Global baseline pollution studies XI: Congener specific determination of polychlorinated biphenyls (PCB) and occurrence of alpha- and gamma-hexachlorocyclohexane (HCH), 4,4′-DDE and 4,4′-DDT in continental air

The hexachlorocyclohexane-isomers (HCH), hexachlorobenzene (HCB), the polychlorinated biphenyls (PCB), 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (4,4′-DDT) and 1,1-dichloro-2,2-bis(p-chlorophenyl)ethene (4,4′-DDE) have been measured in urban and rural air around the city of Ulm (F. R. G., 48.4° N, 10.0° E). The sampling stations are typical for continental air in the westerlies of the northern hemisphere including local and regional influences. The analytical method consists of adsorptive sampling of large volumes (1000 m³) of air on silica gel, solvent desorption with CH₂Cl₂, preseparation of the collected chlorinated C₆/C₁₄ hydrocarbons by liquid adsorption chromatography on silica gel, and high resolution capillary gas chromatography with electron capture-(HRGC/ECD) or mass-selective detection (HRGC/MSD). The concentrations found in the lower troposphere under different meteorological conditions reflect regional input and long range transport. The levels found range from 1 pg/m³ for 4,4′-DDT to 10 ng/m³ for gamma HCH.     

Synthesis of 4,4′-dichloro-3,5,3′,5′-tetramethylbiphenyl by the sandmeyer reaction

4,4′-Dichloro-3,5,3′,5′-tetramethylbiphenyl was prepared by -diazotization of 3,5,3′,5′-tetramethylbenzidine followed by the Sandmeyer reaction. The starting material is a noncarcinogenic analogue of benzidine, and the product may be of interest as a model compound for studying the metabolism of chlorinated biphenyls.     

Degradation of pentachlorobiphenyl by a sequential treatment using Pd coated iron and an aerobic bacterium (H1)

The reductive dechlorination and biodegradation of 2,2^′4,5,5^′-pentachlorobiphenyl (PCB#101) was investigated in a laboratory-scale. Palladium coated iron (Pd/Fe) was used as a catalytic reductant for the chemical degradation of 2,2^′4,5,5^′-pentachlorobiphenyl, and an aerobic bacteria was used for biodegradation following the chemical reaction in this study. Dechlorination was affected by several factors such as Pd loading, initial soil pH and the amount of Pd/Fe used. The results showed that higher Pd loading, higher dosage of Pd/Fe and slightly acid condition were beneficial to the catalytic dechlorination of 2,2^′,4,5,5^′-pentachlorobiphenyl. In laboratory batch experiments, 2,2^′4,5,5^′-pentachlorobiphenyl was reduced in the presence of Pd/Fe bimetal, which was not further degraded by aerobic bacteria. 2,2^′,4-trichlorobiphenyl (PCB#17), a reduction product from 2,2^′4,5,5^′-pentachlorobiphenyl, was readily biodegraded in the presence of a aerobic bacterial strain. It is suggested that an integrated Pd/Fe catalytic reduction-aerobic biodegradation process may be a feasible option for treating PCB-contaminated soil.     

Bioconcentration of metals in the moss Scleropodium purum in the area surrounding a power plant: A geotopographical predictive model for mercury

Samples of the moss Scleropodium purum collected in 1995 and 1997 were used to biomonitor the deposition of metals in the area surrounding a thermal power plant. Significantly higher levels of Cu (p<0.05), Fe (p<0.01), As and Hg (p<0.001) were found in the 1997 samples than in the 1995 samples, due to changes in atmospheric conditions. The influence on bioconcentration of the orientation of the sampling sites relative to the source of emission was studied. It was found that the increase recorded in 1997 generally occurred in the sampling sites in the south east of the study area. Analysis of the effect of distance from the source of emission revealed that the increase in metal levels in 1997 took place close to the power station (10–30 km). Finally, multiple regression analysis was used to construct a model that related different topographical variables to the concentrations of Hg in moss. The model, constructed using the data collected in both sampling periods, included the orientation of the sampling sites relative to the source of emission as well as the height of sampling sites in 1995 and the distance from the emission point in 1997. The model allowed us to determine the extent of the area affected by deposition and to establish the magnitude of deposition.     

