Survey of inorganic arsenic in marine animals and marine certified reference materials by anion exchange high-performance liquid chromatography-inductively coupled plasma mass spectrometry

A method for the determination of inorganic arsenic in seafood samples using high-performance liquid chromatography-inductively coupled plasma mass spectrometry is described. The principle of the method relied on microwave-assisted alkaline dissolution of the sample, which at the same time oxidized arsenite [As(III)] to arsenate [As(V)], whereby inorganic arsenic could be determined as the single species As(V). Anion exchange chromatography using isocratic elution with aqueous ammonium carbonate as the mobile phase was used for the separation of As(V) from other coextracted organoarsenic compounds, including arsenobetaine. The stability of organoarsenic compounds during the sample pretreatment was investigated, and no degradation/conversion to inorganic arsenic was detected. The method was employed for the determination of inorganic arsenic in a variety of seafood samples including fish, crustaceans, bivalves, and marine mammals as well as a range of marine certified reference materials, and the results were compared to values published in the literature. For fish and marine mammals, the results were in most cases below the limit of detection. For other sample types, inorganic arsenic concentrations up to 0.060 mg kg(-)(1) were found. In all samples, the inorganic arsenic content constituted less than 1% of the total arsenic content.     

Determination of water-soluble arsenic compounds in commercial edible seaweed by LC-ICPMS

This paper reports arsenic speciation in edible seaweed (from the Galician coast, northwestern Spain) produced for human consumption. Chondrus crispus , Porphyra purpurea , Ulva rigida , Laminaria ochroleuca , Laminaria saccharina , and Undaria pinnatifida were analyzed. The study focused on arsenosugars, the most frequently occurring arsenic species in algae. As(III) and As(V) were also determined in aqueous extracts. Total arsenic in the samples was determined by microwave digestion and inductively coupled plasma mass spectrometry (ICPMS). For arsenic speciation, a water extraction especially suitable for arsenosugars was used, and the arsenic species were analyzed by liquid chromatography with both anionic and cationic exchange and ICPMS detection (LC-ICPMS). The total arsenic content of the alga samples ranged from 5.8 to 56.8 mg As kg(-1). The mass budgets obtained in the extracts (column recovery × extraction efficiency) ranged from 38 to 92% except for U. pinnatifida (4%). The following compounds were detected in the extracts: arsenite (As(III)), arsenate (As(V)), methylarsonate (MA), dimethylarsinate (DMA), sulfonate sugar (SO(3)-sug), phosphate sugar (PO(4)-sug), arsenobetaine (AB), and glycerol sugar (Gly-sug). The highest concentrations corresponded to the arsenosugars.     

Arsenic speciation in farmed Hungarian freshwater fish

Arsenic speciation analysis was carried out on freshwater farmed fish collected from an area with elevated groundwater arsenic concentrations in Hungary as well as from outside of the area (control samples). The arsenic species were determined by high-performance liquid chromatography-inductively coupled plasma mass spectrometry on methanol extracts of the muscle tissue from the fish. Catfish (Claries gariepinus) were raised in geothermal water where the average total arsenic concentrations were 167 (contaminated sites) and 15.1 ng As mL(-1) (control); they were all fed an artificial diet containing 2880 microg As kg(-1) total arsenic, mostly present as arsenobetaine. In the catfish, the accumulated total arsenic (2510-4720 microg As kg(-1)) was found mostly in the form of arsenobetaine suggesting that uptake of arsenic was dominated by their diet. Carp (Cyprinus carpio) were cultured in surface lakes with no significant arsenic pollution and had total arsenic concentrations ranging from 62 to 363 microg As kg(-1). The arsenic species found in the carp extracts differed markedly from those in the catfish in that no arsenobetaine was detected. Most samples of carp from the investigated sites contained low concentrations of As(III) (arsenite), As(V) (arsenate), MA (methylarsonate), and DMA (dimethylarsinate), and no other compounds were detected. The four individuals from the control site, however, all contained appreciable levels of oxo-arsenosugar-glycerol and oxo-arsenosugar-phosphate. Indeed, the oxo-arsenosugar-phosphate dominated the speciation pattern for these carp contributing about 75% of the sum of species. The contrast between these two freshwater aquaculture species regarding total arsenic and arsenic species has relevant toxicological aspects in terms of food safety.     

