Persistent organic pollutants in atmospheric deposition and biomonitoring with Tillandsia Usneoides (L.) in an industrialized area in Rio de Janeiro state, south east Brazil--Part I: PCDD and PCDF

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 total deposition rates on funnels covered with polyurethane foams. Samples were collected during 78 days in V.R. and 95 days in PNI in winter (dry season, June-August 2003) and during 114 days in both areas in summer (rainy season, December 2003-February 2004). The PCDD/PCDF deposition rates ranged from 0.10 to 1.9 pg WHO-TEQ/(m2 day) in winter and from 0.11 to 2.2 pg WHO-TEQ/(m2 day) in summer. Deposition rates found in V.R. in summer were four- to ninefold higher than those measured in PNI, while in winter deposition rates in both regions were in the same range. Deposition rates in V.R. in summer were about five fold lower than those measured in 1996. PCDD/PCDF levels in biomonitor samples were between 0.95 and 14.6 ng WHO-TEQ/kg d.m. in winter and between 2.2 and 5.2 ng WHO-TEQ/kg d.m. in summer. In winter, concentrations found in V.R. were up to 11 times higher than those found in PNI, while in summer the levels measured in both areas were comparable. The homologue and isomer profiles found in the deposition as well as in the biomonitor samples from V.R. indicate that steel production is the main source of contamination in the region, whereas in PNI, the long range transport of these pollutants is the predominant contamination pathway.     

A novel approach for characterization of polycyclic aromatic hydrocarbon (PAH) pollution patterns in sediments from Guanabara Bay, Rio de Janeiro, Brazil

A novel multivariate method based on principal component analysis of pre-processed sections of chromatograms is used to characterize the complex PAH pollution patterns in sediments from Guanabara Bay, Brazil. Five distinct sources of 3- to 6-ring PAHs could be revealed. The harbour is the most contaminated site in the bay, its plume stretches in a South West to North East direction and the chemical profile indicates mainly pyrogenic sources mixed with a fraction of high-molecular-weight petrogenic PAHs. Rio São João de Meriti is the second largest source of PAHs, and introduces mainly a fraction of low-molecular-weight petrogenic PAHs from the western region of Rio de Janeiro. The sites close to the ruptured pipeline at the Duque de Caxias Refinery show a distinctive pollution pattern indicating a heavy petroleum fraction. The method also led to the identification of new potential indicator ratios also involving coeluting peaks (e.g., triphenylene and chrysene).     

Persistent organic pollutants in sea bass (Dicentrarchus labrax L.) in two fish farms in the Mediterranean Sea

We analyzed polychlorobiphenyls (PCBs), perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) in the edible part of farmed sea bass reared in two fish farms in Liguria (Northern Italy). The aim was to determine the contamination levels and human exposure to these chemicals through fish consumption. Concentrations of “dioxin-like” PCBs (DL-PCBs) ranged from 0.033 to 0.759 pg Σ_TEQ-PCB g⁻¹ whole weight (w.w.) in fish farm 1 and from 0.032 to 1.60 pg Σ_TEQ-PCB g⁻¹ w.w. in fish farm 2, and the six indicators of “non-dioxin-like” (NDL-PCBs) from 0.538 to 9.33 ng Σ_6PCB g⁻¹ w.w. and from 1.62 to 27.6 ng Σ_6PCB g⁻¹ w.w. Concentrations were generally lower in farm 1 than in farm 2. One reason for this difference might be the proximity of farm 2 to the seaport of La Spezia, which could be a punctual source of pollutants influencing the contamination of the water in the farm. Principal component analysis (PCA) showed differences also in the congeners profiles for the two sites, with higher-chlorinated PCBs more abundant in farm 1, and lower-chlorinated PCBs were more abundant in farm 2. Most of the concentrations of PFOS and PFOA were below the limit of detection (LOD 0.05 ng g⁻¹ w.w.). Only about 10% of the samples analyzed had levels slightly higher than the LOD. Assessments of exposure using these data showed that consumption of farmed fish may contribute significantly to PCBs through the diet, whereas the contribution of PFOS and PFOA seems to be low.     

