Persistent organic pollutants in atmospheric deposition and biomonitoring with Tillandsia usneoides (L.) in an industrialized area in Rio de Janeiro state, southeast Brazil--Part II: PCB and PAH

Monitoring of immission of persistent organic pollutants in the industrialized area of Volta Redonda (V.R.) and in the National Park of Itatiaia (PNI) in southeast Brazil was performed using an endemic bromeliad species as biomonitor and measuring bulk deposition rates of polychlorinated biphenyls (PCB) and polycyclic aromatic hydrocarbons (PAH). For the sum of PCB, overall deposition rates were between 17 and 314 ng/(m2 day) in winter and between 43 and 81 ng/(m2 day) in summer, respectively. Deposition rates of dioxin-like PCBs ranged from 0.14 to 2.8 pg WHO-TEQ/(m2 day) in winter and from 0.90 to 4.3 pg WHO-TEQ/(m2 day) in summer. PCB deposition rates (total PCB and WHO-TEQ) were in the same range in winter in V.R. and PNI. In summer, contamination levels in V.R. were 6-10-folds higher than in PNI. PCB concentrations in biomonitor samples from V.R. and PNI were in the same range in summer and in winter. Concentrations of total PCB ranged from 14 to 95 microg/kg dry matter (d.m.) in winter and from 18 to 27 microg/kg d.m. in summer, respectively. The TEQ values were between 1.7 and 4.1 ng WHO-TEQ/kg d.m. in winter and between 1.9 and 2.9 ng WHO-TEQ/kg d.m. in summer. PCB concentrations of di-ortho PCB but not of non-ortho PCB were a factor of 2-4 lower in summer in both areas. PCB congener profiles resembled those from technical formulations. The profiles shifted to the higher chlorinated congeners in summer, probable due to revolatilisation of the lighter components at higher temperatures. PCB profiles in biomonitor resembled those from deposition samples and the shift to the heavier congeners in summer was even more pronounced. PAH deposition rates were in a similar range in both areas (131-2415 ng/(m2 day)). PAH levels in biomonitor samples from V.R. were about one order of magnitude higher than in samples from PNI indicating the impact of local sources. PAH profiles revealed stationary thermal processes as main source of contamination in V.R. whereas in PNI, biomass burning seems to be the main contamination source.     

Ozone pre-treatment as improver of PAH removal during anaerobic digestion of urban sludge

Polycyclic aromatic hydrocarbons are ubiquitous persistent pollutants. They may accumulate in sludge during wastewater treatment because of their low biodegradability and their hydrophobic characteristics. Combination of ozonation and anaerobic digestion may be efficient to remove PAHs naturally present in sludge. The objective of this study was to investigate the impact of ozone pre-treatment, with and without surfactant addition, on the anaerobic degradation of 12 PAHs (from low to high molecular weight). Under anaerobic digestion without ozonation pre-treatment, the highest removals were obtained for the lightest PAHs (3-aromatic rings). Ozonation pre-treatment of sludge allowed to increase biodegradability or bioavailability of each PAH, and the PAH removals were well correlated to the PAH solubility. Finally, addition of tyloxapol before sludge ozone pre-treatment had antagonist effects on PAH removal during anaerobic digestion: negative impact on anaerobic ecosystem activity and improvement of PAH bioaccessibility (particularly the PAHs with the highest octanol water partition coefficients).     

Exemplifying whole-plant ozone uptake in adult forest trees of contrasting species and site conditions

Whole-tree O3 uptake was exemplified for Picea abies, Fagus sylvatica and Larix decidua in stands at high and low altitude and contrasting water availability through sap flow measurement in tree trunks, intrinsically accounting for drought and boundary layer effects on O3 flux. O3 uptake of evergreen spruce per unit foliage area was enhanced by 100% at high relative to low elevation, whereas deciduous beech and larch showed similar uptake regardless of altitude. The responsiveness of the canopy conductance to water vapor and, as a consequence, O3 uptake to soil moisture and air humidity did not differ between species. Unifying findings at the whole-tree level will promote cause-effect based O3 risk assessment and modeling.     