Speciation of arsenic in different types of nuts by ion chromatography-inductively coupled plasma mass spectrometry

In this work the quantitative determination and analytical speciation of arsenic were undertaken in different types of nuts, randomly purchased from local markets. The hardness of the whole nuts and high lipid content made the preparation of this material difficult for analysis. The lack of sample homogeneity caused irreproducible results. To improve the precision of analysis, arsenic was determined separately in nut oil and in the defatted sample. The lipids were extracted from the ground sample with the two portions of a mixture of chloroform and methanol (2:1). The defatted material was dried and ground again, yielding a fine powder. The nut oil was obtained by combining the two organic extracts and by evaporating the solvents. The two nut fractions were microwave digested, and total arsenic was determined by inductively coupled plasma mass spectrometry (ICP-MS). The results obtained for oils from different types of nuts showed element concentration in the range 2.9-16.9 ng g(-)(1). Lower levels of arsenic were found in defatted material (<0.1 ng g(-)(1) with the exception of Brazil nuts purchased with and without shells, 3.0 and 2.8 ng g(-)(1) respectively). For speciation analysis of arsenic in nut oils, elemental species were extracted from 2 g of oil with 12 mL of chloroform/methanol (2:1) and 8 mL of deionized water. The aqueous layer, containing polar arsenic species, was evaporated and the residue dissolved and analyzed by ion chromatography-ICP-MS. The anion exchange chromatography enabled separation of As(III), dimethylarsinic acid (DMAs(V)), monomethylarsonic acid (MMAs(V)), and As(V) within 8 min. Several types of nuts were analyzed, including walnuts, Brazil nuts, almonds, cashews, pine nuts, peanuts, pistachio nuts, and sunflower seeds. The recovery for the speciation procedure was in the range 72.7-90.6%. The primary species found in the oil extracts were As(III) and As(V). The arsenic concentration levels in these two species were 0.7-12.7 and 0.5-4.3 ng g(-)(1), respectively. The contribution of As in DMAs(V) ranged from 0.1 +/- 0.1 ng g(-)(1) in walnuts to 1.3 +/- 0.3 ng g(-)(1) in pine nuts. MMAs(V) was not detected in almonds, peanuts, pine nuts, sunflower seeds, or walnuts, and the highest concentration was found in pistachio nuts (0.5 +/- 0.2 ng g(-)(1)).     

Bioaccessibility and transport by Caco-2 cells of organoarsenical species present in seafood

Organoarsenical standards and raw and cooked seafood (DORM-2, sole, and Greenland halibut) were subjected to in vitro gastrointestinal digestion to estimate arsenic bioaccessibility (maximum soluble concentration in gastrointestinal medium). The in vitro digestion did not modify the chemical form of the organoarsenic species standards. In seafood, bioaccessibility was 67.5-100% for arsenobetaine (AB), 30% for dimethylarsinic acid (DMA), 45% for tetramethylarsonium ion (TETRA), and >50% for trimethylarsine oxide (TMAO). Cooking induced no changes in bioaccessible contents. In addition, transport by Caco-2 cells, an intestinal epithelia model, was evaluated from organoarsenical standards and DORM-2. For standards, transport ranged from 1.7% for AB to 15.5% for TETRA. In DORM-2, transport was observed for only AB (12%), with far higher efficiency than in the case of the standard solution, thus illustrating the interest of using whole foods for studying bioavailability.     