Accumulation and elimination of C-PCBs by daphnia magna straus 1820

The accumulation of chlorinated biphenyls in shows a tendency to increase with decreasing water solubility. The depuration times of PCBs from daphnia depend on the temperature of the test water and possibly on the water solubility of the substance. The water solubilities of 2,2′-dichlorobiphenyl, 2,5,4′-trichlorobiphenyl, 2,4,6,2′-tetrachlorobiphenyl and 2,4,6,2′,4′-pentachlorobiphenyl have been determined using ¹⁴C-labelled substances.     

Bioconcentration kinetics of 2,4,5- tri- and 3,3′,4,4′-tetrachlorobiphenyl and 2,4,5- tri- and 3,3′,4,4′-tetrachlorodiphenylether in fish

The rates of uptake and elimination of 2,4,5 tri- and 3,3′,4,4′-tetrachlorodiphenylether in fish after aqueous exposure are comparable to those of similarly substituted chlorobiphenyls. Mass balance data suggest that 2,4,5- trichlorobiphenyl and 2,4,5- trichlorodiphenylether are metabolized with rates approximately twice as high as the rates of elimination of the parent compounds.The bioconcentration factors of the 3,3′,4,4′-tetrachloro- biphenyl and 3,3′,4,4′- tetrachlorodiphenyl ether are only determined by the hydrophobic nature of these chemicals and are not influenced by metabolism. Congener specific uptake and elimination processes as have been reported for chlorinated dibenzo-p-dioxins and dibenzofurans does not seem to be important for chlorinated biphenyls and diphenylethers.     

Serum levels of organochlorine pesticides in healthy adults from five regions of Spain

The aim of this study was to measure of serum levels of p,p′-dichlorodiphenyl trichloroethane (p,p′-DDT), p,p′-dichlorodiphenyl dichlorethylene (p,p′-DDE), β-hexachlorocyclohexane (β-HCH), and hexachlorobenzene (HCB) in healthy adults in Spain. Furthermore, we also analyzed these levels according to dietary, other lifestyle factors and anthropometric characteristics. We measured the concentrations of such organochlorine pesticides (OCPs) in serum samples collected during 1992–1996 from 953 subjects aged 35–64 years, they were residents of five Spanish regions, they were randomly selected from the European Prospective Investigation into Cancer and Nutrition (EPIC) cohort. OCPs were determined by means of gas chromatography with electron-capture detection (GC-ECD). The most frequent compound found in serum was p,p′-DDE, present in 98% of the samples, followed by HCB and β-HCH, found in 89% and 77% of samples, respectively, while p,p′-DDT could be measured only in 26% of subjects. The geometric means of serum concentrations (ng/g lipid) were 822 for p,p′-DDE, 167 for β-HCH, and 379 for HCB. The concentrations of all OCPs were positively associated with age and body mass index, and decreased along the period of blood collection. No association was found between OCPs levels and dietary factors. The concentrations of p,p′-DDE and β-HCB were higher in Murcia, one of southern regions, most likely associated with intensive past use of pesticides related to agricultural practices, while higher levels of HCB were found in Navarra, located in the north, maybe due to industrial use rather than agricultural application.     

Assessment and prediction of exposure to benzene of filling station employees

In the present study, the exposure to benzene of employees working in two filling stations (one urban and one rural) was estimated, through the method of passive sampling. Additional data (30′ measurements of benzene exposure through active sampling to employees dealing with different activities, meteorological and traffic data) were collected. The measurements campaign was performed in both summer and wintertime to determine the seasonal variation of the exposure pattern.In addition, a set of artificial neural networks (ANNs) was developed to predict benzene exposure pattern for the filling station employees based on active sampling data and the parameters related to the employees’ exposure. The quantification of the contribution of each parameter to the overall exposure pattern was also attempted.The results showed that although vapour recovery technologies are installed in the refuelling systems and benzene emissions are significantly reduced compared to the past, filling station employees are still highly exposed to benzene (52–15 μg m⁻³). Benzene exposure is strongly correlated to car refuelling (exposure levels up to 85 μg m⁻³), while activities like car washing or working in cash machine inside an office contribute to lower exposure levels (up to 44 and 24 μg m⁻³ respectively). In rural filling station, exposure levels were in general lower compared to the urban ones, due to the smaller amount of gasoline that was traded and the absence of any significant traffic effect or urban background concentration. The developed ANN seemed to be a promising technique in the prediction of the exposure pattern giving very good results, and the quantification of the parameters affirmed the importance of the refueling procedure to the exposure levels.     

