Long-term trends of continental-scale PCB patterns studied using a global atmosphere–ocean general circulation model

Continental-scale distribution and inter-continental transport of four polychlorinated biphenyl (PCB) congeners (28, 101, 153, 180) from 1950 to 2010 were studied using the global multicompartment chemistry transport model MPI-MCTM. Following identical primary emissions for all PCB congeners into air, most of the burden is stored in terrestrial (soil and vegetation) compartments. Thereby, PCB-28, PCB-101 and PCB-153 show a shift of the soil burden maxima from source to remote regions. This shift is downwind with regard to the westerlies for Eurasia and upwind for North America and more prominent for the lighter PCBs than for PCB-153 or PCB-180. In meridional direction, all congeners' distributions underwent a northward migration in Eurasia and North America since the 1950s. Inter-continental transport from Eurasian sources accounts largely for contamination of Alaska and British Columbia and determines the migration of the PCB distribution in soil in North America. Trans-Pacific transport occurs mainly in the gas phase in boreal winter (December-January-February) at 3-4 km altitude and is on a multi-year time scale strongly linked to the atmospheric pressure systems over the Pacific. Inter-continental transport of the lighter, more volatile PCBs is more efficient than for the heavier PCBs.     

Testing the capability of the chemistry transport model LOTOS-EUROS to forecast PM10 levels in the Netherlands

Since particulate matter has a direct and adverse impact on public health, a good air quality forecast is important. Several European countries presently use statistical forecasting models, which have their limitations, especially for PM10. An alternative approach is to use a chemistry transport model. Here, the ability of the chemical transport model LOTOS-EUROS to forecast PM10 concentrations in the Netherlands was investigated. LOTOS-EUROS models several PM10 components individually. For sulphate, nitrate and ammonium aerosol the evaluation against observations shows that the modelled annual mean concentrations are within 20% of the measured concentration and that the temporal correlation is reasonably good (R > 0.6). For sea salt the model tended to overestimate the measured concentrations. For elemental carbon the correspondence with black smoke observations was reasonable. However, total PM10 is seriously underestimated, due to unmodelled components (secondary organic aerosols, mineral dust) and missing sources. Therefore, a simple bias correction for four seasons was derived based on the years 2004–2006. The model was compared with the Dutch operational statistical model PROPART and ground-level observations. With bias correction, LOTOS-EUROS performed better than PROPART regarding the timing of events. The major flaw of LOTOS-EUROS was that high values (>50 μg m^?3) were still underestimated. Another advantage of LOTOS-EUROS over the statistical model was the more detailed information in space and time, which facilitates communication of the forecast to the general public.     

Multicompartmental fate of persistent substances

Background, Aim and Scope Modelling of the fate of environmental chemicals can be done by relatively simple multi-media box models or using complex atmospheric transport models. It was the aim of this work to compare the results obtained for both types of models using a small set of non-ionic and non-polar or moderately polar organic chemicals, known to be distributed over long distances. Materials and Methods Predictions of multimedia exposure models of different types, namely three multimedia mass-balance box models (MBMs), two in the steady state and one in the non-steady state mode, and one non-steady state multicompartment chemistry-atmospheric transport model (MCTM), are compared for the first time. The models used are SimpleBox, Chemrange, the MPI-MBM and the MPI-MCTM. The target parameters addressed are compartmental distributions (i.e. mass fractions in the compartments), overall environmental residence time (i.e. overall persistence and eventually including other final sinks, such as loss to the deep sea) and a measure for the long-range transport potential. These are derived for atrazine, benz-[a]-pyrene, DDT, α and γ-hexachlorocyclohexane, methyl parathion and various modes of substance entry into the model world. Results and Discussion Compartmental distributions in steady state were compared. Steady state needed 2–10 years to be established in the MCTM. The highest fraction of the substances in air is predicted by the MCTM. Accordingly, the other models predict longer substance persistence in most cases. The results suggest that temperature affects the compartmental distribution more in the box models, while it is only one among many climate factors acting in the transport model. The representation of final sinks in the models, e.g. burial in the sediment, is key for model-based compartmental distribution and persistence predictions. There is a tendency of MBMs to overestimate substance sinks in air and to underestimate atmospheric transport velocity as a consequence of the neglection of the temporal and spatial variabilities of these parameters. Therefore, the long-range transport potential in air derived from MCTM simulations exceeds the one from Chemrange in most cases and least for substances which undergo slow degradation in air. Conclusions and Perspectives MBMs should be improved such as to ascertain that the significance of the atmosphere for the multicompartmental cycling is not systematically underestimated. Both types of models should be improved such as to cover degradation in air in the particle-bound state and transport via ocean currents. A detailed understanding of the deviations observed in this work and elsewhere should be gained and multimedia fate box models could then be ‘tuned in’ to match better the results of comprehensive multicompartmental transport models. ESS-Submission Editor: Prof. Dr. Michael Matthies (matthies@uos.de)     