Spatial trends of polyfluorinated compounds in guillemot (Uria aalge) eggs from North-Western Europe

Polyfluorinated alkyl compounds (PFCs) are a group of chemicals of growing concern that have been detected in biological and abiotic samples worldwide. This study reports the concentrations of a suite of PFCs: perfluorooctyl sulfonate (PFOS), perfluorooctyl sulfonamide (PFOSA) and perfluorinated carboxylic acids (PFCAs) in guillemot (Uria aalge) eggs, collected in North-Western Europe, from Iceland, the Faroe Islands, Sweden and two locations in Norway. The highest concentrations of PFOS were found in samples from Sweden (mean 400 ng g(-1) wet weight (w.w.)), which were almost five times higher than concentrations found in Norwegian samples (mean 85 ng g(-1)w.w. from both sample sites). The concentrations found in Icelandic and Faroe samples were lowest (mean 16 and 15 ng g(-1)w.w., respectively). Only Swedish samples differed significantly from the other locations. In general, PFCAs show a different spatial trend than PFOS. Perfluorooctanoic acid (PFOA) was not detected in any sample and perfluorononanoic acid (PFNA) was only detected in samples from Sweden. The most abundant PFCA was perfluoroundecanoic acid (PFUA) with highest concentrations in samples from Sweden (mean 82 ng g(-1)w.w.), samples from the Faroe Islands had the second highest concentration (mean 57 ng g(-1)w.w.) and samples from Iceland and Norway had concentrations ranging between 18 and 30 ng g(-1)w.w. The original hypothesis was based on the idea that PFC concentrations are the highest close to more densely populated and industrialized areas and lower levels in remote areas. However, the geographic pattern is more complicated than predicted and varies among different PFCs.     

Polycyclic aromatic hydrocarbon sampling in wastewaters using semipermeable membrane devices: accuracy of time-weighted average concentration estimations of truly dissolved compounds

Semipermeable membrane devices (SPMDs) previously spiked with performance reference compounds were exposed in wastewater. After 6 days of exposure, 13 polycyclic aromatic hydrocarbons (PAHs) were quantified in SPMDs. Exchange rate constants and time-weighted average (TWA) concentrations of SPMD-available PAHs in water were calculated. The bias of using SPMDs to estimate an actual TWA concentration if the concentration in water fluctuates, as can be expected in wastewater, was studied with numerical simulations. The bias increased with the exchange rate constant. However, most exchange rate constants evaluated in SPMDs exposed in wastewater were small enough for SPMDs to estimate a TWA concentration of PAHs even when the water concentration varied. TWA-SPMD-available concentrations were always below total dissolved (operationally defined as 0.7 microm) concentrations, indicating that part of the dissolved PAHs was not available for sampling. In situ partitioning coefficients K(DOC) were computed and found to be slightly higher than data from the literature. This confirms that only truly dissolved PAHs should be sampled by SPMDs in wastewater.     

Sorption of native polyaromatic hydrocarbons (PAH) to black carbon and amended activated carbon in soil

Organic pollutants (e.g. polyaromatic hydrocarbons (PAH)) strongly sorb to carbonaceous sorbents such as black carbon and activated carbon (BC and AC, respectively). For a creosote-contaminated soil (Sigma15PAH 5500 mg kg(dry weight(dw))(-1)) and an urban soil with moderate PAH content (Sigma15PAH 38 mg kg(dw)(-1)), total organic carbon-water distribution coefficients (K(TOC)) were up to a factor of 100 above values for amorphous (humic) organic carbon obtained by a frequently used Linear-Free-Energy Relationship. This increase could be explained by inclusion of BC (urban soil) or oil (creosote-contaminated soil) into the sorption model. AC is a manufactured sorbent for organic pollutants with similar strong sorption properties as the combustion by-product BC. AC has the potential to be used for in situ remediation of contaminated soils and sediments. The addition of small amounts of powdered AC (2%) to the moderately contaminated urban soil reduced the freely dissolved aqueous concentration of native PAH in soil/water suspensions up to 99%. For granulated AC amended to the urban soil, the reduction in freely dissolved concentrations was not as strong (median 64%), especially for the heavier PAH. This is probably due to blockage of the pore system of granulated AC resulting in AC deactivation by soil components. For powdered and granulated AC amended to the heavily contaminated creosote soil, median reductions were 63% and 4%, respectively, probably due to saturation of AC sorption sites by the high PAH concentrations and/or blockage of sorption sites and pores by oil.     

