Dissolved antimony concentrations in contrasted watersheds: the importance of lithogenic origin

A large series of data on dissolved antimony concentrations (900 values) from the hydrological network of Canton Geneva, Switzerland, has been statistically analysed. Data were collected from 90 sampling sites over 12 years. The watercourses surveyed (178 km) accounted for 73% of the total network. Previous studies have classified these rivers as belonging to three clearly-differentiated lithogenic zones: Alps (rivers draining crystalline regions), Jura (rivers draining carbonate-rich zones) and Plain (rivers draining molasses derived from the Alps). Antimony concentrations in the different river waters have been found to be significantly dependent on the geological characteristics of the drainage basins (median values: 0.13, 0.08 and 0.16 microg L(-1) for Alps, Jura and Plain, respectively). For antimony, it is thus possible to define background levels of the element adapted to the lithogenic characteristics for a system of interest. Since establishing background levels is an unavoidable preliminary step in any study aiming to identify and evaluate the various sources of pollution, the behaviour described here has undeniable implications for environmental surveys.     

Critical appraisal of available thermodynamic data for the complexation of antimony(III) and antimony(V) by low molecular mass organic ligands

Antimony is an element of increasing environmental significance but one whose chemical speciation has received little attention and, until recently, one which had not been modelled in any comprehensive way. This paper reports thermodynamic data for computer speciation models of antimony in aqueous, multicomponent solutions of environmental and biological interest involving low molecular mass organic ligands. The available data have been critically evaluated and entered into a thermodynamic database. The JESS suite of computer programs has been used to develop the thermodynamically-consistent mass balance equations used for modelling purposes. No data could be found for Sb(V) complexes and only a few of the existing data for Sb(III) complexes can be considered as being reliably described.     

Observations on the measurement of total antimony and antimony species in algae, plant and animal tissues

This paper describes our experiences with undertaking measurements of total antimony and antimony speciation in algae, plant and animal tissues. Digestion with nitric acid alone is suitable to release antimony from animal tissues. When organisms have high silica contents, e.g. some plants and algae, the addition of tetrafluorboric acid is required to dissolve silica as some antimony is retained by silica in extracts. Antimony in digested extracts is present as Sb5+ and hydride generation procedures can be used to determine total antimony concentrations, as total antimony in extracts will not be under estimated. Relatively non-aggressive solvents such as water, dilute nitric acid, sodium hydroxide and enzymes remove highly variable amounts of antimony (2-84%) from algae, plant and animal tissues. Addition of Sb3+ and Sb5+ to NIST CRM 1572 Citrus Leaves, pre- and post-extraction with water showed that Sb3+ is oxidised to Sb5+ while Sb5+ is redistributed amongst binding sites giving rise to artefacts. DOLT-2 and algae extracts indicated the presence of only inorganic antimony. A moss sample had inorganic antimony and a number of unknown antimony species in extracts. Future studies should explore the nature of the binding of antimony in tissues as solvents commonly used to extract metals and metalloids from algae, plant and animal tissues are not appropriate.     

A passive sampler for hydrogen sulfide

The silver nitrate/fluorescein mercuric acetate fluorimetric method for the measurement of atmospheric hydrogen sulfide has been adapted to passive sampling. Standard samplers have been tested and used in both indoor and outdoor environments. Sampler performance was not dependent on construction materials or sunlight intensity and gave similar results to active sampling. Two case studies were carried out, one in the Horniman Museum and its associated storage and study building, London, UK, and the other in the vicinity of a pulp and paper mill and geothermal area North Island, New Zealand. The detection limit of the samplers (50 ppt average for a one-week exposure) provides the opportunity to make measurements in a variety of locations provided exposure times are sufficiently long, i.e., up to one month in areas of low hydrogen sulfide concentration.     