Olive tree, Olea europaea L., leaves as a bioindicator of atmospheric PCB contamination

Olive tree leaf samples were collected to investigate their possible use for biomonitoring of lipophilic toxic substances. The samples were analyzed for 28 polychlorinated biphenyls (PCB) congeners. Twelve congeners were detected in the samples. PCB-60, 77, 81, 89, 105, 114, and 153 were the most frequently detected congeners ranging from 32 % for PCB-52 to 97 % for PCB-81. Σ₁₂PCBs concentration varied from below detection limit to 248 ng/g wet weight in the sampling area, while the mean congener concentrations ranged from 0.06 ng/g (PCB-128?+?167) to 64.2 ng/g wet weight (PCB-60). Constructed concentration maps showed that olive tree leaves can be employed for the estimation of spatial distrubution of these congeners.     

Kinetics on the decomposition of polychlorinated biphenyls with activated carbon-supported iron

The process of destroying polychlorinated biphenyls (PCBs) generates exhaust gases that contain low quantities of PCBs, which cannot be disposed of easily. Activated carbon (AC) can be used to adsorb residual PCBs after disposal of high-level PCBs. We examined the chemical reactivity of AC-supported iron as a catalyst to decompose PCB-153, and varied three decomposition parameters (temperature, time and iron concentration) under an atmosphere of either air or N(2). We measured the Brunauer-Emmett-Teller (BET) surface area and pore volume of AC to assess the adsorption capacity of AC before and after decomposition. At low temperatures the adsorption process was more important than the decomposition process. The decomposition process was completed within 30 and 60 min under air and N(2), respectively. The efficiency of PCB-153 decomposition at 350 degrees C for 120 min was approximately 100.0% and 97.1% under air and N(2), respectively. Analysis of inorganic chloride ions revealed that PCB-153 was effectively destroyed during decomposition. The differences between decomposition under air and N(2) reflected differences in BET surface and pore volume.     

Regional background monitoring of PBT compounds. The comparison of the results from measurements and modelling

A comparison of the modelling results of persistent, bioaccumulative and toxic (PBT) chemicals is presented with measurements. Contribution will present mean annual concentrations calculated and observed at EMEP stations and their ratios. The comparison of the calculated results with older results indicates that the model modification improved the agreement with measurement data. PBT compounds in ambient air are monitored in the area of Kosetice observatory (professional observatory of the Czech Hydrometeorological Institute located in south Bohemia). Calculated and measured mean annual concentrations of PBTs in precipitation, soil, vegetation and their ratios are presented. It should be mentioned that the number of measurements in such compartments as seawater, soil and vegetation is insufficient for model verification at present. The agreement between results from MSC-East models and results from long-term regional air background monitoring in Central Europe is good.     

Modelling the fate of persistent organic pollutants in Europe: parameterisation of a gridded distribution model

