A compilation of field surveys on gaseous elemental mercury (GEM) from contrasting environmental settings in Europe, South America, South Africa and China: separating fads from facts.

Mercury is transported globally in the atmosphere mostly in gaseous elemental form (GEM, [Formula: see text]), but still few worldwide studies taking into account different and contrasted environmental settings are available in a single publication. This work presents and discusses data from Argentina, Bolivia, Bosnia and Herzegovina, Brazil, Chile, China, Croatia, Finland, Italy, Russia, South Africa, Spain, Slovenia and Venezuela. We classified the information in four groups: (1) mining districts where this contaminant poses or has posed a risk for human populations and/or ecosystems; (2) cities, where the concentration of atmospheric mercury could be higher than normal due to the burning of fossil fuels and industrial activities; (3) areas with natural emissions from volcanoes; and (4) pristine areas where no anthropogenic influence was apparent. All the surveys were performed using portable LUMEX RA-915 series atomic absorption spectrometers. The results for cities fall within a low GEM concentration range that rarely exceeds 30 ng m(-3), that is, 6.6 times lower than the restrictive ATSDR threshold (200 ng m(-3)) for chronic exposure to this pollutant. We also observed this behavior in the former mercury mining districts, where few data were above 200 ng m(-3). We noted that high concentrations of GEM are localized phenomena that fade away in short distances. However, this does not imply that they do not pose a risk for those working in close proximity to the source. This is the case of the artisanal gold miners that heat the Au-Hg amalgam to vaporize mercury. In this respect, while GEM can be truly regarded as a hazard, because of possible physical-chemical transformations into other species, it is only under these localized conditions, implying exposure to high GEM concentrations, which it becomes a direct risk for humans.

Analysis of soil reference materials for vanadium(+5) species by electrothermal atomic absorption spectrometry.

Solid Certified Reference Materials (CRMs) with known vanadium(+5) content are currently not commercially available. Because of this, vanadium species have been determined in solid CRMs of soil, viz. CRM023-50, CRM024-50, CRM049-50, SQC001 and SQC0012. These CRMs are certified with only total vanadium content. Vanadium(+5) was extracted from soil reference materials with 0.1M Na(2)CO(3). The quantification of V(+5) was carried out by electrothermal atomic absorption spectrometry (ET-AAS). The concentration of V(+5) in the analyzed CRMs was found to be ranging between 3.60 and 86.0 microg g(-1). It was also found that SQC001 contains approximately 88% of vanadium as V(+5) species. Statistical evaluation of the results of the two methods by paired t-test was in good agreement at 95% level of confidence.

Speciation of Cr(VI) in environmental samples in the vicinity of the ferrochrome smelter.

The impact of ferrochrome smelter on the contamination of its environment with toxic hexavalent chromium, Cr(VI), was assessed by analyzing smelter dusts, soil, grass and tree barks. For the separation of Cr(VI) from Cr(III), solid samples were treated with 0.1M Na(2)CO(3) and filtered through hydrophilic PDVF 0.45 microm filter prior to the determination of Cr(VI) by electrothermal atomic absorption spectrometry (ET-AAS). Ferrochrome smelter dust was found to contain significant levels of Cr(VI), viz. 43.5 microg g(-1) (cyclone dust), 2710 microg g(-1) (fine dust), and 7800 microg g(-1) (slimes dust) which exceeded the maximum acceptable risk concentration (20 microg g(-1)). The concentration of Cr(VI) in environmental samples of grass (3.4+/-0.2), soil (7.7+/-0.2), and tree bark (11.8+/-1.2) collected in the vicinity of the chrome smelter were higher as compared with the same kind of samples collected from uncontaminated area. The results of the investigation show that ferrochrome smelter is a source of environmental pollution with contamination factors of Cr(VI) ranging between 10 and 50.

The leaching of vanadium(V) in soil due to the presence of atmospheric carbon dioxide and ammonia.

The natural leaching of vanadium(V) with CO2 from soil-water in the presence of ammonia, a known precursor to atmospheric aerosols, has been tested by bubbling carbon dioxide through soil suspension with varying amount of ammonia. It was found that the leaching of V(V) is enhanced in the presence of ammonia. From the results of the investigation, it could be concluded that atmospheric CO2 in the presence of ammonia (the only atmospheric gas that increases the pH of soil-water) could naturally leach V(V) from soil. Furthermore, it was also shown that the presence of (NH4)2CO3 in soil could enhance the leaching of toxic V(V) species thereby making it bioavailable for both plants and animals.

Monitoring mercury in two South African herbaria.

