Role of volcanic dust in the atmospheric transport and deposition of polycyclic aromatic hydrocarbons and mercury

The role of volcanic ash as scavenger of atmospheric pollutants, in their transport and final deposition to the ground is examined. Attention is focused on polycyclic aromatic hydrocarbons (PAHs) and on particulate mercury (Hgp). The ash-fall deposits studied belong to the 2001 and 2002 eruptive activity of Mount Etna, Southern Italy, and were investigated at three (2001) and four (2002) sites downwind of the major tephra dispersal pattern. The dry deposition of mercury and PAHs was determined, and, in particular, a downward flux to the ground of PAHs (approximately 7.29 microg m(-2) per day) and mercury (750 ng m(-2) per day) was estimated in Catania from October 26 to October 28, 2002. Finally, evidence on the anthropogenic origin of PAHs scavenged from the troposphere by volcanic ash is supported by the analysis of PAH compositions in granulometrically homogeneous fractions.     

Trophic transfer and accumulation of mercury in ray species in coastal waters affected by historic mercury mining (Gulf of Trieste,northern Adriatic Sea)

Total mercury (Hg) and monomethylmercury (MMHg) were analysed in the gills, liver and muscle of four cartilaginous fish species (top predators), namely, the eagle ray (Myliobatis aquila), the bull ray (Pteromylaeus bovinus), the pelagic stingray (Dasyatis violacea) and the common stingray (Dasyatis pastinaca), collected in the Gulf of Trieste, one of the most Hg-polluted areas in the Mediterranean and worldwide due to past mining activity in Idrija (West Slovenia). The highest Hg and MMHg concentrations expressed on a dry weight (d.w.) basis were found in the muscle of the pelagic stingray (mean, 2.529 mg/kg; range, 1.179–4.398 mg/kg, d.w.), followed by the bull ray (mean, 1.582 mg/kg; range, 0.129–3.050 mg/kg d.w.) and the eagle ray (mean, 0.222 mg/kg; range, 0.070–0.467 mg/kg, d.w.). Only one specimen of the common stingray was analysed, with a mean value in the muscle of 1.596 mg/kg, d.w. Hg and MMHg contents in the bull ray were found to be positively correlated with species length and weight. The highest MMHg accumulation was found in muscle tissue. Hg and MMHg were also found in two embryos of a bull ray, indicating Hg transfer from the mother during pregnancy. The number of specimens and the size coverage of the bull rays allowed an assessment of Hg accumulation with age. It was shown that in bigger bull ray specimens, the high uptake of inorganic Hg in the liver and the slower MMHg increase in the muscle were most probably due to the demethylation of MMHg in the liver. The highest Hg and MMHg contents in all organs were found in the pelagic stingray, which first appeared in the northern Adriatic in 1999. High Hg and MMHg concentrations were also found in prey species such as the banded murex (Hexaplex trunculus), the principal prey of the eagle rays and bull rays, the anchovy (Engraulis encrasicholus) and the red bandfish (Cepola rubescens), which are preyed upon by the pelagic stingray, as well as in zooplankton and seawater. Based on previously published data, a tentative estimation of MMHg bioamagnification was established. The average increase in MMHg between seawater, including phytoplankton, and zooplankton in the Gulf was about 10⁴, and MMHg in anchovy was about 50-fold higher than in zooplankton. The bioaccumulation of MMHg between seawater and small pelagic fish (anchovy) amounted to 10⁶ and between water and the muscle of larger pelagic fish (pelagic stingray) to 10⁷. The MMHg increase between surface sediment and benthic invertebrates (murex) and between benthic invertebrates and small benthic fish was 10². Ultimately, the trophic transfer resulted in a 10³ accumulation of MMHg between water and muscle of larger benthic fish (bull ray, eagle ray, common stingray), suggesting lower bioaccumulation by benthic feeding species.     

Accumulation of mercury and methylmercury by mushrooms and earthworms from forest soils

Accumulation of total and methyl-Hg by mushrooms and earthworms was studied in thirty-four natural forest soils strongly varying in soil physico-chemical characteristics. Tissue Hg concentrations of both receptors did hardly correlate with Hg concentrations in soil. Both total and methyl-Hg concentrations in tissues were species-specific and dependent on the ecological groups of receptor. Methyl-Hg was low accounting for less than 5 and 8% of total Hg in tissues of mushrooms and earthworms, respectively, but with four times higher concentrations in earthworms than mushrooms. Total Hg concentrations in mushrooms averaged 0.96 mg Hg kg⁻¹ dw whereas litter decomposing mushrooms showed highest total Hg and methyl-Hg concentrations. Earthworms contained similar Hg concentrations (1.04 mg Hg kg⁻¹ dw) whereas endogeic earthworms accumulated highest amounts of Hg and methyl-Hg.     

Serum concentrations of indicator PCB congeners in the Czech adult population

In 2006, levels of seven indicator polychlorinated biphenyl congeners (PCB28, 52, 101, 118, 138, 153, and 180) in blood serum of 202 blood donors residing for more than 2 years in five urban areas included in the Czech Human Biomonitoring project were measured by GC/MS/MS method. PCB congeners 138, 153 and 180 accounted for about 97% of the sum of the indicator congeners analyzed. Overall, the median and 95th percentile of the most abundant congener PCB 153 were 438 ng/g lipid and 1079 ng/g lipid, respectively. The highest median levels were found in Uherské Hradiste (669 ng/g lipid) and Ostrava (672 ng/g lipid in males compared to 341 ng/g lipid in females). Serum PCB concentrations were significantly associated with age, gender, place of residence and smoking habit, but not with body mass index and education. The results suggest the importance of PCB body burden in the Czech general population and the existence of hot spots.     

