is not well characterized. Using the global EMAC model with atmospheric chemistry and surface compartments coupled, we investigate the formation, abundance, and fate of two secondarily formed NPAHs, 2-nitrofluoranthene (2-NFLT) and 2-nitropyrene (2-NPYR). The default reactivity scenario, the model with the simplest interpretation of parameters from the literature, tends to overestimate both absolute concentrations and NPAH/PAH ratios at observational sites. Sensitivity scenarios indicate that NO2-dependent NPAH formation leads to better agreement between measured and predicted NPAH concentrations and that photodegradation is the most important loss process of 2-NFLT and 2-NPYR. The highest concentrations of 2-NFLT and 2-NPYR are found in regions with strong PAH emissions, but because of continued secondary formation from the PAH precursors, these two NPAHs are predicted to be spread across the globe.

Oxygenated and Nitrated Polycyclic Aromatic Hydrocarbons in Ambient Air-Levels, Phase Partitioning, Mass Size Distributions, and Inhalation Bioaccessibility.

Among the nitrated and oxygenated polycyclic aromatic hydrocarbons (NPAHs and OPAHs) are some of the most hazardous substances to public health, mainly because of their carcinogenicity and oxidative potential. Despite these concerns, the concentrations and fate of NPAHs and OPAHs in the atmospheric environment are largely unknown. Ambient air concentrations of 18 NPAHs, 5 quinones, and 5 other OPAHs were determined at two urban and one regional background sites in central Europe. At one of the urban sites, the total (gas and particulate) concentrations of Σ10OPAHs were 10.0 ± 9.2 ng/m3 in winter and 3.5 ± 1.6 ng/m3 in summer. The gradient to the regional background site exceeded 1 order of magnitude. Σ18NPAH concentrations were typically 1 order of magnitude lower than OPAHs. Among OPAHs, 9-fluorenone and (9,10)-anthraquinone were the most abundant species, accompanied by benzanthrone in winter. (9,10)-Anthraquinone represented two-thirds of quinones. We found that a large fraction of the target substance particulate mass was carried by submicrometer particles. The derived inhalation bioaccessibility in the PM10 size fraction is found to be ≈5% of the total ambient concentration of OPAHs and up to ≈2% for NPAHs. For 9-fluorenone and (9,10)-anthraquinone, up to 86 and 18%, respectively, were found at the rural site. Our results indicate that water solubility could function as a limiting factor for bioaccessibility of inhaled particulate NPAHs and OPAHs, without considerable effect of surfactant lipids and proteins in the lung lining fluid.

Fast Formation of Nitro-PAHs in the Marine Atmosphere Constrained in a Regional-Scale Lagrangian Field Experiment.

Polycyclic aromatic hydrocarbons (PAHs) and some of their nitrated derivatives, NPAHs, are seemingly ubiquitous in the atmospheric environment. Atmospheric lifetimes may nevertheless vary within a wide range, and be as short as a few hours. The sources and sinks of NPAH in the atmosphere are not well understood. With a Lagrangian field experiment and modeling, we studied the conversion of the semivolatile PAHs fluoranthene and pyrene into the 2-nitro derivatives 2-nitrofluoranthene and 2-nitropyrene in a cloud-free marine atmosphere on the time scale of hours to 1 day between a coastal and an island site. Chemistry and transport during several episodes was simulated by a Lagrangian box model i.e., a box model coupled to a Lagrangian particle dispersion model, FLEXPART-WRF. It is found that the chemical kinetic data do capture photochemical degradation of the 4-ring PAHs under ambient conditions on the time scale of hours to 1 day, while the production of the corresponding NPAH, which sustained 2-nitrofluoranthene/fluoranthene and 2-nitropyrene/pyrene yields of (3.7 ± 0.2) and (1.5 ± 0.1)%, respectively, is by far underestimated. Predicted levels of NPAH come close to observed ones, when kinetic data describing the reactivity of the OH-adduct were explored by means of theoretically based estimates. Predictions are also underestimated by 1-2 orders of magnitude, when NPAH/PAH yields reported from laboratory experiments conducted under high NOx conditions are adopted for the simulations. It is concluded that NPAH sources effective under low NOx conditions, are largely underestimated.