Application of HPLC-ICP-MS and HPLC-ESI-MS procedures for arsenic speciation in seaweeds

Speciation of arsenic in seaweeds was carried out using ion chromatography (IC) for separation and inductively coupled mass spectrometry (ICP-MS) for detection. The arsenic species studied were arsenite [As(III)], arsenate [As(V)], monomethylarsonic acid (MMA), dimethylarsinic acid (DMA), arsenobetaine (AsB), and arsenocholine (AsC). Chromatographic separation of all the species was achieved in <9 min in gradient elution mode using (NH(4))(2)CO(3) and methanol at pH 8.5. The outlet of the IC column was directly connected to the nebulizer of ICP-MS for the determination of arsenic. The speciation of arsenic has been carried out in several seaweed samples. A microwave-assisted extraction method was used for the extraction of arsenic species from seaweed samples. With a mixture of mobile phase A and methanol as extractant, the extraction efficiency was >84%, and the recoveries from spiked samples were in the range of 90-106%. The unknown compounds detected in different seaweeds were identified by coupling IC directly with electrospray ionization-mass spectrometry (ESI-MS). Two arsenosugars and tetramethylarsonium ion (TETRA) were identified in different seaweeds. A fat-soluble arsenolipid compound was identified in the extract of certified reference material BCR-279 Ulva lactuca when 1% HNO(3) was used as the extractant. The precision between sample replicates was >9% for all determinations. The limits of detection were in the range of 0.006-0.015 μg L(-1) for various arsenic species based on peak height.     

Arsenic Accumulation in Two Vegetables Grown in Soils Amended with Arsenic-Bearing Chicken Manures

The use of organoarsenic roxarsone as a feed additive, which is widely used as a growth promoter in animal production, has caused concern over potential negative environmental impacts. A pot experiment was conducted to investigate the growth and arsenic (As) uptake of pakchoi cabbage and tomatoes grown in a gray Fluvo-aquic soil amended with 2% As-bearing chicken manures to which 50 mg kg^?1 and 80 mg kg^?1 roxarsone were added, respectively. Arsenic accumulation factors of pakchoi cabbage were significantly greater than those of shoots of tomato. The biomass, As content, and As accumulation factors of both vegetables showed significant differences with species. The correlations between As contents and biomass of the vegetables were positive in pakchoi cabbage and negative in tomato. Arsenic accumulation was apparent in pakchoi cabbage; therefore, crop species with a potential to accumulate As, such as pakchoi cabbage, should be avoided when fertilizing with As-polluted manures due to food safety concerns.     

Demethylation of Dimethylarsinic Acid and Arsenobetaine in Different Organic Soils

Methylation and demethylation of arsenic may change substantially the toxicity and mobility of arsenic in soils. Little is known about demethylation of organic arsenic species in organic soils. We incubated dimethylarsinic acid (DMA) and arsenobetaine (AsB) in soils and aqueous soil extracts from a forest floor and fen, in order to investigate demethylation processes. Incubations were conducted at 5°C in the dark under oxic or anoxic conditions. Arsenobetaine demethylated rapidly in all soil extracts with half-lives of 3.6–12 days, estimated from first order kinetic. Demethylation of DMA was relatively slow with half-lives of 187 and 46 days in the forest floor extracts and oxic fen extracts, respectively. In comparison, DMA was stable for 100 days in anoxic fen extracts. The apparent half-lives were much shorter in soils for DMA (1.3–12.6 days) and AsB (0.5–1.9 days) than in soil extracts, suggesting also irreversible AsB and DMA adsorption to soils beside demethylation. An unknown arsenic species and DMA were detected as metabolites of AsB demethylation. The results indicate rapid demethylation of AsB probably via the pathway AsB → Dimethylarsenoylacetate → DMA, followed up by slow demethylation of DMA → monomethylarsonic acid → inorganic As species.     

