The effect of heavy metal speciation in sediment on bioavailability to tubificid worms

The bioavailability of heavy metals in sediment to freshwater tubificid worms was compared with measures of chemical extractability using a sequential extraction procedure. In order to provide a range of test sediments of different quality, various mineral phases were prepared, in which the metals were spiked by adsorption or coprecipitation and these were then mixed with a bulk base sediment in known proportions. Results indicated good correlation between worm metal burden and metal mobilised from the sediments in the first (exchangeable) sequential extraction step for Cd, Cu and Pb. Of the other metals tested, Zn levels in the worms were found to be constant, suggesting regulation, and Ni uptake was too small for accurate measurement. In general, metals spiked to the sediment directly, or adsorbed on the clay mineral phase were found to be much more available than those bound to sewage sludge, carbonate or hydrous ferric oxide phases.     

Toxicity and speciation analysis of organotin compounds

Abstract

The use of antifouling paints in shipbuilding has led to a significant concentration of organotin compounds in the marine environment. Antifouling paints have become the main source of tributyltin and triphenyltin derivatives loaded into the sea. The toxicity of organotin compounds has been of great concern. High concentrations of organotin compounds are associated with growth abnormalities in mussels and oysters and have also resulted to the decline in their abundance. High concentration of organotin compounds have also been found in the tissues of marine mammals and its presence has been linked to mass mortalities of marine mammals. It causes imposex and calcification anomalities in mollusks. Seafood is thought to be a possible source of organotin compounds in human. Therefore, to evaluate the environmental distribution and fate of these compounds and to determine the effectives of legal provisions adopted by a number of countries, a variety of analytical methods have been developed for the speciation of organotin compounds in the environment. A detailed review of the toxicity and chemical speciation of organotin compounds is given.     

Microbial reporters of metal bioavailability

When attempting to assess the extent and the implications of environmental pollution, it is often essential to quantify not only the total concentration of the studied contaminant but also its bioavailable fraction: higher bioavailability, often correlated with increased mobility, signifies enhanced risk but may also facilitate bioremediation. Genetically engineered microorganisms, tailored to respond by a quantifiable signal to the presence of the target chemical(s), may serve as powerful tools for bioavailability assessment. This review summarizes the current knowledge on such microbial bioreporters designed to assay metal bioavailability. Numerous bacterial metal‐sensor strains have been developed over the past 15 years, displaying very high detection sensitivities for a broad spectrum of environmentally significant metal targets. These constructs are based on the use of a relatively small number of gene promoters as the sensing elements, and an even smaller selection of molecular reporter systems; they comprise a potentially useful panel of tools for simple and cost‐effective determination of the bioavailability of heavy metals in the environment, and for the quantification of the non‐bioavailable fraction of the pollutant. In spite of their inherent advantages, however, these tools have not yet been put to actual use in the evaluation of metal bioavailability in a real environmental remediation scheme. For this to happen, acceptance by regulatory authorities is essential, as is a standardization of assay conditions.     

Influence of Pak choi plant cultivation on Se distribution,speciation and bioavailability in soil

Background and aims

The combination of plant breeding and agronomic biofortification is the most reasonable approach to minimize zinc (Zn) deficiency-related problems in humans, but also in crop production. However, its efficiency and suitability under Mediterranean conditions and its effects on the grain yield and quality parameters are not well known.

Methods

Field experiments were conducted over two years in south-eastern Portugal, where soils are deficient in Zn. Ten advanced breeding lines and three commercial varieties of bread-making wheat were fertilized with four Zn treatments as following: i) control, ii) soil Zn application, iii) foliar Zn application and iv) both soil and foliar Zn application.

Results

Low rainfall produced 46 % more of grain Zn concentration but about 67 % less of grain yield. Grain Zn concentration varied greatly across treatments and cultivars with INIAV-1, INIAV-6, INIAV-9 and the commercial varieties being the most efficient. There were no significant increases in Zn concentrations due to soil Zn application, but gains higher than 20 mg kg^?1 were obtained both with foliar and soil+foliar Zn applications. Grain yield was not significantly higher in foliar application, but increased to about 10 % in soil, and about 7 % in soil+foliar applications, respectively.

Conclusions

In soils with low Zn availability, the best strategy to improve grain Zn concentrations has been to select the most efficient cultivars for Zn accumulation with the added application of Zn in soil+foliar form.

     

Chemical speciation in wound fluid leading to enhanced bioavailability for healing

ABSTRACT

ECCLES computer modelling is used to speciate Ca²⁺, Zn²⁺, Cu²⁺, Mn²⁺ and Fe³⁺ in wound fluid samples analysed for total metal content using Potentiometric stripping analysis. Bioavailability of metals, related to lipid soluble net-neutral complexes, was assessed and found to be broadly similar to the speciation in blood plasma. These appear to be benefits worthy of clinical investigation of keeping the wound fluid at pH = 6.4 and of raising the total cysteine concentration levels in wound fluid.     

