Arsenic in the food chains of a revegetated metalliferous mine tailings pond.

The environmental distribution, transfer and ecotoxicological risk associated with arsenic in a grassland ecosystem established on metalliferous mine tailings has been determined. High levels of arsenic in the mine tailings (630 +/- 34 mg kg-1) were not reflected in live vegetation due to the physico-chemical nature of the tailings which mitigate against plant uptake. However, elevated levels of arsenic were associated with plant litter. Low concentrations of arsenic in herbivorous invertebrates mirrored those found in their food, although there was evidence of minor detrivoral food chain transfer. Dietary exposure of small mammals to arsenic was well below that demonstrated to induce a toxicological response, and tissue concentrations were consistently below analytical detection limits. There appears to be little ecotoxicological risk associated with arsenic residues at the mine site investigated.     

Accumulation of Hg and other heavy metals in the Javan mongoose (Herpestes javanicus) captured on Amamioshima Island, Japan

Concentrations of 22 elements (Mg, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Rb, Sr, Mo, Ag, Cd, Sb, Cs, Ba, Tl, total Hg (T-Hg), Pb) and organic Hg (O-Hg) were examined in the liver, kidney and brain of the Javan mongoose (Herpestes javanicus) and in liver of the Amami rabbit (Pentalagus furnessi) from Amamioshima Island in Japan. Relatively high levels of T-Hg levels (from 1.75 to 55.5 microg g-1 wet wt.) were found in the Javan mongoose. As for a comparison of hepatic T-Hg concentrations between the two areas, there was no significant difference between the Javan mongoose in Amamioshima and those in the Okinawa islands. In addition, T-Hg levels in the livers of the Amami rabbit were the same as in the livers of other herbivorous mammals. Taken together, it suggested that T-Hg accumulation in the livers of the Javan mongoose was not affected by the environment but by a specific physiological mechanism. The comparison of Hg and other heavy metal accumulations between terrestrial mammals (13 species, 61 individuals) including the Javan mongoose and marine mammals (18 species, 508 individuals) were also discussed.     

Risk assessment of metals and organic pollutants for herbivorous and carnivorous small mammal food chains in a polluted floodplain (Biesbosch, The Netherlands)

A risk assessment was made for a carnivorous and a herbivorous food chain in a heavily polluted natural estuary (Biesbosch), by determining the most critical pollutants and the food chain most at risk. Exposure of food chains to metals, polycyclic aromatic hydrocarbons (PAHs), and polychlorinated biphenyls (PCBs) was assessed by analyzing dietary concentrations, internal concentrations, and biomarkers of exposure. Common shrew (Sorex araneus) and bank vole (Clethrionomys glareolus) were selected as representative small mammal species for the carnivorous and herbivorous food chain, respectively, and earthworms (Lumbricus rubellus) and snails (Cepaea nemoralis) as representative prey species for the carnivorous food chain. Metals contributed most to the total risk for small mammals and earthworms. PCBs, but not PAHs, contributed to the overall risk for S. araneus at regularly flooded locations. The carnivorous food chain appeared most at risk given the higher exposure levels and bioaccumulating potency found for contaminants in S. araneus.     

Antimony distribution and mobility in topsoils and plants (Cytisus striatus, Cistus ladanifer and Dittrichia viscosa) from polluted Sb-mining areas in Extremadura (Spain)

A study about topsoil antimony distribution and mobility from the soils to the biomass has been afforded in three abandoned Sb mining areas located at Extremadura. Physico-chemical characteristics of the soils and total antimony levels were measured in soils and autochthonous plant species (Cytisus striatus, Cistus ladanifer and Dittrichia viscosa). Comparison with corresponding values in reference areas isolated from the mining activities is discussed. Antimony mobility in the soils was estimated by measuring the water extractable fraction; low results were obtained for the three soil areas, with no statistical differences. Plant ability to accumulate antimony was estimated by use of plant accumulation coefficients (PAC). Seasonal (spring vs. autumn) effects on the antimony content in the plant species. Cytisus striatus from Mari Rosa mine presented antimony excluder characteristics, whereas Dittrichia viscosa specimens growing in San Antonio mine showed a significant antimony bioaccumulation.     