Contribution to the understanding of biologic concentrations of arsenic in children living in an urban area from Rio de Janeiro,Brazil

Environmental Science and Pollution Research - There are few studies about children’s environmental exposure to arsenic (As) in Brazil, most of them being in mining regions. The objective of...     

Heavy metals, PCDD/F and PCB in sewage sludge samples from two wastewater treatment facilities in Rio de Janeiro State, Brazil

Two sewage sludge samples collected from an urban as well as a rural area in Brazil and one sludge sample originating from the city of Balingen, Baden-Württemberg, South Germany, were investigated in respect to contamination with heavy metals, PCDD/F and PCB. The results were compared to PCDD/F and indicator-PCB mean values found in the region of Baden-Württemberg. The observed toxicity equivalents of PCDD/F found in the Brazilian samples, were below the upper limit specified by German legislation for final disposal or agricultural use in soils. Both the PCB and heavy metal values exceeded this limit. The PCDD/F congener/homologue profiles found in the Brazilian samples indicated that the urban sewage sludge shows a contamination where both chlorophenols and depositional sources appear to be contributing to the contamination pool. The enrichment of highly chlorinated PCDD/F groups in the sludge of semi-rural origin is probably due to transport phenomena effects. For the German sludge sample, depositional sources seem to be the main PCDD/F contamination pathway. Regarding PCB, both Brazilian samples show a homologue profile that indicates a contamination stemming from technical PCB formulations like Clophen A50 and Clophen A60 or equivalent.     

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

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

Atmospheric concentrations, occurrence and deposition of persistent organic pollutants (POPs) in a Mediterranean coastal site (Etang de Thau, France)

Atmospheric concentrations and deposition fluxes of PCDD/F and PCB have been evaluated over a 1-year period in a Mediterranean coastal lagoon (Etang de Thau, France). Indicative PBDE air concentrations in the hot season are also reported in this work. ∑2,3,7,8-PCDD/Fs and ∑18PCBs (gas + particulate) air concentrations ranged from 67 to 1700 fg m⁻³ and from 13 to 95 pg m⁻³, respectively whereas ∑8PBDEs (gas + particulate) summer time levels varied from 158 to 230 pg m⁻³. The PCDD/F and PCB atmospheric occurrence over Thau lagoon and subsequent inputs to the surface waters are determined by an assemble of factors, being the seasonality of atmospheric concentration, the air mass origin and meteorological conditions important drivers. Total (wet + dry) ∑2,3,7,8-PCDD/Fs and ∑18PCBs deposition fluxes to Thau Lagoon waters are 117 and 715 pg m⁻² d⁻¹, respectively.     

Persistent organic pollutants,heavy metals and parasites in the glaucous gull (Larus hyperboreus) on Spitsbergen

The prediction of a higher parasite infection as a consequence of an impaired immune system with increasing persistent organic pollution (POP) and heavy metal levels were investigated in adult glaucous gull (Larus hyperboreus) from Svalbard. The levels of chlorinated pesticides, polychlorinated biphenyls (PCBs), toxaphenes and polybrominated diphenyl ethers (PBDEs) were measured in liver. Cupper, cadmium, lead, mercury, selenium and zinc were measured in kidney samples. An elevated ratio of PCB-118 was found, suggesting that local contamination from the settlement was detectable in the glaucous gull. Eight cestodes, four nematodes, two acanthocephalan and three trematode helminth species were found in the intestine. A positive correlation was found between cestode intensities and selenium levels and between acanthocephalan intensities and mercury levels. No correlation was found between parasite intensities and POP concentrations. It is concluded that the contaminant levels found in glaucous gulls do not cause immune suppression severe enough to affect parasite intensity.     