Arsenic transport and transformation associated with MSMA application on a golf course green

The impact of extensively used arsenic-containing herbicides on groundwater beneath golf courses has become a topic of interest. Although currently used organoarsenicals are less toxic, their application into the environment may produce the more toxic inorganic arsenicals. The objective of this work was to understand the behavior of arsenic species in percolate water from monosodium methanearsonate (MSMA) applied golf course greens, as well as to determine the influences of root-zone media for United State Golf Association (USGA) putting green construction on arsenic retention and species conversion. The field test was established at the Fort Lauderdale Research and Education Center (FLREC), University of Florida. Percolate water was collected after MSMA application for speciation and total arsenic analyses. The results showed that the substrate composition significantly influenced arsenic mobility and arsenic species transformation in the percolate water. In comparison to uncoated sands (S) and uncoated sands and peat (S + P), naturally coated sands and peat (NS + P) showed a higher capacity of preventing arsenic from leaching into percolate water, implying that the coatings of sands with clay reduce arsenic leaching. Arsenic species transformation occurred in soil, resulting in co-occurrence of four arsenic species, arsenite (As(III)), arsenate (As(V)), monomethylarsonic acid (MMA), and dimethylarsinic acid (DMA) in percolate water. The results indicated that substrate composition can significantly affect both arsenic retention in soil and arsenic speciation in percolate water. The clay coatings on the soil particles and the addition of peat in the soil changed the arsenic bioavailability, which in turn controlled the microorganism-mediated arsenic transformation. To better explain and understand arsenic transformation and transport after applying MSMA in golf green, a conceptual model was proposed.     

土壤中砷的生物转化及砷与抗生素抗性的关联

砷是一种广泛存在于自然环境中毒性较强的类金属元素,农田生态系统中的植物(尤其水稻)很容易吸收积累土壤环境中的砷。植物中的砷沿食物链向高等动物传递,威胁人类健康。除土壤本身的理化性质外,土壤中砷的生物转化也强烈影响砷的生物有效性。目前研究发现异化砷酸盐(As(V))呼吸性还原、细胞质As(V)还原、亚砷酸盐(As(III))氧化、As(III)甲基化和有机砷的去甲基化在土壤砷的生物地球化学过程中起重要作用。随着分析化学和分子生物学技术的进步,最新研究发现土壤生物也参与了砷糖、砷糖磷脂、砷甜菜碱、砷代草丁膦、硫代砷等有机砷的合成,其中三价一甲基砷和砷代草丁膦可作为新型抗生素,但其合成机制及生态学功能有待进一步研究。本文还详细介绍了为适应复合污染环境微生物通过自身的进化对抗生素和重金属形成的四种共选择抗性机制:共抗性,交叉抗性、共调控和生物膜感应,特别提出了土壤中砷污染与抗生素抗性相关联这一新的研究方向。最后对砷生物转化和砷与抗生素共抗机制的未来研究方向做了展望。     

Surrogate measures for assessing cryptic faunal biodiversity on macroalgal-dominated subtidal reefs

A major impediment to the identification of priority areas for marine biodiversity conservation is a fundamental lack of information about the distribution of many marine species. Comprehensive species inventories for many areas currently do not exist, and performing detailed taxonomic surveys is often prohibitively expensive and time-consuming. Accordingly, there is a need to develop simple and reliable rapid-assessment techniques for mapping marine biodiversity. One potential approach is to use ‘surrogates’ that function as proxies for the distribution of other, less easily sampled, ‘cryptic’ biota. Two potential surrogates for predicting arthropod faunal biodiversity on rock subtidal reefs were investigated in this study: (1) macroalgae, and (2) faunal subsets derived by aggregating the arthropod fauna at higher taxonomic levels. Faunal and macroalgal assemblage composition was only weakly correlated across sites reflecting broad faunal responses to changes in algal structural complexity and/or common environmental gradients. This suggests that algal species composition may not be very informative in mapping patterns of faunal species distribution on reefs. Instead, the best surrogates were related (i.e. nested), subsets of the faunal assemblages such as family-level taxon richness which was found to be a good predictor of arthropod species richness at independent test sites.     