Immobilization of antimony waste slag by applying geopolymerization and stabilization/solidification technologies

During the processing of antimony ore by pyrometallurgical methods, a considerable amount of slag is formed. This antimony waste slag is listed by the European Union as absolutely hazardous waste with a European Waste Catalogue code of 10 08 08. Since the levels of antimony and arsenic in the leachate of the antimony waste slag are generally higher than the landfilling limits, it is necessary to treat the slag before landfilling. In this study, stabilization/solidification and geopolymerization technologies were both applied in order to limit the leaching potential of antimony and arsenic. Different combinations of pastes by using Portland cement, fly ash, clay, gypsum, and blast furnace slag were prepared as stabilization/solidification or geopolymer matrixes. Sodium silicate–sodium hydroxide solution and sodium hydroxide solution at 8 M were used as activators for geopolymer samples. Efficiencies of the combinations were evaluated in terms of leaching and unconfined compressive strength. None of the geopolymer samples prepared with the activators yielded arsenic and antimony leaching below the regulatory limit at the same time, although they yielded high unconfined compressive strength levels. On the other hand, the stabilization/solidification samples prepared by using water showed low leaching results meeting the landfilling criteria. Use of gypsum as an additive was found to be successful in immobilizing the arsenic and antimony.

ImplicationsDespite the wide use of antimony for industrial purposes, disposal options for an antimony waste such as slag from thermal processing of antimony ore were not reported in the existing literature. This study aimed to develop a disposal strategy for the hazardous antimony waste slag. The findings of this study would contribute to understand the immobilization mechanisms of antimony and arsenic and will also be of interest to the owners of the antimony ore processing plants and to researchers investigating the efficiency of stabilization/solidification and geopolymerization technologies.     

Formation of involatile methylantimony species by Clostridium spp

Trimethylantimony was detected by gas chromatography-mass spectrometry (GC-MS) in the headspace of a soil enrichment culture designed to promote growth of clostridia. Clostridial isolates from the soil enrichment culture were shown to biomethylate inorganic antimony in monseptic culture, using hydride generation-gas chromatographyatomic absorption spectrometry (HG-GC-AAS). GC-MS profiles of headspace gases from soil enrichment cultures shown to generate trimethylantimony, were used to select characterised Clostridium spp for assessment of antimony biomethylation capability. Involatile methylantimony species (up to 21 microg Sb dm(-3)) were detected by HG-GC-AAS in the medium of monoseptic cultures of C. acetobutylicum, C. butyricum and C. cochlearium. The relative quantities of involatile mono-, di- and trimethylantimony species produced over the course of a 28-day cultivation period is consistent with trimethylantimony oxide being a final product of antimony biomethylation by these bacteria, with mono- and dimethylantimony species appearing transiently in the cultures as intermediates of an antimony biomethylation pathway. Clostridia may be the principal agents of antimony biomethylation in methanogenic environments and could give rise to methylated forms of antimony in both the aqueous and gaseous phases.     

Status and dynamics of the Kobresia pygmaea ecosystem on the Tibetan plateau

This paper provides information about the distribution, structure, and ecology of the world's largest alpine ecosystem, the Kobresia pygmaea pastures in the southeastern Tibetan plateau. The environmental importance of these Cyperaceae mats derives from the extremely firm turf, which protects large surfaces against erosion, including the headwaters of the Huang He, Yangtze, Mekong, Salween, and Brahmaputra. The emphasis of the present article is on the climate-driven evolution and recent dynamics of these mats under the grazing impact of small mammals and livestock. Considering pedological analyses, radiocarbon datings, and results from exclosure experiments, we hypothesize that the majority of K. pygmaea mats are human-induced and replace forests, scrub, and taller grasslands. At present, the carrying capacity is increasingly exceeded, and reinforced settlement of nomads threatens this ecosystem especially in its drier part, where small mammals become strong competitors with livestock and the removal of the turf is irreversible. Examples of rehabilitation measures are given.     

Antimony in municipal waste.