PCB contamination in farmed and wild sea bass (Dicentrarchus labrax L.) from a coastal wetland area in central Italy

Food consumption is by far the main exposure route for polychlorinated biphenyls (PCBs) for the general population, and fish and fishery products seem to be the main contributors to the total dietary intake of these pollutants. In recent years some investigations have suggested that farmed fish may be more significantly contaminated than wild fish, because of polluted feed. This study measured the levels of PCBs in wild and farmed sea bass (Dicentrarchus labrax L.), one of the most valuable and popular fish in the Italian diet, and assessed the exposure to these pollutants through fish intake. Concentrations of summation operator (Sigma59PCBs) and dioxin-like PCBs (DL-PCBs), as toxic equivalency (TEQ), in fish samples, ranged from 2.2 to 32ngg(-1) and from 0.1 to 4.0pg TEQ((2006) DL-PCBs)g(-1) whole weight, respectively. Farmed sea bass were as average two times more contaminated. Even if the concentrations of DL-PCBs were below the regulation limits, intake of these compounds from nine fish meals per month can in itself exceed the WHO Provisional Tolerable Monthly Intake (PTMI).     

The importance of atmospheric deposition, charge and atomic mass to the dynamics of minor and rare elements in developing, ageing, and wilted leaves of beech (Fagus sylvatica L.)

The amounts of sixty elements in developing, maturing, senescent and wilting leaves, and in the wintering dead leaves attached to the branches, are reported for a beech (Fagus sylvatica) forest on mor Podzol in south Sweden, a site with no local sources of pollution or geological anomalies. The amounts (contents per leaf) of K (potassium), Rb (rubidium), Cs (caesium), Cu (copper) and P (phosphorus) were highest in young leaves, decreasing throughout the growing season and usually in the subsequent winter. The entirely opposite pattern with a continuous, mostly even increase of the amounts was measured with Be (beryllium), Ba (barium), Hg (mercury), Al (aluminium), Tl (thallium), Pb (lead), Bi (bismuth), V (vanadium), W (tungsten), As (arsenic), Sb (antimony), and Se (selenium). Amounts of rare-earth elements and some transition metals, such as Co (cobalt), Ti (titanium), and the actinides Th (thorium) and U (uranium) were more stable during the growing season, after an initial increase in early summer, but increased greatly in the winter. This winter increase in dead attached leaves has to be accounted for by uptake from long-distance transported constituents in dry and wet deposition. It was similar to deposition rate estimates using moss carpets from the same locality. A passive uptake was positively related to ionic charge and atomic mass. However, the amounts of several, mainly non-essential elements, such as Ni (nickel), Sc (scandium), Zr (zirconium), Cr (chromium), Ag (silver), and Cd (cadmium) were not much lower in the young or maturing leaves than in the wintered dead leaves of this deciduous (hardwood) forest and a proportion apparently originated from internal translocation in the trees. Seasonal fluxes or cycling of many of the scarce or rare elements reported here have never been studied before in forest ecosystems.     

High levels of heavy metals in rice (Oryza sativa L.) from a typical E-waste recycling area in southeast China and its potential risk to human health

Very few studies have investigated the heavy metal contents in rice samples from a typical E-waste recycling area. In this study, 10 heavy metals (As, Ba, Cd, Co, Cr, Cu, Hg, Mn, Ni and Pb) in 13 polished rice and relevant hull samples, six relevant paddy soil samples were investigated. The geometric mean concentrations of Cd, Cu and Hg in soil samples were 1.19, 9.98 and 0.32 microg g(-1), respectively, which were 4.0, 2.0 and 1.1-folds of the maximum allowable concentration (MAC) (0.30, 50.00, 0.30 microg g(-1), respectively) for Chinese agricultural soils. The analyzed metal concentrations were significantly different between rice and relevant hull except for As, Cd and Hg (p<0.05). All metal concentrations, except for Co, in rice hull were higher than those in polished rice. The geometric mean of Pb in polished rice reached 0.69 microg g(-1), which was 3.5-folds higher than the MAC (0.20 microg g(-1)) by the safety criteria for milled rice. Cd contents in 31% of the rice samples exceeded the national MAC (0.20 microg g(-1)), and the arithmetic mean also slightly exceeded national MAC. In addition, Cd and Pb contents in local rice were much higher than commercial rice samples examined in this work and previous studies. Comparing the tolerable daily intakes given by FAO/WHO with the mean estimated daily intakes; Pb daily intake through rice consumption in this area was 3.7 microg day(-1)kg(-1) body weight (bw), which already exceeded the FAO tolerable daily intake, and the Cd daily intake (0.7 microg day(-1)kg(-1) bw) through rice had already taken up 70% of the total tolerable daily intake (1 microg day(-1)kg(-1) bw). The daily intake of Hg and As through rice was much lower than the tolerable daily intakes, but bioaccumulation of Hg through the food chain and intake of As from other food stuff should also be of concern.     