Water-soluble and lipid-soluble arsenic compounds in japanese flying squid Todarodes pacificus

Water-soluble and lipid-soluble arsenic compounds in Japanese flying squid Todarodes pacificus were analyzed. Regardless of the tissues, the major water-soluble arsenic compound was identified as arsenobetaine by LC/ESI-MS analysis, as reported for a number of marine animals. Lipid-soluble arsenic compounds were found at relatively high levels in liver and testis. LC/ESI-MS analysis of water-soluble arsenic compounds released from liver phospholipids by either chemical hydrolysis or phospholipase D hydrolysis demonstrated that the major arsenolipids are dimethylarsinic acid (DMA)-containing glycerophospholipid (phosphatidyldimethylarsinic acid) and DMA-containing sphingomyelin where the choline moiety of sphingomyelin is replaced by DMA. This is the first work to report the presence of DMA-containing phospholipids in marine invertebrates.     

Plant Colonization and Arsenic Uptake on High Arsenic Mine Wastes, New Zealand

Substrates associated with two historic gold mining sites in north Westland, New Zealand, have locally very high arsenic concentrations (commonly 10–40 wt% As). The substrates consist of iron oxyhydroxide precipitates, and processing mill residues. Waters associated with some of these substrates have high dissolved arsenic (commonly 10–50 mg/L As). Natural revegetation of these very high arsenic sites has occurred over the past 50 years, although some areas of substrate remain bare. Revegetating species include native and adventive shrubs, adventive grasses, rushes, and mosses, and native ferns. Revegetation by higher plants follows initial colonization by mosses, and some shrubs are growing directly in high-arsenic substrate. Shrubs, especially manuka (Leptospermum scoparium), gorse (Ulex europaeus), tree fuchsia (Fuchsia excorticata) and broadleaf (Griselinia littoralis) largely exclude arsenic from their shoots (<?10 mg/kg dry weight) irrespective of the As content of the substrate. Likewise, most grasses, and reeds (Juncus spp.), have only modest As contents (typically <?100 mg/kg dry weight). However, mosses growing on high-arsenic substrates have strongly elevated arsenic contents (>?0.2% dry weight). In particular, the moss Pohlia wahlenbergii acts as a hyperaccumulator, with up to 3% (dry weight) As. Antimony (Sb) contents of all plants are about one thousandth of that of arsenic, reflecting the As/Sb ratio of the substrates. Plant establishment in the high-As substrates may be locally limited by low nutrient status, rather than arsenic toxicity. The shrubs, grasses, and reeds identified in this study are arsenic tolerant and largely exclude arsenic from their shoots so that revegetation with these species, can help to isolate the high-arsenic substrates from the surface environment. These species could be used as phytostabilisation agents on high-arsenic sites that are remote from human habitation. In contrast, the mosses, despite their high arsenic tolerance, are a less desirable component of revegetation of high-arsenic substrates because they actively transfer arsenic from the substrate to the biosphere.     

吉林西部土壤砷的形态分布及其与土壤性质的关系研究

按照生态地球化学土壤样品元素形态分析方法,将土壤无机砷分成水溶态、离子交换态、碳酸盐态、腐植酸结合态、铁锰氧化物结合态、强有机结合态和残渣态。通过对吉林西部36个表层土壤样品的测试,分析了土壤不同形态砷的分布和不同形态砷与土壤性质的关系。研究表明,洮南市不同形态砷的分布为：残渣态（65．30％）〉腐植酸结合态（17．39％）〉铁锰氧化物结合态（10．70％）〉碳酸盐态（2．23％）〉水溶态（2．17％）〉强有机结合态（1．17％）〉离子交换态（1．04％）。通榆县不同形态砷的分布为：残渣态（56．66％）〉腐植酸结合态（23．82％）〉铁锰氧化物结合态（11．08％）〉碳酸盐态（2．81％）〉水溶态（2．18％）〉离子交换态（1．98％）〉强有机结合态（1．46％）。残渣态砷是吉林西部土壤砷的主要形态。土壤水溶态砷和铁锰氧化物结合态砷与土壤pH值皆呈极显著正相关;残渣态砷与土壤有机质皆呈极显著负相关,而与土壤阳离子交换量呈极显著正相关。离子交换态砷、碳酸盐态砷、铁锰氧化物结合态砷和强有机结合态砷与土壤矿质元素的关系不大,而水溶态砷、腐植酸结合态砷和残渣态砷与土壤矿质元素的关系密切。     