Long-term survey of heavy-metal pollution, biofilm contamination and diatom community structure in the Riou Mort watershed, South-West France

In a metal-polluted stream in the Riou Mort watershed in SW France, periphytic biofilm was analyzed for diatom cell densities and taxonomic composition, dry weight and metal bio-accumulation (cadmium and zinc). Periphytic diatom communities were affected by the metal but displayed induced tolerance, seen through structural impact (dominance of small, adnate species) as well as morphological abnormalities particularly in the genera Ulnaria and Fragilaria. Species assemblages were characterized by taxa known to occur in metal-polluted environments, and shifts in the community structure expressed seasonal patterns: high numbers of Eolimna minima, Nitzschia palea and Pinnularia parvulissima were recorded in Summer and Autumn, whereas the species Surirella brebissonii, Achnanthidium minutissimum, Navicula lanceolata and Surirella angusta were dominant in Winter and Spring. Commonly used indices such as the Shannon diversity index and Specific Pollution Sensitivity Index reflected the level of pollution and suggest seasonal periodicity, the lowest diversities being observed in Summer.     

Dioxins in adipose tissue of women in Southern Spain

Seventeen polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were quantified in adipose tissue samples of non-occupationally exposed women living in Southern Spain. Geometric mean levels of sum of congeners and WHO(PCDD/F)-TEQ(2005) were 410 and 17.9pgg(-1) fat, respectively. Among PCDDs, octachlorodibenzo-p-dioxin (OCDD) showed the highest concentration with a mean value of 265pgg(-1) fat, followed by 1,2,3,6,7,8-HxCDD (49.3pgg(-1) fat) and 1,2,3,4,6,7,8-HpCDD (45.2pgg(-1) fat). These three congeners were responsible for around 90% of the sum of all PCDD/F congeners in adipose tissue. The geometric mean 2,3,7,8-TCDD value was 1.87pgg(-1) fat. 2,3,4,7,8-PeCDF (8.43pgg(-1) fat) showed the highest concentration among the PCDFs, followed by 1,2,3,4,7,8-HxCDF (4.17pgg(-1) fat) and 1,2,3,6,7,8-HxCDF (3.28pgg(-1) fat), and these three congeners were responsible for 4% of the sum of all studied PCDD/F congeners in adipose tissue and 76% of the sum of ten PCDFs. 1,2,3,7,8,9-HxCDF was the only congener not quantified in any sample, while 1,2,3,4,7,8,9-HpCDF, 1,2,3,7,8-PeCDF, OCDF and 2,3,7,8-TCDF were found in 5, 16, 16 and 19 samples, respectively. All other congeners were quantifiable in all 20 samples. Congeners contributing most to the WHO(PCDD/F)-TEQ(2005) were 1,2,3,7,8-PeCDD (31.6%), 1,2,3,6,7,8-HxCDD (28.3%) and 2,3,4,7,8-PeCDF (14.6%). The body burden of log-transformed WHO(PCDD/F)-TEQ(2005) levels increased with age (B=0.02; 95% CI=0.01, 0.03; p=0.02). Although these adipose tissue PCDD/F levels are similar to previously published findings in Spain and other European countries, further research is needed to determine trends in the exposure of women to these chemical residues.     

Complex host marking in the cabbage root fly

Summary. The cabbage root fly marks an oviposition site with two different chemical messages. Plants that were exposed to ovipositing flies are less acceptable than control plants, while sand particles that were closely associated with an actual oviposition site stimulate oviposition. By combining the information from these opposing messages, the cabbage root fly may be able to optimise the size of its egg clusters in relation to the food available for the larvae. The findings might account for the aggregated oviposition observed in this species.     

Polycyclic aromatic hydrocarbons (PAHs) in surface sediments from the Bizerte Lagoon,Tunisia: levels,sources, and toxicological significance

To assess the status of polycyclic aromatic hydrocarbon (PAH) contamination in sediments from the Bizerte Lagoon (northern Tunisia), 18 surface sediment samples were collected in March 2011 and analyzed for 14 US Environmental Protection Agency priority PAHs by high-performance liquid chromatography. The total concentrations of the 14 PAHs (ΣPAHs) ranged from 16.9 to 394.1 ng g^?1 dry weight (dw) with a mean concentration of 85.5 ng g^?1 dw. Compared with other lagoons, coasts, and bays in the world, the concentrations of PAHs in surface sediments of the Bizerte Lagoon are low to moderate. The PAHs’ composition pattern was dominated by the presence of four-ring PAHs (45.8 %) followed by five-ring (26.8 %) and three-ring PAHs (12.7 %). The PAH source analysis suggested that the main origin of PAHs in the sediments of the lagoon was mainly from pyrolytic sources. According to the numerical effect-based sediment quality guidelines of the USA, the levels of PAHs in the Bizerte Lagoon should not exert adverse biological effects. The total benzo[a]pyrene toxicity equivalent values calculated for the samples varied from 3.1 to 53.7 ng g^?1 dw with an average of 10.6 ng g^?1 dw.