Gas-phase ozonolysis of the monoterpenoids (S)-(+)-carvone, (R)-(−)-carvone, (−)-carveol, geraniol and citral

Biogenic emissions of volatile organic compounds (VOCs) play a fundamental role in atmospheric chemistry. Vegetation is the most abundant natural source of VOCs, while terpenoids, as limonene, α and β pinene and mircene, top the plants emission list. Much interest has been demonstrated in oxidation and photooxidation reactions of VOCs, particularly of monoterpenoids, owing to their diversity and to uncertainties regarding their mechanism of reaction. Quantification of primary carbonylic compounds, as well as of biradical reaction components, is highly relevant to the understanding of the major reactions. In this context, taking into account both structural factors and the fact that these compounds are found in the essential oils of plants typically found in Brazil and that they may be present in the atmosphere from emission by the plants, the monoterpenoids (S)-(+)-carvone, (R)-(−)-carvone, (−)-carveol, geraniol and citral (a mixture of the isomers geranial and neral) were selected for this study.The ozonolysis reactions of the monoterpenoids were carried out under dark conditions for all experiments, due to their photochemical reactivity. The analysis of the results lets us propose a mechanism by which these reactions occur. The observed results of the ozonolysis of S and R carvone suggest that the stereochemistry of asymmetric carbon does not affect either in the yields of both formaldehyde and of OH radicals produced in the reaction, or in the reactivity of these compounds, for which the rate constants were in the scale of 10⁻⁶ s⁻¹.We found that, in the (−)-carveol's cis and trans mixture, even though the hydroxyl in the axial position—in the case of trans-(C) and cis-(D′) isomers—favors the attack by the ozone molecule on the external double bond, thus increasing the mixture's reactivity , it affects the average production of formaldehyde. The presence of geraniol and citral led to the production of formaldehyde, propanone, glyoxal, methyl–glyoxal and cyclohexanone (OH radicals) as reaction products. The influence of an electron attractor group bonded to the carbon of the double bond, on the reactivity of the double bond, could not be observed in the case of citral, due to strong interference occurring in the instrument in all experiments with this monoterpenoid. For this reason, only the kinetics of geraniol was monitored .     

Occurrence and distribution of atmospheric organic micropollutants in conifer needles

The distribution of some chlorinated hydrocarbons(p,p′-DDT, p,p′-DDE,α-HCH,γ-HCH,HCB) in spruce (Picea abies) needles was investigated. A comparision of concentrations in the wax with that of the remaining needle and time-resolved washing of the needle-surface shows the distribution behaviour of these substances.     

Organochlorine pesticides accumulation and degradation products in vegetation samples of a contaminated area in Galicia (NW Spain)

The content of 21 organochlorine pesticides were studied in vegetation samples of a highly contaminated area by isomers of hexachlorocyclohexane (HCH) located close to a former industrial area in Galicia (NW Spain). Five species of plants were collected at different points of the contaminated area and the different parts of the plants were separated in order to study differences in accumulation capabilities. Samples were extracted employing microwave energy followed by a clean-up step using solid phase extraction and finally determined by GC–ECD. The results obtained show that the most abundant pesticides are HCHs isomers, being the main isomers β-HCH and -HCH in all samples whereas δ-HCH and γ-HCH were at lower levels. Some other pesticides such as p,p′-DDT, p,p′-DDD and p,p′-DDE were also present in much lower amount in some of the samples. Several degradation products of HCH were also identified in some samples by GC–MS.     