Heterogeneous OH Oxidation, Shielding Effects, and Implications for the Atmospheric Fate of Terbuthylazine and Other Pesticides.

Terbuthylazine (TBA) is a widely used herbicide, and its heterogeneous reaction with OH radicals is important for assessing its potential to undergo atmospheric long-range transport and to affect the environment and public health. The apparent reaction rate coefficients obtained in different experimental investigations, however, vary by orders of magnitude depending on the applied experimental techniques and conditions. In this study, we used a kinetic multilayer model of aerosol chemistry with reversible surface adsorption and bulk diffusion (KM-SUB) in combination with a Monte Carlo genetic algorithm to simulate the measured decay rates of TBA. Two experimental data sets available from different studies can be described with a consistent set of kinetic parameters resolving the interplay of chemical reaction, mass transport, and shielding effects. Our study suggests that mass transport and shielding effects can substantially extend the atmospheric lifetime of reactive pesticides from a few days to weeks, with strong implications for long-range transport and potential health effects of these substances.

Aerosol Health Effects from Molecular to Global Scales.

Poor air quality is globally the largest environmental health risk. Epidemiological studies have uncovered clear relationships of gaseous pollutants and particulate matter (PM) with adverse health outcomes, including mortality by cardiovascular and respiratory diseases. Studies of health impacts by aerosols are highly multidisciplinary with a broad range of scales in space and time. We assess recent advances and future challenges regarding aerosol effects on health from molecular to global scales through epidemiological studies, field measurements, health-related properties of PM, and multiphase interactions of oxidants and PM upon respiratory deposition. Global modeling combined with epidemiological exposure-response functions indicates that ambient air pollution causes more than four million premature deaths per year. Epidemiological studies usually refer to PM mass concentrations, but some health effects may relate to specific constituents such as bioaerosols, polycyclic aromatic compounds, and transition metals. Various analytical techniques and cellular and molecular assays are applied to assess the redox activity of PM and the formation of reactive oxygen species. Multiphase chemical interactions of lung antioxidants with atmospheric pollutants are crucial to the mechanistic and molecular understanding of oxidative stress upon respiratory deposition. The role of distinct PM components in health impacts and mortality needs to be clarified by integrated research on various spatiotemporal scales for better evaluation and mitigation of aerosol effects on public health in the Anthropocene.

Diurnal Variations of Air-Soil Exchange of Semivolatile Organic Compounds (PAHs, PCBs, OCPs, and PBDEs) in a Central European Receptor Area.

Concentrations of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), and polybrominated diphenyl ethers (PBDEs) in air and soil, their fugacities, and the experimental soil-air partitioning coefficient (KSA) were determined at two background sites in the Gt. Hungarian Plain in August 2013. The concentrations of the semivolatile organic compounds (SOCs) in the soil were not correlated with the organic carbon content but with two indirect parameters of mineralization and aromaticity, suggesting that soil organic matter quality is an important parameter affecting the sorption of SOCs onto soils. Predictions based on the assumption that absorption is the dominant process were in good agreement with the measurements for PAHs, OCPs, and the low chlorinated PCBs. In general, soils were found to be a source of PAHs, high chlorinated PCBs, the majority of OCPs and PBDEs, and a sink for the low chlorinated PCBs and γ-hexachlorocyclohexane. Diurnal variations in the direction of the soil-air exchange were found for two compounds (i.e., pentachlorobenzene and p,p'-dichlorodiphenyldichloroethane), with volatilization during the day and deposition in the night. The concentrations of most SOCs in the near-ground atmosphere were dominated by revolatilization from the soil.