原子荧光法和电感耦合等离子体质谱法测定水中锑的比较

分别用原子荧光法(AFS)和电感耦合等离子体质谱法(ICP-MS)测定水中锑。AFS法和ICP-MS法均线性良好,相关系数分别为0.999 8和0.999 9,检出限分别为0.17和0.03μg/L,相对标准偏差均1.15%,加标回收率分别为96.6%~111.9%和95.4%~111.5%,2种方法均能很好地用于水中锑的测定。其中,ICP-MS法适合较清洁地表水和地下水样品中锑的分析,AFS法则对地表水、地下水和废水样品均适用。     

Diffusive Sampling of Volatile Organic Compounds in Ambient Air

The Building Research Establishment (BRE) has been using diffusive samplers for the study of VOCs in indoor and outdoor air since 1989. The Perkin Elmer type sampler packed with Tenax TA adsorbent is used for the diffusive sampling of C6-C16 organic compounds. This method was applied in a major study of relationships between the environment and child health carried out during 1990-1993 in the Avon area of the UK. The present paper reports results of an investigation into the repeatability of the sampler in outdoor air and measurements of 6 aromatic hydrocarbons inside and outside a home over a 5 year period and inside and outside an office building over a 12 month period. Both the home and the office were located in Hertfordshire, England. Concentrations of VOCs recorded are similar to those found in the Avon area. Higher concentrations of each of the six compounds were recorded inside the home than outside, whilst greater amounts of benzene and toluene were found inside the office than outside. Seasonal variations in concentrations are observed and measurements recorded outdoors are similar to those recorded by other workers.     

Investigation into antimony mobility in sewage sludge fermentation

Antimony is distributed in the environment in inorganic and organic species with different solubility and mobility characters. Here we investigate the transformation of antimony in view of biomethylation during sewage sludge fermentation as a case study for an anaerobic environment. Our approach was to identify if antimony methylation follows the Challenger pathway by using isotopically enriched antimonite (123Sb(v)). The antimony source was subjected to methylation in sewage sludge, an anaerobic dominant methanogenic Archaea community. The antimony species were determined in the gas phase using cryotrapping (CT)-GC-ICP-MS, and in the medium (sewage slude) by hydride generation (HG) prior CT-GC-ICP-MS. The determined 123/121Sb isotope ratios in the volatile trimethylstibine and non-volatile methylantimony species indicated that the methylation follows the proposed methylation pathway. With this approach we were able to quantify 123Sb incorporation into monomethyl-, dimethyl- and trimethylantimony, respectively. The incorporation decreased with further methylation from 91% to 82% and 73%. Volatilisation as trimethystibine was generally lower than 0.1%, however, up to 0.8% of added antimony was found methylated to methylantimony species and mainly accumulated in the cell. Moreover, antimony biomethylation was enhanced by stimulation of the anaerobic communities of methanogenic Archaea and sulfate reducing bacteria (SRB), with the methanogens showing a higher activity.     

Molybdenum distributions and variability in drinking water from England and Wales

An investigation has been carried out of molybdenum in drinking water from a selection of public supply sources and domestic taps across England and Wales. This was to assess concentrations in relation to the World Health Organization (WHO) health-based value for Mo in drinking water of 70 μg/l and the decision to remove the element from the list of formal guideline values. Samples of treated drinking water from 12 water supply works were monitored up to four times over an 18-month period, and 24 domestic taps were sampled from three of their supply areas. Significant (p?p?>?0.05) were detected. Tap water samples collected from three towns (North Wales, the English Midlands, and South East England) supplied uniquely by upland reservoir water, river water, and Chalk groundwater, respectively, also showed a remarkable uniformity in Mo concentrations at each location. Within each, the variability was very small between houses (old and new), between pre-flush and post-flush samples, and between the tap water and respective source water samples. The results indicate that water distribution pipework has a negligible effect on supplied tap water Mo concentrations. The findings contrast with those for Cu, Zn, Ni, Pb, and Cd, which showed significant differences (p?England and Wales.     