A regionally segmented multimedia fate model for the European continent is described together with an illustrative steady-state case study examining the fate of gamma-HCH (lindane) based on 1998 emission data. The study builds on the regionally segmented BETR North America model structure and describes the regional segmentation and parameterisation for Europe. The European continent is described by a 5 degrees x5 degrees grid, leading to 50 regions together with four perimetric boxes representing regions buffering the European environment. Each zone comprises seven compartments including; upper and lower atmosphere, soil, vegetation, fresh water and sediment and coastal water. Inter-regions flows of air and water are described, exploiting information originating from GIS databases and other georeferenced data. The model is primarily designed to describe the fate of Persistent Organic Pollutants (POPs) within the European environment by examining chemical partitioning and degradation in each region, and inter-region transport either under steady-state conditions or fully dynamically. A test case scenario is presented which examines the fate of estimated spatially resolved atmospheric emissions of lindane throughout Europe within the lower atmosphere and surface soil compartments. In accordance with the predominant wind direction in Europe, the model predicts high concentrations close to the major sources as well as towards Central and Northeast regions. Elevated soil concentrations in Scandinavian soils provide further evidence of the potential of increased scavenging by forests and subsequent accumulation by organic-rich terrestrial surfaces. Initial model predictions have revealed a factor of 5-10 underestimation of lindane concentrations in the atmosphere. This is explained by an underestimation of source strength and/or an underestimation of European background levels. The model presented can further be used to predict deposition fluxes and chemical inventories, and it can also be adapted to provide characteristic travel distances and overall environmental persistence, which can be compared with other long-range transport prediction methods.     

Sequential box models for indoor air quality: Application to airliner cabin air quality

In this paper we present the development and application of a model for indoor air quality. The model represents a departure from the standard box models typically used for indoor environments which has applicability in residences and office buildings. The model has been developed for a physical system consisting of sequential compartments which communicate only with adjacent compartments. Each compartment may contain various source and sink terms for a pollutant as well as leakage, and air transfer from adjacent compartments. The mathematical derivation affords rapid calculation of equilibrium concentrations in an essentially unlimited number of compartments. The model has been applied to air quality in the passenger cabin of three commercial aircraft. Simulations have been performed for environmental tobacco smoke (ETS) under two scenarios, CO₂ and water vapor. Additionally, concentrations in one aircraft have been simulated under conditions different from the standard configuration. Results of the simulations suggest the potential for elevated concentrations of ETS in smoking sections of non-air-recirculating aircraft and throughout the aircraft when air is recirculated. Concentrations of CO₂ and water vapor are consistent with expected results. We conclude that this model may be a useful tool in understanding indoor air quality in general and on aircraft in particular.     

Sea salt concentrations across the European continent

The oceans are a major source for particles that play an important role in many atmospheric processes. In Europe sea salt may contribute significantly to particulate matter concentrations. We have compiled sodium concentration data as a tracer for sea salt for 89 sites in Europe to provide more insight in the distribution of sea salt across Europe. The annual average sea salt concentrations above land were estimated to range between 0.3 and almost 13 μg m^?3. Maximum concentrations are found at the Irish coast. At coastal sites along the Atlantic and North Sea coast concentrations tend to be around 5 μg m^?3. More inland locations up to about 300 km away from the coast tend to show concentrations between 2 and 5 μg m^?3, whereas sites further away from the coast are characterized by lower concentrations. An analysis of the representativity of the data with respect to a long term average showed that the long average is associated with a standard deviation of around 15%. The compilation of observations provides an improved overview of sea salt concentrations in Europe as well as an improved basis for model validation. Verification of the results of the LOTOS-EUROS model learned that the model represents well the spatial variability of the observed sea salt concentrations very well. However, the absolute concentrations are significantly overestimated due to large uncertainties in the emission and dry deposition parameterizations. Using the high explained variability in the gradients across Europe, the bias-corrected modelled distribution serves as a best estimate of the sea salt distribution across Europe for 2005.     

A revised estimate of copper emissions from road transport in UNECE-Europe and its impact on predicted copper concentrations