Evaluation of a Conceptual Model for Gas-Particle Partitioning of Polycyclic Aromatic Hydrocarbons Using Polyparameter Linear Free Energy Relationships.

A model for gas-particle partitioning of polycyclic aromatic hydrocarbons (PAHs) was evaluated using polyparameter linear free energy relationships (ppLFERs) following a multiphase aerosol scenario. The model differentiates between various organic (i.e., liquid water-soluble (WS)/organic soluble (OS) organic matter (OM), and solid/semisolid organic polymers) and inorganic phases of the particulate matter (PM). Dimethyl sulfoxide and polyurethane were assigned as surrogates to simulate absorption into the above-mentioned organic phases, respectively, whereas soot, ammonium sulfate, and ammonium chloride simulated adsorption processes onto PM. The model was tested for gas and PM samples collected from urban and nonurban sites in Europe and the Mediterranean, and the output was compared with those calculated using single-parameter linear free energy relationship (spLFER) models, namely Junge-Pankow, Finizio, and Dachs-Eisenreich. The ppLFER model on average predicted 96 ± 3% of the observed partitioning constants for semivolatile PAHs, fluoranthene, and pyrene, within 1 order of magnitude accuracy with root-mean-square errors (RMSE) of 0.35-0.59 across the sites. This was a substantial improvement compared to Finizio and Dachs-Eisenreich models (37 ± 17 and 46 ± 18% and RMSE of 1.03-1.40 and 0.94-1.36, respectively). The Junge-Pankow model performed better among spLFERs but at the same time showed an overall tendency for overestimating the partitioning constants. The ppLFER model demonstrated the best overall performance without indicating a substantial intersite variability. The ppLFER analysis with the parametrization applied in this study suggests that the absorption into WSOSOM could dominate the overall partitioning process, while adsorption onto salts could be neglected.

Atmospheric transport of persistent organic pollutants to and from the Arctic under present-day and future climate.

The long-term atmospheric cycling and fate of persistent organic pollutants under the influence of a changing climate is a concern. A GCM's realization of present-day (1970-1999) and future (2070-2099) climate, the latter under a medium scenario of greenhouse gas emissions, is used to study meridional transports and their correlations with the Arctic and North Atlantic Oscillations (AO and NAO). Regions of import and export maxima into the Arctic are identified along the Arctic Circle. It is found that, under future climate conditions, the net export of PCB153 out of the Arctic will increase. The meridional net flux pattern of this substance is expected to become independent of AO and NAO. For DDT, a trend of decreasing net Arctic import will reverse to an increasing trend 100 years after peak emission, which is partly due to more frequent AO and NAO positive phases. It is concluded that the long-term accumulation trends in the Arctic of other persistent pollutants, including so-called emerging pollutants, are subject to the substances' specific behavior and fate in the environment and need to be studied specifically.

Spatial distribution of old and emerging flame retardants in Chinese forest soils: sources, trends and processes.

The levels and distribution of polybrominated diphenylethers (PBDEs), novel brominated flame retardants (NBFRs) and Dechlorane Plus (DP) in soils and their dependence on environmental and anthropological factors were investigated in 159 soil samples from 30 background forested mountain sites across China. Decabromodiphenylethane (DBDPE) was the most abundant flame retardant (25-18,000 pg g(-1) and 5-13,000 pg g(-1) in O-horizon and A-horizon, respectively), followed by BDE 209 (nd-5900 pg g(-1) and nd-2400 pg g(-1) in O-horizon and A-horizon, respectively). FRs distributions were primarily controlled by source distribution. The distributions of most phasing-out PBDEs, DP isomers and TBPH were in fact correlated to a population density-based index used as proxy of areas with elevated usage and waste of FR containing products. High concentrations of some NBFRs were however observed in industrialized regions and FR manufacturing plants. Strongly positive correlations were observed between PBDEs and their replacement products suggesting similar emission pattern and environmental behavior. Exposure of mineral subsoils depended on precipitations driving leaching of FRs into the soil core. This was especially evident for some emerging BFRs (TBE, TBPH, and TBB etc.) possibly indicating potential for diffuse groundwater contamination.