Measurement of total antimony and antimony species in mine contaminated soils by ICPMS and HPLC-ICPMS

This paper describes the measurement of total antimony and antimony species in "real world" mine contaminated sediments using ICPMS and HPLC-ICPMS. Low and high temperature microwave extraction procedures (90 degrees C and 150 degrees C, respectively) using a range of nitric-hydrochloric acid combinations were examined as to their efficacy to extract antimony from six mine contaminated soils and a certified reference material. The use of the higher temperature with nitric-hydrochloric acid (1:2 (v/v)) was suitable to release antimony from sediments and the certified reference material, NIST 2710 Montana soil. Antimony concentrations obtained using this acid mixture were similar to those obtained using a more aggressive extraction with nitric, hydrochloric, perchloric and hydrofluoric acid mixture. A 25 mM citric acid solution at 90 degrees C for 15 min extracted 47-78% of antimony from soils. A Hamilton PRP X-100 anion exchange column with 20 mM EDTA mobile phase, pH 4.5, flow rate 1.5 mL min(-1) and column temperature of 50 degrees C was used to separate antimony species. Column recoveries ranged from 78-104%. The predominant form of antimony was Sb(5+). Little conversion of Sb(5+) occurred (<5%) during extraction, however, significant conversion of Sb(3+) occurred (approximately 36%). The extraction of antimony species with citric acid should be useful in the determination of inorganic antimony available to plants, as plants commonly excrete carboxylic acids, including citric acid, into their rhizospheres to mobilise trace elements for nutritional purposes.     

Organophosphorus flame retardants and plasticizers in air from various indoor environments

Eleven organophosphorus compounds (OPs) that are used as plasticizers and flame retardants were analysed in duplicate samples of indoor air from 17 domestic and occupational environments. Solid-phase extraction (SPE) columns were used as adsorbents and analysis was performed using GC with a nitrogen phosphorus selective detector. The total amounts of OPs in the air samples ranged between 36 and 950 ng m(-3); tris(chloropropyl) phosphate (TCPP) and tris(2-chloroethyl) phosphate (TCEP) being the most abundant (0.4 to 730 ng m(-3)), followed by tributyl phosphate (0.5-120 ng m(-3)). Public buildings tended to have about 3-4 times higher levels of OPs than domestic buildings. The relative amounts of individual OPs varied between the sites and generally reflected the building materials, furniture and consumer products used in the sampled environments. Potential sources of these compounds include, inter alia, acoustic ceilings, upholstered furniture, wall coverings, floor polish and polyvinylchloride floor coverings. A correlation was observed between the TCEP concentrations in the air in the sampled environments and previously reported concentrations in dust, but no such correlation was seen for the heavier and less volatile tris(2-butoxyethyl) phosphate (TBEP). Based on estimated amounts of indoor air inhaled and dust ingested, adults and children in the sampled environments would be exposed to up to 5.8 microg kg(-1) day(-1) and 57 microg kg(-1) day(-1) total OPs, respectively.     

An observational case study of ozone and precursors inflow to South East England during an anticyclone

Summertime photochemical air pollution episodes within the United Kingdom have been proposed via modelling studies to be strongly influenced by regional scale inflow of air from the continental European boundary layer. We present a vertically resolved case study using measurements made from the NERC/Met Office BAe 146 research aircraft on 18th August 2005 over the South East of England and the North Sea during a weak anticyclone centred over Northern Europe. The vertical distribution of ozone, CO, NO(x), peroxyacetyl nitrate (PAN) and a wide range of both nonmethane hydrocarbons (NMHC) and oxygenated volatile organic compounds (OVOCs) were determined between 500 ft (approximately 152 m) and 7000 ft (approximately 2134 m) over the East Anglia coastline and 50 km inland. In excess of 80 ppbV ozone was observed within inflowing boundary layer air over the North Sea coast in a broad N-S sloping feature around 60 km wide. The inflowing feature of European origin was also observed further inland within the boundary layer albeit with lower, more variable, ozone mixing ratios. The increased variability in ozone over land was a product of titration by fresh surface emissions of NO via rapid upward transport in thermals, a hypothesis supported by the observed vertical wind speed component. Fast boundary layer mixing over land was further illustrated by a uniform distribution in reactive alkenes. A comparison between aircraft and surface O(3) UK AUN (Automatic Urban Network) measurements showed good agreement with the inland site, Sibton, but marked differences with the coastal monitoring site at Weybourne, potentially due to gradients established by ocean deposition in stably stratified marine air.     