Synthesis of branched para-nonylphenol isomers: occurrence and quantification in two commercial mixtures

Eight tertiary nonanols were synthesized via Grignard reaction and coupled by Friedel–Crafts alkylation with phenol to the corresponding nonylphenols. Six branched para-nonylphenols (NP) were obtained: 4-(3′-methyl-3′-octyl)phenol (33NP), 4-(2′-methyl-2′-octyl)phenol (22NP), 4-(2′,5′-dimethyl-2′-heptyl)phenol (252NP), 4-(2′,5′,5′-trimethyl-2′-hexyl)phenol (2552NP), 4-(2′,4′-dimethyl-2′-heptyl)phenol (242NP) and 4-(4′-ethyl-2′-methyl-2′-hexyl)phenol (4E22NP). Their structures were confirmed by GC–MS and NMR spectroscopy. These six isomers as well as the earlier synthesized 4-(3′,5′-dimethyl-3′-heptyl)phenol (353NP), 4-(3′,6′-dimethyl-3′-heptyl)phenol (363NP) and 4-(2′,6′-dimethyl-2′-heptyl)phenol (262NP) were compared with commercial NP mixtures purchased from Acros and Fluka by GC–MS (equipped with a 100 m polysiloxane column). The analyses revealed that all obtained isomers are occurring in different quantities in both commercial NP mixtures.     

Emission of trans,trans-2,4-decadienal from restaurant exhausts to the atmosphere

Cooking exhausts may contribute significant organic compounds to the atmosphere. It has been shown that trans,trans-2,4-decadienal (tt-DDE) is an important toxic compound in cooking oil fumes (COF). In this study, the emissions of tt-DDE were quantified in both gaseous and particulate phases of three kinds of restaurant exhausts (Chinese, western and barbecue). Samples of exhausts were collected with a sampling system meeting the criteria of US EPA Modified Method 5. The tt-DDE was analyzed by HPLC–MS/MS. The results indicate that the emission factors of tt-DDE in terms of μg customer⁻¹ were in sequence: barbecue (1990)>Chinese (570)>western (63.8). The average proportion of tt-DDE in the particulate phase of the exhausts was 83% for the 16 investigated restaurants. Evidently, the majority of tt-DDE in the exhausts was in the particulate phase. There was no evident correlation found between phase distribution of tt-DDE and exhaust temperature in the restaurants investigated. The efficiencies of removal of particulate tt-DDE by air pollution control devices (APCDs) were assessed. The removal efficiencies of electrostatic precipitator (ESP), ESP and activated carbon in series, and wet scrubber were 64.2%, 86.3% and 71.3%, respectively.     

Declining levels of PCB, HCB and p,p′-DDE in adipose tissue from food producing bovines and swine in Sweden 1991–2004

The official control programme for organochlorine (OC) contaminants in food producing animals in Sweden was used to study temporal and spatial trends of the polychlorinated biphenyl CB 153, hexachlorobenzene (HCB) and p,p′-DDE in adipose tissue from bovines and swine 1991–2004. Our results show that efforts to decrease OC contamination of animal feed and the environment have had a positive impact on the contamination of the animal production. OC concentrations declined significantly in almost all studied regions of Sweden. OC temporal trends were slower in bovines (6–8% per year) than in swine (10–12%). Power analyses showed that data from more than 10 years of sampling were needed for a detection of an annual OC level change of 5% in both species in the control programme, due to large within- and between-year variation in OC levels. CB 153 and p,p′-DDE levels were higher in southern than in northern Sweden. Levels decreased with age in milk cows, but not in young nulliparous cows (heifers) and bulls. Moreover, milk cows and bulls had significantly lower OC levels than heifers. Levels were not age-dependent among swine, but castrated male swine (barrows) had significantly lower OC levels than young female swine (gilts). Levels of the studied OCs are now in many cases below the LOQ of the analytical method used. Future time trend studies of these OCs thus depend on lowered LOQs in the control programme.     

PCDD/Fs in ambient air in north-east Italy: The role of a MSWI inside an industrial area

The stack gases of a municipal solid waste incinerator (MSWI), and ambient air were sampled in four locations around the plant for the analysis of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/Fs). The sampling area was close to an industrial area near Trieste, in north-east Italy. The purpose of the study was to estimate the impact of the MSWI emissions and to distinguish the contribution of these emissions from other potential emission sources in the industrial area.PCDD/F atmospheric concentrations were similar to those generally detected in urban–rural areas with one location about 2–3 times more contaminated than the others. Since the most contaminated location was inside the industrial area but upwind of the MSWI, principal component analysis (PCA) was used to establish whether other sources were the cause. This analysis clearly showed that a local steel plant’s emission was the main source of PCDDs/Fs in ambient air. This study highlights the usefulness of multivariate data analysis such as PCA to identify, among different potential emission sources, the one really responsible for the contamination.     