Chemical reactivity and long-range transport potential of polycyclic aromatic hydrocarbons--a review.

Polycyclic aromatic hydrocarbons (PAHs) are of considerable concern due to their well-recognised toxicity and especially due to the carcinogenic hazard which they present. PAHs are semi-volatile and therefore partition between vapour and condensed phases in the atmosphere and both the vapour and particulate forms undergo chemical reactions. This article briefly reviews the current understanding of vapour-particle partitioning of PAHs and the PAH deposition processes, and in greater detail, their chemical reactions. PAHs are reactive towards a number of atmospheric oxidants, most notably the hydroxyl radical, ozone, the nitrate radical (NO3) and nitrogen dioxide. Rate coefficient data are reviewed for reactions of lower molecular weight PAH vapour with these species as well as for heterogeneous reactions of higher molecular weight compounds. Whereas the data for reactions of the 2-3-ring PAH vapour are quite extensive and generally consistent, such data are mostly lacking for the 4-ring PAHs and the heterogeneous rate data (5 and more rings), which are dependent on the substrate type and reaction conditions, are less comprehensive. The atmospheric reactions of PAH lead to the formation of oxy and nitro derivatives, reviewed here, too. Finally, the capacity of PAHs for long range transport and the results of numerical model studies are described. Research needs are identified.

Air-soil cycling of oxygenated, nitrated and parent polycyclic aromatic hydrocarbons in source and receptor areas.

Polycyclic aromatic hydrocarbons (PAHs) and their oxygenated and nitrated derivatives, OPAHs and NPAHs, are semivolatile air pollutants which are distributed and cycling regionally. Subsequent to atmospheric deposition to and accumulation in soils they may re-volatilise, a secondary source which is understudied. We studied the direction of air-soil mass exchange fluxes of 12 OPAHs, 17 NPAHs, 25 PAHs and one alkylated PAH in two rural environments being influenced by the pollutant concentrations in soil and air, by season, and by land cover. The OPAHs and NPAHs in samples of topsoil, of ambient air particulate and gas phases and in the gas-phase equilibrated with soil were analysed by GC-APCI-MS/MS. The pollutants soil burdens show a pronounced seasonality, a winter maximum for NPAHs and PAHs and a summer maximum for OPAHs. One order of magnitude more OPAH and parent PAH are found stored in forest soil than in nearby grassland soil. Among a number of 3-4 ring PAHs, the OPAHs benzanthrone and 6H-benzo(c,d)pyren-6-one, and the NPAHs 1- and 2-nitronaphthalene, 9-nitrophenanthrene and 7-nitrobenz(a)anthracene are found to re-volatilise from soils at a rural background site in central Europe in summer. At a receptor site in northern Europe, net deposition of polycyclic aromatic compounds (PACs) prevails and re-volatilisation occurs only sporadic. Re-volatilisation of a number of PACs, including strong mutagens, from soils in summer and even in winter indicates that long-range atmospheric transport of primary PAC emissions from central Europe to receptor areas might be enhanced by secondary emissions from soils.

Sources of polychlorinated biphenyls (PCBs) in sediments of the East China marginal seas: Role of unintentionally-produced PCBs.