Determination of antimony in human blood with inductively coupled plasma-mass spectrometry

A method is presented for the determination of antimony in whole human blood samples with an ICP-MS instrument using a quadrupole mass analyzer. A nitric acid/hydrogen peroxide open digestion procedure was employed for the blood sample treatment and preparation for analysis. The precision and accuracy of the method were evaluated by analyzing several Seronorm trace elements whole blood reference materials. The precision of the method at various antimony levels was better than 4% RSD and the recovery was greater than 92% at all levels. The detection limit, calculated as three times the standard deviation of the blank (3sigma, n= 12), was 0.03 microg L(-1). The method was successfully applied for the determination of antimony in blood samples from school children in rural areas of Kwazulu/Natal, South Africa and adults from Dearborn, Michigan. Blood antimony levels ranged from <0.03 to 3.82 microg L(-1) in children and 1.40 to 4.35 microg L(-1) for adults.     

Chrysotile asbestos exposure in the manufacturing of thermal insulating boards

Exposure to asbestos fibers has been extensively studied in milling, mining of asbestos fibers, and in industries manufacturing asbestos—cement sheets, pipes, etc. However, very few studies have been reported in asbestos textiles, brake lining workers, and insulation products. In the present investigation, chrysotile exposure monitoring was carried out in a small thermal insulating boards manufacturing facility. Twenty-eight samples were analyzed from various locations like feeding of raw materials, weighing, pressing, machine grinding, and hand finishing of final products. Twenty-five percent of the samples were found to be above ACGIH TLV of 0.1 fibers per milliliter. However, mean fiber concentrations were found to be lower than 0.1 fibers per milliliter, except for the process of feeding of raw materials where the mean fiber concentration was 0.1087 ± 0.0631 fibers per milliliter.     

Behaviors of dissolved antimony in the Yangtze River Estuary and its adjacent waters

Antimony is a naturally occurring and cumulatively toxic element. With increasing concern as an inorganic contaminant, research on its environmental behavior is becoming a necessity. However, very little is known about this element. To further understand its biogeochemical behaviors and roles in the ecosystem, the main species of dissolved inorganic antimony (Sb(iii) and Sb(v)) in Yangtze River Estuary and its adjacent waters were determined by hydride generation and atomic fluorescence (HG-AFS) in our study. Results show that in surface water, the concentration for Sb(iii) and Sb(v) were in the range 0.029 μg L(-1)～ 0.736 μg L(-1) and 0.121 μg L(-1)～ 2.567 μg L(-1), with averages of 0.152 μg L(-1) and 0.592 μg L(-1), respectively. While concentrations of Sb(iii) and Sb(v) in the bottom layer were much lower, ranging from 0.023 μg L(-1) to 0.116 μg L(-1) (average of 0.050 μg L(-1)) and from 0.047 μg L(-1) to 0.441 μg L(-1) (average of 0.194 μg L(-1)), respectively. Data analysis further demonstrates that the major processes controlling antimony geochemistry in the area are riverine input, atmospheric deposition, incursion of Taiwan Warm Current, and release from particulate phase. The surface-enrichment and bottom-depletion depth profile reveals it does appear as a mildly scavenged element but is less like arsenic than previously believed. Sb(v) was the predominant speciation in aquatic environment of our research, and Sb(iii) was a minor constituent of the total antimony. Regarding the adsorption-desorption process onto SPM, Sb(iii) has a higher affinity to particulate phase than Sb(v). Furthermore, the significant correlation between antimony and nutrients indicates it is an element with great biological potential, which is also an important behavior for antimony.     