Antimony content in municipal waste was studied. Sampled municipal waste was dried, crushed and analyzed. Antimony determinations were performed by Kjeldahl decomposition--batch hydride generation spectrometry and neutron activation analysis. Overall content of antimony in waste was 40-50 g/t raw waste. It was estimated than 20% of the annual production of antimony was discarded as municipal waste in Japan. Leaching of antimony from antimony-added materials may occur, because "small tips" involved considerable amounts of antimony.     

Evidence of recycling of lead battery waste into highly leaded jewelry

Inexpensive highly leaded jewelry, much of it imported from China, remains widely available in the United States. The source materials for these items are unknown. Due to the low cost of much of this trinket jewelry, it seems likely that scrap materials may be used in their manufacture. Thirty-nine jewelry items previously determined to contain 90% or more lead by weight were analyzed for antimony content. The average antimony content of these thirty-nine items was 3.0%. The range of antimony content in the samples was from 0.3% to 6.2% antimony by weight, with twenty-seven of the samples in the range of 2-4% antimony by weight. By comparison, battery lead standard reference material obtained from the US National Institute of Standards and Technology contains 2.95% antimony by weight. While the evidence is circumstantial, the similarity in composition of these samples to battery lead is striking and supports the hypothesis that some battery lead is being recycled into highly leaded jewelry items. These results suggest that the recycling of this waste in China needs to be investigated, as the use of lead battery waste as a source material for children's jewelry poses a clear threat to children's health.     

Organochlorine pesticides and polychlorinated biphenyl congeners in wild terrestrial mammals and birds from Chubu region, Japan: Interspecies comparison of the residue levels and compositions

In order to understand the residue levels of organochlorine compounds (OCs) and their accumulation patterns in wildlife inhabiting Chubu region, Japan, the concentrations of polychlorinated biphenyls (PCBs), hexachlorocyclohexane isomers (HCHs), DDT compounds (DDTs) and hexachlorobenzene (HCB) were measured in 8 species of terrestrial mammals and 10 species of birds. In view of feeding habits, the contamination levels of OCs were found to be higher in omnivorous mammals than in herbivorous ones, and in fish-eating ones and raptores than in omnivorous birds. In fox and dog, PCB-180 (2, 2′, 3, 4, 4′, 5, 5′-heptachlorobiphenyl) was the most dominant PCB congener, while in the other species PCB-153 (2, 2′, 4, 4′, 5, 5′-hexachlorobiphenyl) was the most persistent. The ratios of lower chlorinated PCB congeners (tri- to tetra-) to total PCBs were larger in fish-eating birds than in the other birds. The results indicate that the compositions of PCB congeners would reflect the differences of feeding habits and xenobiotic metabolizing systems among each species.     

Antimony accumulation in Achillea ageratum, Plantago lanceolata and Silene vulgaris growing in an old Sb-mining area

Preliminary data of a biogeochemical survey concerning antimony transfer from soil to plants in an abandoned Sb-mining area are presented. Achillea ageratum, Plantago lanceolata and Silene vulgaris can strongly accumulate antimony when its extractable fraction in the soil is high (139-793 mg/kg). A. ageratum accumulates in basal leaves (1367 mg/kg) and inflorescences (1105 mg/kg), P. lanceolata in roots (1150 mg/kg) and S. vulgaris in shoots (1164 mg/kg). In these plant species, the efficiency of antimony accumulation decreases when the antimony availability in the soil is high. In A. ageratum and S. vulgaris, the death of the epigeal target part at the end of the growing season contributes to a reduction of the antimony load in the plant. A study to test the use of these species as bioindicators of antimony availability in soil is suggested by our results.     