Quantitation of toxic arsenic species and arsenobetaine in Pacific oysters using an off-line process with hydride generation-atomic absorption spectroscopy

An off-line process-based speciation technique was devised here to quantitatively determine toxic inorganic arsenic (iAs), methylarsonic acid (MA), dimethylarsinic acid (DMA), and the dominant, albeit virtually nontoxic, arsenobetaine (AB) in Pacific oysters (Crassostrea gigas). Oysters were extracted with fresh methanol-water (8+2), and this was replicated three times. They were then evaporated to near dryness and subsequently redissolved in pure water; defatting was then performed with a C18 cartridge. The trace hydride active arsenic species, that is, iAs, MA, and DMA, in the defatted solutions were determined with a sensitive hydride generation-packed coldfinger trap-atomic absorption spectrometric (HG-PCFT-AAS) coupled system. The arsenicals that were desorbed from the cation-exchange resin (Dowex 50W-X8) in the washings of 4 M NH3 were categorized on the basis of AB + DMA. The total quantity of arsenic in the recovered AB + DMA was determined with a commercial hydride generation-atomic absorption spectrometric (HG-AAS) system, and finally, AB was calculated from (AB + DMA) - DMA. The average concentrations of iAs, MA, DMA, AB, and total arsenic (TAs) in the oysters collected from six aquacultural sites along the west coast of Taiwan were, respectively, 0.15, 0.06, 0.64, 6.93, and 13.74 mg kg(-1) of dry weight. AB was the major species, whereas iAs (arsenite + arsenate) were the most toxic species, although the iAs made up only approximately 1% of the TAs in the oysters. The lifetime target cancer risk, as determined by the concentration of iAs on a fresh weight basis in the oysters, was well below the ordinary health protection criteria (10(-6)).     

土壤中砷的形态和生物有效性研究现状与趋势

砷在自然界中分布极为广泛,与人类生活密切相关,在工农业生产活动中得到了广泛应用。但砷是高毒元素,在微量水平上就能对动植物体产生一定危害。砷的危害通过生物有效性予以表达,其生物有效性与其在土壤中的累积量及形态密切相关。本文就砷在土壤中的存在价态、与土壤胶体的结合形态、砷生物有效性及不同形态砷的测定技术与方法等方面进行了简要综述,并对未来相关领域的研究发展趋势作了展望,以期为深入开展土壤中砷形态及其生物有效性研究提供科学参考。     

Modeling of arsenic immobilization by zero valent iron

Ground waters in geothermal regions contain arsenic concentrations that exceed the recommended drinking water standards. In addition, when these regions have agricultural activities, the waters also contain high levels of nitrates and phosphates. These contaminants can be removed from the water with the use of filters containing zero valent iron (ZVI). The objective of this study was to model the removal of arsenate (As(V)) and arsenite (As(III)) by ZVI and to model the effect of competing ions (phosphate and nitrate) on arsenate removal. Arsenic immobilization by ZVI columns was simulated by the HM-1D chemical transport and speciation model and an one-dimensional analytical solution model. Laboratory column studies were conducted in order to obtain representative experimental data for simulation with both models. Arsenic speciation and the presence of competing ions greatly affect arsenic removal by ZVI. Most arsenic is precipitated/co-precipitated on ZVI and on the corrosion products formed on ZVI. The simulations suggested that As(V) process parameters are higher than the As(III) parameters and that they are affected by the presence of nitrates and phosphates in the system. Such models can be used to design treatment units by incorporating the impact of nitrates and phosphates in the removal of arsenic by ZVI as well as the impact of temperature on the process.     