Soil Aquifer Treatment (SAT) as a Natural and Sustainable Wastewater Reclamation/Reuse Technology: Fate of Wastewater Effluent Organic Matter (EfOM) and Trace Organic Compounds

Through the use of innovative analytical tools, the removal/transformation of wastewater effluent organic matter (EfOM) have been tracked through soil aquifer treatment (SAT). While the total amount of EfOM is significantly reduced by SAT, there are trends of shorter term versus longer term removals of specific EfOM fractions. The preferential removal of non-humic components (e.g., proteins, polysaccharides) of EfOM occurs over shorter travel times/distances while humic components (i.e., humic substances) are removed over longer travel times/distances, with the removal of both by sustainable biodegradation. Dissolved organic nitrogen (DON), a surrogate for protein-like EfOM, is also effectively removed over shorter term SAT. There is some background humic-like natural organic matter (NOM), associated with the drinking water source within the watershed, that persists through SAT. While most effluent-derived trace organic compounds are removed to varying degrees as a function of travel time and redox conditions, a few persist even through longer term SAT.     

Desertification of subtropical thicket in the Eastern Cape,South Africa: Are there alternatives?

The Eastern Cape Subtropical Thicket (ECST) froms the transition between forest, semiarid karroid shrublands, and grassland in the Eastern Cape, South Africa. Undegraded ECST forms an impenetrable, spiny thicket up to 3 m high consisting of a wealth of growth forms, including evergreen plants, succulent and deciduous shrubs, lianas, grasses, and geophytes. The thicket dynamics are not well understood, but elephants may have been important browsers and patch disturbance agents. These semiarid thickets have been subjected to intensive grazing by domestic ungulates, which have largely replaced indigenous herbivores over the last 2 centuries. Overgrazing has extensively degraded vegetation, resulting in the loss of phytomass and plant species and the replacement of perennials by annuals. Coupled with these changes are alterations of soil structure and secondary productivity. This rangeland degradation has largely been attributed to pastoralism with domestic herbivores. The impact of indigenous herbivores differs in scale, intensity, and nature from that of domestic ungulates. Further degradation of the ECST may be limited by alternative management strategies, including the use of wildlife for meat production and ecotourism. Producing meat from wildlife earns less income than from domestic herbivores but is ecologically sustainable. The financial benefits of game use can be improved by developing expertise, technology, and marketing. Ecotourism is not well developed in the Eastern Cape although the Addo Elephant National Park is a financial success and provides considerable employment benefits within an ecologically sustainable system. The density of black rhinoceros and elephant in these thickets is among the highest in Africa, with high population growth and the lowest poaching risk. The financial and ecological viability of ecotourism and the conservation status of these two species warrant expanding ecotourism in the Eastern Cape, thereby reducing the probability of further degradation of ECST.     

Modelling the Transport of Oil–Mineral-Aggregates (OMAs) in the Marine Environment and Assessment of Their Potential Risks

Spilled oil can interact with suspended particles in marine environments and form oil–mineral aggregates (OMAs). Some OMAs with densities higher than seawater density can settle to the seedbed to pose potential risks to benthic organisms. To understand the transport and fate of oil associated with OMAs and evaluate their potential risks, an integrated hydrodynamic and fate/transport model has been used in a hypothetical case study of 1,000 tonnes of South Louisiana oil spilled in the Bristol Channel. Several scenarios have been simulated under different wave and current conditions. By using OMA properties derived from laboratory measurements reported in literature, it has been found that the risk to the benthos is unlikely for the two hypothetical cases with strong currents, but it is likely for the wave only (weak current) case. The effects of other factors such as OMA properties and sediment concentration were also examined in terms of their effects on the transport process and risks.     

Assessing the risk to firefighters from chemical vapors and gases during vehicle fire suppression