Comparisons of measured and model-predicted atmospheric copper concentrations show a severe underestimation of the observed concentrations by the models. This underestimation may be (partly) due to underestimated emissions of copper to air. Since the phase out of asbestos brake lining material, the composition of brake lining material has changed and may contain up to ∼15% copper. This makes brake wear from vehicles potentially an important source of atmospheric (particulate) copper concentrations. In this paper, we reassess the copper emissions due to exhaust emissions and brake wear from road transport. Overall, our reassessments result in an estimate of total copper emission to air in UNECE-Europe of 4.0–5.5 ktonnes yr⁻¹, which is substantially higher than the previous estimate of 2.8 ktonnes yr⁻¹. Copper concentrations over Europe are calculated with the LOTOS-EUROS model using the revised emission data as model input. The results show that the revised emission estimates are a major step towards gap closure of predicted versus observed copper concentrations in ambient air. Brake wear emissions may be responsible for 50–75% of the total copper emissions to air for most of Western Europe. The hypothesis that road transport is an important source of copper emissions is tested and confirmed by (1) reviewing available literature data of chemically speciated PM data from road tunnel studies and (2) the gradient observed in copper concentrations from ambient PM monitoring going from rural sites to street stations. The literature review and observational data suggest that the majority of the emitted PM10 brake wear particles is in the PM2.5–10 size range. The results of this study indicate that modification of brake lining composition is an important mitigation option to reduce copper exposure of the population in Western Europe.     

A multimedia environmental model of chemical distribution: fate, transport, and uncertainty analysis

This paper presented a framework for analysis of chemical concentration in the environment and evaluation of variance propagation within the model. This framework was illustrated through a case study of selected organic compounds of benzo[alpha]pyrene (BAP) and hexachlorobenzene (HCB) in the Great Lakes region. A multimedia environmental fate model was applied to perform stochastic simulations of chemical concentrations in various media. Both uncertainty in chemical properties and variability in hydrometeorological parameters were included in the Monte Carlo simulation, resulting in a distribution of concentrations in each medium. Parameters of compartmental dimensions, densities, emissions, and background concentrations were assumed to be constant in this study. The predicted concentrations in air, surface water and sediment were compared to reported data for validation purpose. Based on rank correlations, a sensitivity analysis was conducted to determine the influence of individual input parameters on the output variance for concentration in each environmental medium and for the basin-wide total mass inventory. Results of model validation indicated that the model predictions were in reasonable agreement with spatial distribution patterns, among the five lake basins, of reported data in the literature. For the chemical and environmental parameters given in this study, parameters associated to air-ground partitioning (such as moisture in surface soil, vapor pressure, and deposition velocity) and chemical distribution in soil solid (such as organic carbon partition coefficient and organic carbon content in root-zone soil) were targeted to reduce the uncertainty in basin-wide mass inventory. This results of sensitivity analysis in this study also indicated that the model sensitivity to an input parameter might be affected by the magnitudes of input parameters defined by the parameter settings in the simulation scenario. Therefore, uncertainty and sensitivity analyses for environmental fate models was suggested to be conducted after the model output was validated based on an appropriate input parameter settings.     

Methyl tertiary hexyl ether and methyl tertiary octyl ether as gasoline oxygenates: assessing risks from atmospheric dispersion and deposition

Methyl tertiary hexyl ether (MtHxE) and methyl tertiary octyl ether (MtOcE) are currently being developed as replacement oxygenates for methyl tertiary butyl ether (MtBE) in gasoline. As was the case with MtBE, the introduction of these ethers into fuel supplies guarantees their introduction into the environment as well. In this study, a screening-level risk assessment was performed by comparing predicted environmental concentrations (PEC) of these ethers to concentrations that might cause adverse effects to humans or ecosystems. A simple box model that has successfully estimated urban air concentrations of MtBE was adapted to predict atmospheric concentrations of MtHxE and MtOcE. Expected atmospheric concentrations of these ethers were also estimated using the European Union System for the Evaluation of Substances (EUSES) multimedia fate model, which simultaneously calculates PECs in the various environmental compartments of air, water, soil, and sediment. Because little or no data are available on the physicochemical, environmental, and toxicological properties of MtHxE and MtOcE, estimation methods were used in conjunction with EUSES to predict both the PECs and the concentrations at which these ethers might pose a threat. The results suggest that these ethers would contaminate the air of a moderately sized U.S. city (Boston, MA) at levels similar to those found previously for MtBE. The risk assessment module in EUSES predicted risk characterization ratios of 10(-3) and 10(-2) for MtHxE and MtOcE, respectively, in Boston, and 10(-2) and 10(-1) in very large urban centers, suggesting that these ethers pose only a minimal threat to ecosystems at the anticipated environmental concentrations. The assessment also indicates that these compounds are possible human carcinogens and that they may be present in urban air at concentrations that pose an unacceptable cancer risk. Therefore, testing of the toxicological properties of these compounds is recommended before they replace MtBE in gasoline.     