Mercury [Hg] emissions from old plant collections treated with mercuric chloride (HgCl(2)) may present a high health risk for staff working in certain herbaria. The present study evaluated Hg concentrations in ambient air, plant specimens and biological samples from staff working in the Pretoria National Herbarium (PRE) and the H.G.W.J. Schweickerdt Herbarium (PRU), University of Pretoria. Biological samples from a group of 15 people exposed to HgCl(2) in herbaria and a non-exposed control group of five people were studied. Additionally, plant samples from herbarium specimens treated and non-treated with HgCl(2) were analysed. Plant materials treated with HgCl(2) had persistent high concentrations of Hg in the range of 114-432 microg g(-1), whereas untreated materials were in the range of 0.20-0.45 microg g(-1). The HgCl(2)-treated plant specimens induced elevated concentrations of Hg into the herbarium rooms near storage cabinets, where up to 1 microg m(-3) of Hg was measured in the air of both herbaria. However, no significant difference in mean Hg concentrations in hair was found between herbarium workers and members of the control group, 0.46 and 0.64 microg g(-1) respectively (p0.05, Student's t-test). For both groups, Hg concentrations were lower than that indicated by the World Health Organization [WHO] for non-exposed adults, namely 2 microg g(-1). The mean concentration of total Hg in urine from the mercury-exposed herbarium group, 2.28 microg g(-1) creatinine, was significantly higher than in the control group, 1.05 microg g(-1) of creatinine. For both populations, the concentrations of Hg in their urine were below the threshold Hg values set by the WHO, i.e., 5 microg g(-1) creatinine. We concluded that there was no strong response by individual herbarium staff from long-term exposure to Hg concentrations in the range of 0.28-1.1 microg m(-3).

Electrothermal atomic absorption spectrometric determination of Cr(VI) during ferrochrome production.

The level of the generation of hexavalent chromium during ferrochrome production was checked. The concentration of Cr(VI) increases with each stage of ferrochrome production, 7070microgg(-1) being the highest concentration encountered in the last stage of production (dust). This concentration exceeds the maximum acceptable total Cr concentration per 8h by a factor of more than 1000. It was further observed that there is a higher contamination of soil by this pollutant closer to the plant than further away. The highest concentrations of Cr(VI) in soil and grass were found to be 12.7 and 4.2microgg(-1), respectively. The results of the investigation indicate that the consumption of such grass by animals do not pose any health hazard, for concentrations of the toxic Cr species are very low. Therefore, the release of emissions, including dust, during ferrochrome production, is a major contributor to occupational diseases and death to people working in ferrochrome production plant or mine.

The application of tree bark as bio-indicator for the assessment of Cr(VI) in air pollution.

The impact of a chromium smelter on pollution was evaluated by determining Cr(VI) in topsoil, grass and tree bark by electrothermal atomic absorption spectrometry (ETAAS). It was found that bark reflected the levels of air pollution better than soil and grass due to its high accumulative ability of Cr(VI). The tree bark was contaminated with Cr(VI) by a factor of 9 than in soil. It is therefore suggested that the bark be used as an indicator of air pollution for long-term exposure. The concentration of Cr(VI) in the bark was always a fraction of the total concentration of Cr and ranges between 1.6 and 3%. The method used in the preparation of samples was validated by the analysis of certified reference materials.

Electrothermal atomic absorption spectrometric determination of total and hexavalent chromium in atmospheric aerosols.

A method was developed which allow separate determination of Cr(VI) and total Cr from the same minute sample of atmospheric aerosols. Cr(VI) was leached was with 0.1M Na(2)CO(3) and the total Cr concentrations were determined after acid digestion. The method was validated by the analysis of certified reference materials, CRM 545, Mess-3 and Pacs-2 with good agreement between certified and found values. Cr concentrations in air samples taken around the chromium smelter show concentrations that exceed the maximum allowed levels in 8h with higher values closer to the smelter. The limit of detection (LOD) of the method for Cr(VI) determination in air samples was found to be 0.2 ng m(-3), i.e. lower than offered by the commonly preferred spectrophotometric and colorimetric techniques.

Speciation analysis of plants in the determination of V(V) by ETAAS.

Vanadium(IV) and vanadium(V) were easily separated from each other in the same plant sample and be determined independently by ETAAS (electrothermal atomic absorption spectrometry). This was achieved by treating the sample with 1M (NH(4))(2)HPO(4) which transfer only insoluble V(V) species into solution leaving V(IV) species in the solid part of the sample solution. V(IV) was then transferred into solution by ashing the precipitates and dissolving them in dilute acid. Statistical evaluations indicate that the sum of the concentrations of V(IV) and V(V) species is the same as the total concentration of vanadium determined by an independent method from the same plant sample at 95% level of confidence. The maximum concentrations for V(V) and total vanadium in plants around the vanadium mine were found to be 24.3 and 350mugg(-1), respectively.