The production and use of intentionally-produced polychlorinated biphenyls (PCBs) in China have a short history compared with countries of North America and Europe, where technical PCB mixtures were manufactured in large amounts for decades before being banned. Unintentionally-produced PCB emissions increased dramatically in China, leading to unique profiles of PCB burdens. This study first time evaluated 208 individual PCB congeners at 94 sites from surface sediments of the East China Marginal Seas (ECMSs) and explored their sources. Non-technical PCBs transported from atmospheric transport and river discharge played a dominant role in most areas of the ECMSs, while historical residuals of technical PCBs occupied the fine-grained sediments in muddy areas of the central Yellow Sea (YS), regarding to the low sedimentation rate in the central YS. Furthermore, emissions from Taizhou located on the coast of the East China Sea (ECS), which is an important electronic waste dismantling site in East China, contributed additional technical PCBs to the inner shelf of the ECS. Our results indicate that non-technical PCBs have become the dominant PCB species in the ECMSs, and emphasize the synergistic effects of large riverine input, long-range atmospheric transport, and muddy shelf deposition on PCB source and sink of in marginal seas.

Is the oxidative potential of components of fine particulate matter surface-mediated?

Redox-active substances in fine particulate matter (PM) contribute to inhalation health risks through their potential to generate reactive oxygen species in epithelial lung lining fluid (ELF). The ELF's air-liquid interface (ALI) can play an important role in the phase transfer and multi-phase reactions of redox-active PM constituents. We investigated the influence of interfacial processes and properties by scrubbing of coated nano-particles with simulated ELF in a nebulizing mist chamber. Weakly water-soluble redox-active organics abundant in ambient fine PM were reproducibly loaded into ELF via ALI mixing. The resulting oxidative potential (OP) of selected quinones and other PAH derivatives were found to exceed the OP resulting from bulk mixing of the same amounts of redox-active substances and ELF. Our results indicate that the OP of PM components depends not only on the PM substance properties but also on the ELF interface properties and uptake mechanisms. OP measurements based on bulk mixing of phases may not represent the effective OP in the human lung.

Industrial source identification of polyhalogenated carbazoles and preliminary assessment of their global emissions.

Polyhalogenated carbazoles (PHCZs) are emerging global pollutants found in environmental matrices, e.g., 3000 tonnes of PHCZs have been detected in the sediments of the Great Lakes. Recognition of PHCZ emissions from ongoing industrial activities worldwide is still lacking. Here, we identify and quantify PHCZ emissions from 13 large-scale industries, 12 of which previously have no data. Congener profiles of PHCZs from investigated industrial sources are clarified, which enables apportioning of PHCZ sources. Annual PHCZ emissions from major industries are estimated on the basis of derived emission factors and then mapped globally. Coke production is a prime PHCZ emitter of 9229 g/yr, followed by iron ore sintering with a PHCZ emission of 3237 g/yr. China, Australia, Japan, India, USA, and Russia are found to be significant emitters through these industrial activities. PHCZ pollution is potentially a global human health and environmental issue.

Environmental signature and health risk assessment of polybrominated diphenyl ethers (PBDEs) emitted from a landfill fire in Santiago de Chile.

Polybrominated diphenyl ethers (PBDEs) have been used as flame retardants in building materials, electronics, furnishings, vehicles, airplanes, plastics, polyurethane foams, and textiles for many years. Currently, the primary commercial mixtures, penta-, octa-, and deca-BDE, are globally restricted. Still, products containing PBDEs are expected to impact waste management and the environment for many years. In January 2016, an open fire in the Santa Marta landfill close to Santiago de Chile affected the city and surroundings. The fire caused several acute health effects and an increase in emergency hospitalizations. We measured PBDE levels in the areas affected by the fire in the air (gaseous and particulate) and soil, and PBDE emissions were estimated using a dispersion model. The results showed an increase in PBDE concentrations by a factor of 2-4 one day after the start of the fire. However, PBDE concentrations measured after the fire in PM10 and the gas phase were considered low compared to other regions. Interestingly, PBDEs' patterns differed across the sites; however, BDE209 was the dominant congener for all environmental matrices. A preliminary risk assessment was conducted using the daily exposure dose (DED) by air inhalation estimation. The results showed low DED values for adults and children and suggested no direct health risk due to PBDE exposure. This study brings new data useful for future solid waste management initiatives in the country.