Phosalone applied to cotton (Gossypium hirsutum L.): its deposition and persistence on foliages, soils and final residues in seeds

Phosalone, O,O-diethyl-S-(6-chloro-1,3-benzoxazol-2(3H)-onyl)methyl phosphorodithioate, was field-applied by ground equipment to cotton (Gossypium hirsutum L.) at the rates of 1050 and 2100 g a.i./ha, respectively, to determine its dissipation on leaves and soils and the residues in seeds at harvest. The insecticide concentrations on cotton leaves and soils were measured periodically for 14 days following its application. It was found that the half lives of the insecticide on cotton leaves at the dosages of 1050 and 2100 g a.i./ha were 6.8 and 6.3 days, respectively. And the half lives on soils for the 2 dosages were 7 and 5.8 days, respectively. The residues remaining in soils at harvest time were 0.072 and 0.121 mg/kg 14 days post-application and the residues in cotton seeds were relatively low (less than 0.02-0.12 mg/kg).     

Application of an integrated Weather Research and Forecasting (WRF)/CALPUFF modeling tool for source apportionment of atmospheric pollutants for air quality management: A case study in the urban area of Benxi,China

In this study, the authors endeavored to develop an effective framework for improving local urban air quality on meso-micro scales in cities in China that are experiencing rapid urbanization. Within this framework, the integrated Weather Research and Forecasting (WRF)/CALPUFF modeling system was applied to simulate the concentration distributions of typical pollutants (particulate matter with an aerodynamic diameter <10 μm [PM₁₀], sulfur dioxide [SO₂], and nitrogen oxides [NO_x]) in the urban area of Benxi. Statistical analyses were performed to verify the credibility of this simulation, including the meteorological fields and concentration fields. The sources were then categorized using two different classification methods (the district-based and type-based methods), and the contributions to the pollutant concentrations from each source category were computed to provide a basis for appropriate control measures. The statistical indexes showed that CALMET had sufficient ability to predict the meteorological conditions, such as the wind fields and temperatures, which provided meteorological data for the subsequent CALPUFF run. The simulated concentrations from CALPUFF showed considerable agreement with the observed values but were generally underestimated. The spatial-temporal concentration pattern revealed that the maximum concentrations tended to appear in the urban centers and during the winter. In terms of their contributions to pollutant concentrations, the districts of Xihu, Pingshan, and Mingshan all affected the urban air quality to different degrees. According to the type-based classification, which categorized the pollution sources as belonging to the Bengang Group, large point sources, small point sources, and area sources, the source apportionment showed that the Bengang Group, the large point sources, and the area sources had considerable impacts on urban air quality. Finally, combined with the industrial characteristics, detailed control measures were proposed with which local policy makers could improve the urban air quality in Benxi. In summary, the results of this study showed that this framework has credibility for effectively improving urban air quality, based on the source apportionment of atmospheric pollutants.