Decomposition of 2,2',4,4',5,5'-hexachlorobiphenyl with iron supported on an activated carbon from an ion-exchange resin

An activated carbon (AC) containing a high concentration (374 mg g⁻¹) of Fe was prepared by carbonization of an ion-exchange resin. To examine its chemical reactivity as a catalyst to decompose 2,2′,4,4′,5,5′-hexachlorobiphenyl (PCB-153), the decomposition parameters of temperature and time were varied under air or N₂. Decomposition at 350 °C was achieved within 15 min under air and 30 min under N₂, and the efficiency of PCB-153 decomposition was 99.7% and 98.0%, respectively. An analysis of inorganic chloride ions revealed that PCB-153 was mineralized effectively during the decomposition. The Brunauer-Emmett-Teller (BET) surface area and pore volume of the AC were measured to assess the adsorption capacity before and after the decomposition. The differences between decomposition under air and N₂ reflected the differences in the BET surface and pore volume measurements. A decomposition pathway was postulated, and the reactive characteristics of chlorine atoms loaded on the benzene rings followed the order of para > meta > ortho, which agrees with the calculated results from a density functional theory study.     

Priority assessment of toxic substances in life cycle assessment. Part I: calculation of toxicity potentials for 181 substances with the nested multi-media fate, exposure and effects model USES-LCA

Toxicity potentials are standard values used in life cycle assessment (LCA) to enable a comparison of toxic impacts between substances. In most cases, toxicity potentials are calculated with multi-media fate models. Until now, unrealistic system settings were used for these calculations. The present paper outlines an improved model to calculate toxicity potentials: the global nested multi-media fate, exposure and effects model USES-LCA. It is based on the Uniform System for the Evaluation of Substances 2.0 (USES 2.0). USES-LCA was used to calculate for 181 substances toxicity potentials for the six impact categories freshwater aquatic ecotoxicity, marine aquatic ecotoxicity, freshwater sediment ecotoxicity, marine sediment ecotoxicity, terrestrial ecotoxicity and human toxicity, after initial emission to the compartments air, freshwater, seawater, industrial soil and agricultural soil, respectively. Differences of several orders of magnitude were found between the new toxicity potentials and those calculated previously.     

Methyl Tertiary Hexyl Ether and Methyl Tertiary Octyl Ether as Gasoline Oxygenates: Assessing Risks from Atmospheric Dispersion and Deposition

Abstract

Methyl tertiary hexyl ether (MtHxE) and methyl tertiary octyl ether (MtOcE) are currently being developed as replacement oxygenates for methyl tertiary butyl ether (MtBE) in gasoline. As was the case with MtBE, the introduction of these ethers into fuel supplies guarantees their introduction into the environment as well. In this study, a screening-level risk assessment was performed by comparing predicted environmental concentrations (PEC) of these ethers to concentrations that might cause adverse effects to humans or ecosystems. A simple box model that has successfully estimated urban air concentrations of MtBE was adapted to predict atmospheric concentrations of MtHxE and MtOcE. Expected atmospheric concentrations of these ethers were also estimated using the European Union System for the Evaluation of Substances (EUSES) multimedia fate model, which simultaneously calculates PECs in the various environmental compartments of air, water, soil, and sediment. Because little or no data are available on the physicochemical, environmental, and toxicological properties of MtHxE and MtOcE, estimation methods were used in conjunction with EUSES to predict both the PECs and the concentrations at which these ethers might pose a threat. The results suggest that these ethers would contaminate the air of a moderately sized U.S. city (Boston, MA) at levels similar to those found previously for MtBE. The risk assessment module in EUSES predicted risk characterization ratios of 10^?3 and 10^?2 for MtHxE and MtOcE, respectively, in Boston, and 10^?2 and 10^?1 in very large urban centers, suggesting that these ethers pose only a minimal threat to ecosystems at the anticipated environmental concentrations. The assessment also indicates that these compounds are possible human carcinogens and that they may be present in urban air at concentrations that pose an unacceptable cancer risk. Therefore, testing of the toxicological properties of these compounds is recommended before they replace MtBE in gasoline.     