Antimony biomethylation by Scopulariopsis brevicaulis: characterization of intermediates and the methyl donor

The filamentous fungus Scopulariopsis brevicaulis biomethylates inorganic antimony(III) compounds to trimethylstibine, that can be detected in culture headspace gases. Dimethylantimony and trimethylantimony species have been detected in the medium of these cultures, but the origin of these species was controversial. We now show that the dimethylantimony species is a true intermediate on the pathway to trimethylstibine (rather than arising from trimethylstibine oxidation or as an analytical artifact) because no dimethylantimony species are formed on trimethylstibine oxidation, as determined by using HG-GC-AAS. Furthermore, the dimethylantimony and trimethylantimony species can be separated, by using anion exchange chromatography, and so the dimethylantimony species is not an analytical artifact, formed during the hydride generation process. The antimony biomethylation mechanism was further probed by measuring incorporation of the methyl group, from 13CD3-L-methionine and CD3-D-methionine, into methylantimony species and, for comparison, into methylarsenic species. The percentage incorporation of the labeled methyl group into methylarsenic and methylantimony species was not significantly different. The incorporation from 13CD3-L-methionine was 54% and 47% for antimony and arsenic, respectively. The incorporation from CD3-D-methionine was 20% and 16% for antimony and arsenic, respectively. It appears that the biomethylation of arsenic and antimony occur by very similar, perhaps identical, mechanisms.     

Distribution of antimony in contaminated grassland: 1--Vegetation and soils

Antimony concentrations in surface soils were found to decrease with increasing distance from an antimony smelter. This pattern was also found in moss bags exposed in the same area. At three sites close to the smelter, antimony concentrations in soil and vegetation were much higher than at a rural control site and published background levels. Maximum soil and plant concentrations on a dry weight basis of 1489 mg kg(-1) and 336 mg kg(-1), respectively, were found, compared to background levels of <1 mg kg(-1). Field exposure of grass in pots of uncontaminated soil and a laboratory experiment using soils from near the smelter suggested that the antimony in vegetation was largely due to continued aerial deposition and not to uptake from soil.     

Fate of antimony in municipal solid waste incineration

The average antimony concentration in municipal solid waste is estimated to be about 10-60 ppm. Thermodynamical models predict a volatile behavior for antimony compounds, yet literature mass balances show that about 50% of the antimony input remains in the grate ashes. This fact can be explained by the formation of thermally stable antimonates in the fuel bed due to interactions with alkali or earth-alkali metals. Thermogravimetric experiments revealed an increased thermal stability for antimony oxide in presence of oxygen and calcium oxide. Spiking experiments on the test incinerator TAMARA showed that chlorination processes have a strong effect on antimony volatilization whereas high fuel-bed temperatures and addition of antimony oxide only have a moderate effect. In the grate ashes, antimony shows a pH-depending leaching property, which is typical for anionic species. This fact supports the thesis that antimony is present in the grate ashes in an anionic speciation.     

铁改性海泡石除锑的影响因素研究

选择廉价海泡石, 用氯化铁对其改性。研究铁改性海泡石对锑的吸附特性。结果表明,氯化铁浓度、吸附时间、初始锑浓度以及温度等因素对锑的吸附影响较大,溶液初始pH影响不明显。在初始锑浓度50 mg/L,pH 6.8,5%氯化铁改性海泡石投加量为2 g/L,吸附90 min, 温度35℃下,吸附量可达21.6 mg/g。海泡石对吸附锑具有缓冲特性,溶液的初始pH值在3.1～10.1范围时,吸附后溶液的最终pH值为8～8.5。IMS吸附锑是放热过程。改性后海泡石比表面积增大,表面羟基数量增加,导致其吸附能力增强。通过XRD谱图并未发现铁晶体的存在。     

从含锑烟尘中制备纳米立方晶型Sb_2O_3

以含锑烟尘为原料,经脱杂处理后,采用真空蒸发法制备了立方晶型纳米三氧化二锑,并用XRD衍射和SEM扫描电镜对产物三氧化二锑进行表征。结果表明,制备的三氧化二锑为立方晶型,颗粒粒径为35~100 nm。实验考察了脱杂时间对脱杂效果的影响;考察了蒸发温度、压强、蒸发时间3个因素对三氧化二锑颗粒粒度的影响。     