Processes affecting the movement of organochlorine pesticides (OCPs) between soil and air in an industrial site in Turkey

Soil and atmospheric concentrations, dry deposition and soil-air gas exchange of organochlorine pesticides (OCPs) were investigated at an industrial site in Aliaga, Izmir, Turkey. Current-use pesticides, endosulfan and chlorpyrifos, had the highest atmospheric levels in summer and winter. Summertime total (gas + particle) OCP concentrations in air were higher, probably due to increased volatilization at higher temperatures and seasonal local/regional applications of current-use pesticides. Particle deposition fluxes were generally higher in summer than in winter. Overall average dry particle deposition velocity for all the OCPs was 4.9 ± 4.1 cm s⁻¹ (average ± SD). ΣDDXs (sum of p,p′-DDT, p,p′-DDD, and p,p′-DDE) were the most abundant OCPs in Aliaga soils (n = 48), probably due to their heavy historical use and persistence. Calculated fugacity ratios and average net gas fluxes across the soil-air interface indicated volatilization for α-CHL, γ-CHL, heptachlorepoxide, cis-nonachlor, trans-nonachlor, and p,p′-DDT in summer, and for α-CHL, γ-CHL, trans-nonachlor, endosulfan sulfate, and p,p′-DDT in winter. For the remaining OCPs, soil acted as a sink during both seasons. Comparison of the determined fluxes showed that dry particle, gas-phase, and wet deposition are significant OCP input mechanisms to the soil in the study area.     

Trend studies of polychlorinated biphenyls, dibenzo-p-dioxins and dibenzofurans in human milk

Human milk has been used in studies of long-term changes in the concentrations of organochlorine contaminants in mothers from the Stockholm region. The previously observed decline (1972 to 1985) in the levels of polychlorinated biphenyls (PCBs), dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) seems to have ceased for certain compounds since the levels were about the same in samples collected in 1985 and 1989. Calculating with the proposed toxicity equivalency factors for the different congeners of PCDDs, PCDFs and PCBs it is seen that the congeners of PCBs contribute more to the possible toxicity than those of PCDDs and PCDFs. The mono-ortho substituted congener 2,3′,4,4′,5-pentachlorobiphenyl (IUPAC No. 118) contributes with the largest part.     

Organochlorine pesticides and polybrominated diphenyl ethers in irrigated soils of Beijing, China: Levels, inventory and fate

Limited information on the levels, inventory and fate of Organochlorine pesticides (OCPs) and Polybrominated diphenyl ethers (PBDEs) in the soils irrigated by sewage or wastewater is available. In this study, variation in concentrations, profiles and fate of OCPs and PBDEs were investigated using soil samples collected from a region irrigated by sewage, mixed water and clean water in the east of Beijing, China. No significant variation was observed among groups, except for penta-BDEs. The measured ΣOCPs and ΣPBDEs residues ranged from 6.4 to 171.2 ng g⁻¹ (dw) and 501.9 to 3310.7 pg g⁻¹ (dw), respectively. ΣDDTs and BDE-209 were the most abundant congeners accounting for about 76% of ΣOCPs and 93% of ΣPBDEs. Concentrations of hexachlorocyclohexanes (HCHs), dichlorodiphenyltrichloroethane (DDTs) and its major degradation products, and hexachlorobenzene (HCB) ranged from 1.2 to 11.4 ng g⁻¹ (dw), 4.0 to 155.6 ng g⁻¹ (dw) and 0.3 to 3.4 ng g⁻¹ (dw), respectively. The major DDT degradation products were p,p′-DDT and p,p′-DDE. The major hexachlorocyclohexane (HCH) isomer in irrigated soils is β-HCH, reflecting its higher affinity to solids and resistance to degradation than other isomers. Both α-HCH/β-HCH and p,p′-DDT/p,p′-DDE ratios were log-normally distributed and negatively correlated to log(ΣHCHs) and log(ΣDDTs), respectively, suggesting no significant recent application of OCPs. Individual BDE congeners, ΣPBDEs and ΣOCPs were significantly correlated with total organic carbon (TOC). Moreover, a good correlationship between ΣPBDEs and black carbon (BC) was obtained but not between ΣOCPs and BC. Sewage irrigation did not have obvious effect on their contaminant levels and inventory of OCPs and PBDEs.     