Despite the frequent occurrence of vehicle fires, very few studies investigating firefighters' potential inhalation exposures during vehicle fire suppression have been conducted. In this paper, we present an assessment of firefighters' health risk from vehicle fire suppression that accounts for the mixture of gases and vapors likely to be found in these fires. Summa canisters were used to collect emissions from the engine and cabin fires of a single vehicle and were analyzed for 75 volatile organic compounds (VOCs). Firefighters' breathing zone concentrations (BZCs) of aromatic hydrocarbons, aldehydes, isocyanates, and carbon monoxide were measured during the suppression of three vehicle fires. The Summa canister and BZC data were used to develop a simple model for predicting BZCs for the compounds that were not measured in the firefighters' breathing zones. Hazard quotients (HQs) were calculated by dividing the predicted and measured BZCs by the most conservative short-term exposure limits (STELs) or ceiling limits. Hazard indices (HIs) were determined by adding HQs for compounds grouped by the target organ for acute health effects. Any HIs above unity represented unacceptable risks. According to this mixture analysis, the estimated 95(th) percentile of the exposure distribution for the study population represents ≥ 9.2 times the acceptable level of risk to the respiratory tract and eyes. Furthermore, chemicals known or reasonably anticipated to be human carcinogens contributed to > 45% of these HIs. While STELs are not usually based on carcinogenicity, maintaining exposures below STELs may protect individuals from the biological stress that could result from short-term exposures to carcinogens over time. Although vehicle fires are suppressed quickly (<10 min), this assessment suggests that firefighters have the potential to be overexposed to acute toxins during vehicle fire suppression and should therefore wear self-contained breathing apparatus at all times during vehicle fire response.     

Increasing atmospheric antimony contamination in the northern hemisphere: snow and ice evidence from Devon Island, Arctic Canada

Adopting recently developed clean laboratory techniques, antimony (Sb) and scandium (Sc) deposition were measured in a 63.72 m-long ice core (1842-1996) and a 5 m deep snow pit (1994-2004) collected on Devon Island, Canadian High Arctic. Antimony concentrations ranged from 0.07 to 108 pg g(-1) with a median of 0.98 pg g(-1)(N= 510). Scandium, used as a conservative reference element, revealed that dust inputs were effectively constant during the last 160 years. The atmospheric Sb signal preserved in the ice core reflects contamination from industrialisation, the economic boom which followed WWII, as well as the comparatively recent introduction of flue gas filter technologies and emission reduction efforts. Natural contributions to the total Sb inventory are negligible, meaning that anthropogenic emissions have dominated atmospheric Sb deposition throughout the entire period. The seasonal resolution of the snow pit showed that aerosols deposited during the Arctic winter, when air masses are derived mainly from Eurasia, show the greatest Sb concentrations. Deposition during summer, when air masses come mainly from North America, is still enriched in Sb, but less so. Snow and ice provide unambiguous evidence that enrichments of Sb in Arctic air have increased 50% during the past three decades, with two-thirds being deposited during winter. Most Sb is produced in Asia, primarily from Sb sulfides such as stibnite (Sb2S3), but also as a by-product of lead and copper smelting. In addition there is a growing worldwide use of Sb in automobile brake pads, plastics and flame retardants. In contrast to Pb which has gone into decline during the same interval because of the gradual elimination of gasoline lead additives, the enrichments of Sb have been increasing and today clearly exceed those of Pb. Given that the toxicity of Sb is comparable to that of Pb, Sb has now replaced Pb in the rank of potentially toxic trace metals in the Arctic atmosphere.     

Concentrations, distributions and critical level exceedance assessment of SO2, NO2 and O3 in South Africa

South Africa has been identified as a source of industrial pollution that is significant at a global scale. This study was designed to provide quantitative information, by direct measurement, across northeastern South Africa, which includes the highly industrialised Mpumalanga Highveld. The specific aim of the study was to evaluate whether or not acidic atmospheric pollution poses a threat to soils, plants and water bodies of South Africa. To address this aim, a network of 37 passive sampling sites was established to measure monthly mean concentrations of near-surface SO₂, NO₂ and ozone. The area covered extended over the northern and eastern interior of South Africa while avoiding sources of local emissions such as towns, mines and highways. The field campaign was conducted between August 2005 and September 2007. Spatial distributions and temporal trends for these pollutant gases were assessed. Critical levels analysis comparisons were made against applicable air quality standards, guidelines and limits to evaluate the potential for adverse atmospheric pollution impacts on regional environments. The assessment indicates that only in the central source area of the South African industrial Highveld are some levels exceeded. In remote areas, including the sensitive forested regions of the Drakensberg escarpment, pollutant concentrations are below the critical thresholds for environmental damage.