Mobility of antimony in soil and its availability to plants

In a historical mining area residual material has been filled on land and these locations are used today as agricultural soils or house gardens. The antimony concentrations in these soils are up to 500 mg/kg. Antimony transfer into 19 vegetable and crop species was investigated. In grain and other storage organs up to 0.09 mg Sb/kg were found, whereas maximum antimony concentrations in shoots and leaves were determined to be 0.34 mg Sb/kg and 2.2 mg Sb/kg, respectively. Despite the high antimony contamination of the soils, concentrations in the investigated plants in general corresponded to concentrations only reported for uncontaminated soils. NH4NO3 extraction of some of the soils indicated that the mobile fraction of antimony present was only 0.06-0.59%. In contrast, in leaves of spinach grown under controlled conditions in soils with a high mobile antimony content an accumulation of the element could be observed: a maximum value of 399 mg Sb/kg was detected, and a correlation between the mobile fraction in the soils and antimony in leaves was found.     

Photo-oxidation of Sb(III) in the seawater by marine phytoplankton-transition metals-light system

The photo-oxidation of Sb(III) to Sb(V) by marine microalgae (diatom, green and red algae) with or without the presence of transition metals (Fe(III), Cu(II) and Mn(II)). The influence of marine phytoplankton on the photochemistry of antimony was confirmed for the first time. The conversion ratio of Sb(III) to Sb(V) increased with increasing algae concentration and irradiation time. Different species of marine phytoplankton were found to have different photo-oxidizing abilities. The photochemical redox of transition metals could induce the species transformation of antimony. After photo-induced oxidation by marine phytoplankton and transition metals, the ratio of Sb(V) to Sb(III) was in the range of 1.07-5.48 for six algae (Tetraselmis levis, Chlorella autotrophica, Nannochloropsis sp., Tetraselmis subcordiformis, Phaeodactylum tricornutum, and Porphyridium purpureum), and only 0.92 for Dunaliella salina. The distribution of antimony in the sunlit surface seawater was greatly affected by combined effects of marine phytoplankton (main contributor) and transition metals; both synergistic and antagonistic effects were observed. The results provided further insights into the distribution of Sb(III) and Sb(V) and the biogeochemical cycle of antimony, and have significant implications for the risk assessment of antimony in the sunlit surface seawater.     

Base cation depletion, eutrophication and acidification of species-rich grasslands in response to long-term simulated nitrogen deposition

Pollutant nitrogen deposition effects on soil and foliar element concentrations were investigated in acidic and limestone grasslands, located in one of the most nitrogen and acid rain polluted regions of the UK, using plots treated for 8-10years with 35-140kg Nha(-2)y(-1) as NH(4)NO(3). Historic data suggests both grasslands have acidified over the past 50years. Nitrogen deposition treatments caused the grassland soils to lose 23-35% of their total available bases (Ca, Mg, K, and Na) and they became acidified by 0.2-0.4 pH units. Aluminium, iron and manganese were mobilised and taken up by limestone grassland forbs and were translocated down the acid grassland soil. Mineral nitrogen availability increased in both grasslands and many species showed foliar N enrichment. This study provides the first definitive evidence that nitrogen deposition depletes base cations from grassland soils. The resulting acidification, metal mobilisation and eutrophication are implicated in driving floristic changes.     

Effect of decabromodiphenyl ether and antimony trioxide on controlled pyrolysis of high-impact polystyrene mixed with polyolefins

The controlled pyrolysis of polyethylene/polypropylene/polystyrene mixed with brominated high-impact polystyrene containing decabromodiphenyl ether as a brominated flame-retardant with antimony trioxide as a synergist was performed. The effect of decabromodiphenyl ether and antimony trioxide on the formation of its congeners and their effect on distribution of pyrolysis products were investigated. The controlled pyrolysis significantly affected the decomposition behavior and the formation of products. Analysis with gas chromatograph with electron capture detector confirmed that the bromine content was rich in step 1 (oil 1) liquid products leaving less bromine content in the step 2 (oil 2) liquid products. In the presence of antimony containing samples, the major portion of bromine was observed in the form of antimony bromide and no flame-retardant species were found in oil 1. In the presence of synergist, the step 1 and step 2 oils contain both light and heavy compounds. In the absence of synergist, the heavy compounds in step 1 oil and light compounds in step 2 oils were observed. The presence of antimony bromide was confirmed in the step 1 oils but not in step 2 oils.