Implications: The authors endeavored to build up an effective framework based on the integrated WRF/CALPUFF to improve the air quality in many cities on meso-micro scales in China. Via this framework, the integrated modeling tool is accurately used to study the characteristics of meteorological fields, concentration fields, and source apportionments of pollutants in target area. The impacts of classified sources on air quality together with the industrial characteristics can provide more effective control measures for improving air quality.

Through the case study, the technical framework developed in this study, particularly the source apportionment, could provide important data and technical support for policy makers to assess air pollution on the scale of a city in China or even the world.     

Partitioning of inorganic and organic mercury in cockles Cardium edule (L.) and C. glaucum (Bruguiére) from a chronically polluted area: influence of size and age

Partitioning of inorganic and organic mercury was studied in the cockles Cardium edule and C. glaucum sampled in a chronically polluted area in the Western Limfjord, Denmark. The proportion of organic mercury in the cockles was linearly correlated to age (and weight) but not to total mercury concentration in the cockles. In 2-, 3- and 4-year-old cockles organic mercury constituted c. 30%, 60%, and 90% of total mercury, respectively. The age correlated proportion of organic mercury is discussed in a food chain context.     

Tissues and hair residues and histopathology in wild rats (Rattus rattus L.) and Algerian mice (Mus spretus Lataste) from an abandoned mine area (Southeast Portugal)

Data gathered in this study suggested the exposure of rats and Algerian mice, living in an abandoned mining area, to a mixture of heavy metals. Although similar histopathological features were recorded in the liver and spleen of both species, the Algerian mouse has proved to be the strongest bioaccumulator species. Hair was considered to be a good biological material to monitor environmental contamination of Cr in rats. Significant positive associations were found between the levels of this element in hair/kidney (r=0.826, n=9, p<0.01) and hair/liver (r=0.697, n=9, p=0.037). Although no association was found between the levels of As recorded in the hair and in the organs, the levels of this element recorded in the hair, of both species, were significantly higher in animals captured in the mining area, which met the data from the organs analysed. Nevertheless, more studies will be needed to reduce uncertainty about cause-effect relationships.     

Monitoring and assessment of mercury pollution in the vicinity of a chloralkali plant. II Plant-availability, tissue-concentration and genotoxicity of mercury from agricultural soil contaminated with solid waste assessed in barley (Hordeum vulgare L.)

Barley (Hordeum vulgare L.) was used to assess plant-availability, tissue-concentration and genotoxicity of mercury from the solid waste deposits of a chloralkali plant. Seeds of H. vulgare, presoaked in distilled water, were allowed to germinate and grow on agricultural soil mixed with solid waste containing 2550+/-339 mg Hg kg(-1) at different proportions (0.75, 1.5, 2.5 and 5%). Plants raised from germinating seeds on uncontaminated agricultural soil served as controls. On day 7, germination counts and seedling heights were recorded. The concentration of mercury in soil, and plant tissue (dry weight) were determined at different stages of plant growth from day 7 till maturity and harvest. The availability of mercury from the soil was assessed by extracting mercury at a range of pH values (2-6) and by chemical methods. The embryonic shoots excised at 36 h of germination were subjected to cytological analysis to determine mitotic index and frequency of mitoses with chromosomal aberrations. The pollen mother cells from anthers of young M1-spikes were analysed to score meiotic aberrations. Subsequently, the pollen fertility and seed set were determined. Furthermore, M2-seedlings were analysed for chlorophyll-deficient mutations. The cytogenetic analysis revealed the effects of mercury on the mitotic and meiotic chromosomes which were significantly correlated with soil-mercury. The bioconcentration of mercury in aerial tissues decreased with the age of the plant. Roots, in particular, were found to concentrate most of the mercury taken up by the plant. At the time of harvest, the bioconcentration of mercury in straw was at a minimum. The accumulation of mercury in grain, which was significant, did not increase with the increase in concentration of mercury in soil but maintained a plateau, indicating a restriction of transport of mercury through the phloem. The unique advantage with the use of Hordeum assay is that, besides assessing the germline toxicity, the assay takes into account the possible contamination of the agricultural food-chain.