Model and input uncertainty in multi-media fate modeling: benzo[a]pyrene concentrations in Europe

This paper evaluates the contribution of (i) uncertainty in substance properties, (ii) lack of spatial variability, (iii) intermodel differences and (iv) neglecting sorption to black carbon (BC) to the uncertainty of Benzo[a]pyrene (BaP) concentrations in European air, soil and fresh water predicted by the multi-media fate model Simplebox. Uncertainty in substance properties was quantified using probabilistic modeling. The influence of spatial variability was quantified by estimating variation in predicted concentrations with three spatially explicit fate models (Impact 2002, EVn BETR and BETR Global). Intermodel differences were quantified by comparing concentration estimates of Simplebox, Impact 2002, EVn BETR and the European part of BETR Global. Finally, predictions of a BC-inclusive version of Simplebox were compared with predictions of a BC-exclusive version. For air concentrations of BaP, the lack of spatial variability in emissions was most influential. For freshwater concentrations of BaP, intermodel differences and lack of spatial variability in dimensions of fresh water bodies were the dominant sources of uncertainty. For soil, all sources of uncertainty were of comparable magnitude. Our results indicate that uncertainty in Simplebox can be as large as three orders of magnitude for BaP concentrations in the environment and would be substantially underestimated by focusing on one source of uncertainty only.     

Application of a Three-Layer Photochemical Box Model in an Athens Street Canyon

ABSTRACT

The aim of this paper is to show that a photochemical box model could describe the air pollution diurnal profiles within a typical street canyon in the city of Athens. As sophisticated three-dimensional dispersion models are computationally expensive and they cannot serve to simulate pollution levels in the scale of an urban street canyon, a suitably modified three-layer photochemical box model was applied. A street canyon of Athens with heavy traffic was chosen to apply the aforementioned model. The model was used to calculate pollutant concentrations during two days with meteorological conditions favoring pollutant accumulation. Road traffic emissions were calculated based on existing traffic load measurements. Meteorological data, as well as various pollutant concentrations, in order to compare with the model results, were provided by available measurements. The calculated concentrations were found to be in good agreement with measured concentration levels and show that, when traffic load and traffic composition data are available, this model can be used to predict pollution episodes. It is noteworthy that high concentrations persisted, even after additional traffic restriction measures were taken on the second day because of the high pollution levels.     

Concentrations of organochlorine pesticides and polychlorinated biphenyls in human serum and their relation with age,gender, and BMI for the general population of Bizerte,Tunisia

Human serum samples (n?=?113) from Bizerte, northern Tunisia, collected between 2011 and 2012 were analyzed for 8 organochlorine pesticides (OCPs) including p,p′-dichlorodiphenyltrichloroethane (DDT) and its metabolites, hexachlorobenzene (HCB), hexachlorocyclohexane isomers, dieldrin, and heptachlor and 12 polychlorinated biphenyls (PCBs) congeners. Concentrations of these residues in serum were determined by gas chromatography with electron capture detector and total cholesterol (CHOL) and triglycerides (TG) levels were evaluated by enzymatic colorimetric method. HCB, p,p′-DDE, PCB-138, PCB-153, and PCB-180, were the most abundant organochlorine compounds (OCs) detected in >95 % of the study subjects. The mean levels of p,p′-DDE and HCB in serum were 168.8 and 49.1 ng?g^?1 lipid, respectively. The sum PCBs concentrations ranged from 37.5 to 284.6 ng?g^?1 lipid in the samples, with mean and median value of 136.1 and 123.2 ng?g^?1 lipid, respectively. The PCB profile consisted of persistent congeners, such as PCB-138, PCB-153, and PCB-180 which contributed for approximately 82.7 % to the ∑PCBs. Statistical analysis showed that most OCs correlated significantly with age, considering all samples together or with gender differentiation. The present study shows that the levels of p,p′-DDE and ∑DDTs were significantly higher in females than in males (p?<?0.05), while PCBs levels were significantly higher in male (p?<?0.05) than in females. No statistically significant association was found between body mass index and concentration of any organochlorine pesticide or PCB congeners 153, 138, 180, or ∑PCBs.