Estimation and validation of PM2.5/PM10 exhaust and non-exhaust emission factors for practical street pollution modelling

In order to carry out efficient traffic and air quality management, validated models and PM emission estimates are needed. This paper compares current available emission factor estimates for PM₁₀ and PM_2.5 from emission databases and different emission models, and validates these against eight high quality street pollution measurements in Denmark, Sweden, Germany, Finland and Austria.The data sets show large variation of the PM concentration and emission factors with season and with location. Consistently at all roads the PM₁₀ and PM_2.5 emission factors are lower in the summer month than the rest of the year. For example, PM₁₀ emission factors are in average 5–45% lower during the month 6–10 compared to the annual average.The range of observed total emission factors (including non-exhaust emissions) for the different sites during summer conditions are 80–130 mg km⁻¹ for PM₁₀, 30–60 mg km⁻¹ for PM_2.5 and 20–50 mg km⁻¹ for the exhaust emissions.We present two different strategies regarding modelling of PM emissions: (1) For Nordic conditions with strong seasonal variations due to studded tyres and the use of sand/salt as anti-skid treatment a time varying emission model is needed. An empirical model accounting for these Nordic conditions was previously developed in Sweden. (2) For other roads with a less pronounced seasonal variation (e.g. in Denmark, Germany, Austria) methods using a constant emission factor maybe appropriate. Two models are presented here.Further, we apply the different emission models to data sets outside the original countries. For example, we apply the “Swedish” model for two streets without studded tyre usage and the “German” model for Nordic data sets. The “Swedish” empirical model performs best for streets with studded tyre use, but was not able to improve the correlation versus measurements in comparison to using constant emission factors for the Danish side. The “German” method performed well for the streets without clear seasonal variation and reproduces the summer conditions for streets with pronounced seasonal variation. However, the seasonal variation of PM emission factors can be important even for countries not using studded tyres, e.g. in areas with cold weather and snow events using sand and de-icing materials. Here a constant emission factor probably will under-estimate the 90-percentiles and therefore a time varying emission model need to be used or developed for such areas.All emission factor models consistently indicate that a large part (about 50–85% depending on the location) of the total PM₁₀ emissions originates from non-exhaust emissions. This implies that reduction measures for the exhaust part of the vehicle emissions will only have a limited effect on ambient PM₁₀ levels.     

Vertical distribution of polycyclic aromatic hydrocarbons in atmospheric boundary layer of Beijing in winter

Air samples were collected using active samplers at various heights of 8, 15, 32, 47, 65, 80, 102, 120, 140, 160, 180, 200, 240, 280 and 320 m on a meteorological tower in an urban area of Beijing in two campaigns in winter 2006. Altitudinal distributions of polycyclic aromatic hydrocarbons (PAHs) in atmospheric boundary layer of Beijing in winter season were investigated. Meteorological conditions during the studied period were characterized by online measurements of four meteorological parameters as well as trajectory calculation. The mean total concentrations of 15 PAHs except naphthalene of gaseous and particulate phase were 667±450 and 331±144 ng m⁻³ in January and 61±19 and 29±6 ng m⁻³ in March, respectively. Domestic coal combustion and vehicle emission were the dominant PAH sources in winter. Although the composition profiles derived from the two campaigns were similar, the concentrations were different by one order of magnitude. The higher concentrations in January were partly caused by higher emission due to colder weather than March. Moreover, weak wind, passing through the city center before the sampling site, picked up more contaminants on the way and provided unfavorable dispersion condition in January. For both campaigns, PAH concentrations decreased with heights because of ground-level emission and unfavorable dispersion conditions in winter. The concentration ratio of PAHs in gas versus solid phases was temperature dependent and negatively correlated to their octanol–air partition coefficients.