Non-point source mercury emission from the Idrija Hg-mine region: GIS mercury emission model

A mercury emission model was developed to estimate non-point source mercury (Hg) emissions occurring over the year from the Idrijca River catchment, draining the area of the world's second largest Hg mine in Idrija, Slovenia. Site-specific empirical correlations between the measured Hg emission fluxes and the parameters controlling the emission (comprising substrate Hg content, soil temperature, solar radiation and soil moisture) were incorporated into the mercury emission model developed using Geographic Information System technology. In this way, the spatial distribution and significance of the most polluted sites that need to be properly managed was assessed. The modelling results revealed that annually approximately 51 kg of mercury are emitted from contaminated surfaces in the catchment (640 km(2)), highlighting that emission from contaminated surfaces contributes significantly to the elevated Hg concentrations in the ambient air of the region. Very variable meteorological conditions in the modelling domain throughout the year resulted in the high seasonal and spatial variations of mercury emission fluxes observed. Moreover, it was found that mercury emission fluxes from surfaces in the Idrija region are 3-4 fold higher than the values commonly used in models representing emissions from global mercuriferous belts. Sensitivity and model uncertainty analysis indicated the importance of knowing not only the amount but also the type of mercury species and their binding in soils in future model development.     

Mercury emission and dispersion models from soils contaminated by cinnabar mining and metallurgy

The laboratory flux measurement system (LFMS) and dispersion models were used to investigate the kinetics of mercury emission flux (MEF) from contaminated soils. Representative soil samples with respect to total Hg concentration (26-9770 μg g(-1)) surrounding a decommissioned mercury-mining area (Las Cuevas Mine), and a former mercury smelter (Cerco Metalúrgico de Almadenejos), in the Almadén mercury mining district (South Central Spain), were collected. Altogether, 14 samples were analyzed to determine the variation in mercury emission flux (MEF) versus distance from the sources, regulating two major environmental parameters comprising soil temperature and solar radiation. In addition, the fraction of the water-soluble mercury in these samples was determined in order to assess how MEF from soil is related to the mercury in the aqueous soil phase. Measured MEFs ranged from less than 140 to over 10,000 ng m(-2) h(-1), with the highest emissions from contaminated soils adjacent to point sources. A significant decrease of MEF was then observed with increasing distance from these sites. Strong positive effects of both temperature and solar radiation on MEF was observed. Moreover, MEF was found to occur more easily in soils with higher proportions of soluble mercury compared to soils where cinnabar prevails. Based on the calculated Hg emission rates and with the support of geographical information system (GIS) tools and ISC AERMOD software, dispersion models for atmospheric mercury were implemented. In this way, the gaseous mercury plume generated by the soil-originated emissions at different seasons was modeled. Modeling efforts revealed that much higher emissions and larger mercury plumes are generated in dry and warm periods (summer), while the plume is smaller and associated with lower concentrations of atmospheric mercury during colder periods with higher wind activity (fall). Based on the calculated emissions and the model implementation, yearly emissions from the "Cerco Metalúrgico de Almadenejos" decommissioned metallurgical precinct were estimated at 16.4 kg Hg y(-1), with significant differences between seasons.     

Polycyclic aromatic hydrocarbons study in atmospheric fine and coarse particles using diagnostic ratios and receptor model in urban/industrial region

Atmospheric fine and coarse particles were collected in Teflon filters in three cities of the region of the Lower Sinos River Basin of Rio Grande do Sul in the year 2010. The filters were Soxhlet extracted, and 14 priority PAHs were analyzed using a gas chromatograph coupled to a mass spectrometer (GC/MS). The principal emission sources of these compounds were assessed by using diagnostic ratios and receptor model: positive matrix factorization (PMF 3.0) of the US Environmental Protection Agency. The results of PAHs concentration for the studied year showed significant levels of high molecular weight (HMW) PAH, Ind, and BghiP, in PM_2.5 in the winter season, showing the influence of mobile sources. The application of receptor model PMF 3.0 revealed that the main sources of PAHs were vehicle fleet (both diesel and gasoline), followed by coal combustion, wood combustion, and resuspension of dust. The results of the receptor modeling are in agreement with the data obtained by the ratio diagnostic.     

PCDDs, PCDFs, dioxin-like PCBs and indicator PCBs in soil from five selected areas in Slovakia

There is a lack of information regarding persistent organic pollutants (POPs) in soil from Slovakia. This paper reports the concentrations of 17 polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), 12 dioxin-like polychlorinated biphenyls (dl-PCBs) and 6 indicator PCBs associated with 32 soil samples collected in 2007 from areas in the vicinity up to several kilometres from four selected industrial PCDD/F sources in Slovakia and one background area.The results show that the total WHO₁₉₉₈-PCDD/F/dl-PCB-TEQ concentrations varied from 0.34 to 18.05 pg g⁻¹ dry weight (dw) and the average total TEQ concentrations in samples collected at the Šala, Košice, Krompachy and Dubová areas were 3.18, 2.64, 7.80, and 3.19 pg g⁻¹ dw respectively. The average of the total WHO₁₉₉₈-TEQ values in three soil samples representing the background Starina area was 0.66 pg g⁻¹ dw. The predominant contaminants among 2,3,7,8-substituted PCDD/Fs, dl-PCB, and indicator PCBs was OCDD, PCB 118, and PCB 153 respectively. The major contributors to the TEQ were 2,3,4,7,8-PeCDF, PCB 126, 1,2,3,7,8-PeCDD, PCB 156 and 1,2,3,4,7,8-HxCDF + 1,2,3,4,7,9-HxCDF in descending order.