Multicompartmental analysis of POPs and PAHs in Concepciόn Bay, central Chile: Part I - Levels and patterns after the 2010 tsunami.

Persistent organic pollutants (POPs) and polycyclic aromatic hydrocarbons (PAHs) were determined in abiotic samples from Concepción Bay in Central Chile. Samples were soxhlet extracted and injected in gas chromatography-mass spectrometry (GCMS). Polybrominated diphenyl ethers (PBDEs) showed the highest levels in air (3-1100 pg m-3), in water (2-64 pg L-1), in sediment, and soil (1-78 ng g-1 (dw)). PAHs were also high in the air (1-6 ng m-3), in water (1-7 ng L-1), in sediment (90-300 ng g-1 (dw)), and in soil (15-2300 ng g-1 (dw)). The polychlorinated biphenyls (PCBs) and chlorinated pesticides were generally low and did not show clear trends along the water column, with exception of PAHs. New data are presented in this work to assess the health status of a relevant coastal area in central Chile.

Multicompartmental analysis of POPs and PAHs in Concepciόn Bay, central Chile: Part II - Air-sea exchange during Austral summer.

Air-sea exchange of POPs and PAHs was assessed in Concepción Bay during January, summer 2015. Results showed low levels, in air and water, for POPs (1-20 pg m-3, and 6-50 pg L-1, respectively) and for ΣPAHs (1-2 ng m-3 and 1-2 ng L-1, respectively). The highest levels were found for PBDEs (200-20,000 pg L-1) in the water samples (3-fold times higher than PCBs and OCP) and PBDE209 accounted for 90% of total ΣPBDEs. Air-sea exchange fluxes (ng m-2 d-1) were low in general, with exception of PBDEs showing values up to 40,000 ng m-2 d-1. Net deposition was found for PAHs, HCB and some PBDEs; while, BDE99, and BDE100 showed net volatilization. These findings contribute with new data of diffusive air-sea exchange on the southern hemisphere Pacific coast.

Sources of organochlorine pesticides in air in an urban Mediterranean environment: volatilisation from soil.

Organochlorine pesticide (OCP) cycling was studied in the area of Banja Luka, Bosnia and Herzegovina, over 3 days in summer with high temporal (4 h-means) and spatial (3 sites distanced 3-6 km) resolutions. Elevated levels of DDX compounds (i.e. o,p'- and p,p'-isomers of DDT, DDE and DDD, 44-74 pg m(-3) at the urban sites and 27 pg m(-3) as a background level), HCH (α-, ß- and γ-isomers, 52-70 vs. 147 pg m(-3)), HCB (34-48 vs. <0.1 pg m(-3)) and pentachlorobenzene (6.8-9.9 vs. 6.0 pg m(-3)) were found. The variation of OCP levels at the two urban sites was not in phase, except for most DDX compounds. This was related to background levels, which for HCH were higher than in the urban area. Vertical profiles between samples collected from 1.1 and 2.3 m (part of the time 0.6 and 2.3 m) above a soil, which was only moderately contaminated by OCPs (0.12 ng g(-1) HCH, 0.11 ng g(-1) DDX, 0.44 ng g(-1) HCB) were analysed. Volatilisation from the ground caused negative vertical concentration gradients of HCH isomers (day and night), but not for HCB (except for 1 day-time sample) and DDX compounds (except p,p'-DDD, day-time, sporadically). The concentration in air and the vertical concentration gradient of the HCH isomers varied with air temperature (day-time maxima), while the variation of the HCB concentration was inversely related to air temperature and was determined by mixing (night-time maxima). α- and ß-HCH were volatilised from soil throughout the three days, even during periods of cooling. Fugacity calculations, based on the absorption in soil organic matter as the process determining retention in soil, underestimated the volatilisation of ß-HCH and p,p'-DDD. It is concluded that the representativeness of point measurements of OCPs in urban areas is limited by the spatial variability of soil contamination.