Safety evaluation of organoarsenical species in edible Porphyra from the China Sea

A study was carried out to determine arsenic species in Porphyra seaweed originating from the China Sea. Information about arsenic species in Porphyra was provided by HPLC-ICP-MS and ES-MS-MS. The total arsenic concentrations of Porphyra samples from five different producing areas ranged from 2.1 to 21.6 mg/kg. The analysis report also showed that arsenosugars were the only arsenic species that could be detected in all of the extracts of samples. Arsenosugar PO(4) was the major compound in most samples (0.3-13.9 mg/kg of dry weight), followed by arsenosugar OH (0.7-6.2 mg/kg of dry weight). A further experiment was done to investigate the stability of arsenosugars in the process of being heated. It was observed that the arsenosugars were stable during a short-term heating at 100 degrees C. Their stability in human ingestion was also studied. A substantial increase of dimethylarsinic acid (DMA) was detected in urine samples collected from six volunteers after the consumption of this seaweed. The results obtained indicated that arsenosugars had been metabolized to DMA, which is more toxic than arsenosugars. From this point of view, consumers should consider the possible adverse effects of edible Porphyra on human health and choose those Porphyra having lower arsenic concentrations.     

Chemical speciation and bioavailability of Cd,Cu, Pb and Zn in Western Balkan soils

Abstract

Three thermal power plants in Serbia, Croatia and Bosnia of the Western Balkan region were expected to be metal polluting sources, and this study was performed to investigate the bioavailability and chemical speciation of trace metals in soils and soil water extracts, respectively. Surface (0–15 cm) soil samples along with maize and grass samples were collected at a gradient from the pollution source. The chemical speciation of metals was conducted using the Windereme Humic Aqueous Model (WHAM)/Model VI for water, whereas the Diffusion Gradient in Thin Films (DGT) technique was used to estimate plant availability. The chemical speciation indicated that more than 99% of all four metals in soil water extracts were complexed to fulvic acid. This is connected to relatively high soil pH (> 6.5) and high contents of soil organic matter in these soils. The accumulation of trace metals by DGT was not correlated to plant uptake. This is connected to the very low partitioning of free ions in solution, but also to the low variation in metal solubility and metal concentration in plant tissue between sites. In spite of active thermal power plants located in the areas, hardly any differences in concentration of soil metals between sites were seen and the partition of metals in soil waters was insignificant. The latter indicates that these soils have a large metal-retaining capacity. The only significant soil chemical variable affecting the variation in metal solubility was the soil pH. In a time with large infrastructure and industrial expansion in these areas, this investigation indicates the importance of protecting these high-quality soils from industrial use and degradation. High industrial activity has so far had insignificant effect on soil quality with respect to bioavailability of trace metals in these soils.     

煤基腐殖酸对土壤砷赋存形态和小白菜生长及砷吸收分布的影响

为探讨部分煤基腐殖酸性质与土壤砷有效性的关系及其在砷污染土壤修复改良中的潜在利用性和应用方向,通过小白菜盆栽试验研究了4种煤基腐殖酸对土壤砷形态和含量及小白菜生长和砷吸收分布的影响。结果表明:6号和10号煤基腐殖酸显著降低了土壤可交换态和碳酸盐结合态砷含量,从而显著降低土壤有效砷含量,抑制砷向小白菜地上部转移和积累;特别是添加10号煤基腐殖酸土壤可交换态砷含量、有效砷含量和小白菜地上部砷总量分别比As处理降低了49.18%,42.22%和15.17%。而9号和11号煤基腐殖酸增加了土壤可交换态和碳酸盐结合态砷含量,显著增加土壤有效砷含量,对小白菜吸收砷并向地上部转移也有一定促进作用,二者土壤可交换态砷含量、有效砷含量和小白菜地上部砷总量分别比As处理增加了10.58%和5.95%,31.11%和22.22%,20.81%和17.21%。4种煤基腐殖酸对小白菜生长均有一定的促进作用,总体表现为10号6号11号9号。因此,E4/E6值小、分子量大、总酸性基含量较低的6号和10号煤基腐殖酸对土壤砷具有明显的钝化作用,可用于轻度砷污染土壤治理中抑制作物对砷的吸收和向地上部转移,实现作物安全生产;而E4/E6值大、分子量小、总酸性基含量较高的9号和11号煤基腐殖酸对土壤砷具有一定的活化作用,在中度和重度砷污染土壤的植物修复中可作为活化剂强化修复速度和效果。