鄂尔多斯地区公路沿线土壤重金属形态与生物有效性

采用TessierA连续提取法对鄂尔多斯地区公路沿线土壤重金属（Pb、Zn、Cu、Ni、Cr）化学形态进行了测定。同时对土壤pH值、重金属含量和公路绿化植物重金属（Cd、Hg、Pb、Cu、Zn、Ni、Cr、As和Se）含量进行了分析,对该区域重金属的生物有效性与潜在生态风险进行预测。结果表明：土壤重金属有效态占总量百分比的大小序列为Zn〉Pb〉Ni、Cr〉Cu,与重金属元素在绿化植物中含量大小序列Zn〉Cu〉Ni、Cr、As、Pb〉Cd〉Hg并非完全趋于一致。不同公路段土壤重金属与其不同形态存在较大的变幅。公路沿线表层土壤中重金属的有效态占其总量为G109（东胜-准格尔段）15．7％～46．1％,G210（达拉特-东胜段）8．0％-40．9％,G109（东胜-鄂托克段）9．1％～33．9％,而且以有机态和Fe—Mn氧化结合态的比例较大,为各元素有效态的主要形态特征。Cu在不同植物不同器官中的含量较高,可能在鄂尔多斯地区特定环境条件下随植物的蒸腾拉力、水分和营养盐运移的生理生态作用下使其在植物体中富集。土壤重金属Zn的有效态含量较高,而残渣态含量低,须特别注意其对区域生态系统的潜在影响。     

Effects of biochar amendments on speciation and bioavailability of heavy metals in coal-mine-contaminated soil

An incubation experiment was executed on applying biochar as a soil remediation amendment to discuss an effect of the various addition rates on the speciation and bioavailability of heavy metals in mining-contaminated soil. The result showed that the content of Cd in soil was 9.51 times higher than the Huainan soil background values. The contents of Cu, Zn and As were 2.97, 1.60 and 1.42 times the background values, respectively, and the total contents of all heavy metals were higher than the standard values of soil environment quality GB15618-1995 set by the China Ministry of Environmental Protection. Speciation analysis indicated that Cu and Cd were mainly associated with the reducible fraction, while Zn and As were dominated by the residual fraction. After biochar was added to contaminated soil, the residual fractions of heavy metals increased, while the acid-soluble fractions reduced. According to the results of CaCl₂ extraction experiment, CaCl₂-extractable concentrations of Cu, Zn, As, and Cd were observed with a biochar dosage rate of 10%, which were 57.26%, 51.37%, 6.94% and 42.04% lower than those of control soil samples, respectively, but there were no obvious changes of CaCl₂-extractable As.     

Bacterial enzyme activity and metal speciation in urban river sediments

The effects of stormwater and combined sewer overflows on receiving waters were investigated using measurements of bacterial enzyme activity and metal speciation in the sediments of five urban rivers. Free flowing urban rivers had high enzyme activity and low metal concentration in sediments, indicating a lack of contribution by stormwater sediments. More stagnant urban rivers, which tended to trap sewer-discharged sediments, were characterised by inhibited enzyme activity and high ammonium acetate- and EDTA-extractable metal concentrations. Profiles along two urban rivers showed a direct inhibition of enzyme activity at sites of stormwater and industrial discharge. Deposited sewage, from combined sewer overflows, was indicated by highly elevated enzyme activity and metal concentrations.The results of this study demonstrate that the ecologically relevant enzyme activity measurement may be a useful complement to metal speciation analysis when investigating the effects of stormwater discharges on urban rivers.     

Effect of yeast extract on speciation and bioavailability of nickel and cobalt in anaerobic bioreactors

The speciation of metals plays an important role in their bioavailability. In the case of anaerobic reactors for the treatment of wastewaters, the ubiquitous presence of sulfide leads to extensive precipitation of metals like nickel and cobalt, which are essential for the metabolism of the anaerobic microorganisms that carry out the mineralization of the pollutants present in the wastewater. In practice, nickel, cobalt, and iron are added in excessive amounts to full-scale installations. This study is concerned with the complexation of nickel and cobalt with yeast extract and its effect on the biogas production by methanogenic biomass. Adsorptive stripping voltammetry (AdSV) was used to get information about the stability and complexing capacity of the metal-yeast extract complexes formed. Nickel and cobalt form relatively strong organic complexes with yeast extract. The bioavailability of these essential metals in anaerobic batch reactors was dramatically increased by the addition of yeast extract. This is due to the formation of dissolved bioavailable complexes, which favors the dissolution of metals from their sulfides. Trace doses of yeast extract may be effective in keeping additions of essential metals to anaerobic reactors at a minimum.     

稻麦轮作下水稻土重金属形态特征及其生物有效性

在成都平原稻麦轮作下86个土样中重金属全量和各形态含量分析的基础上,采集分析相应点位上种植的主要粮食作物小麦和水稻籽粒的重金属含量,通过描述性统计分析、相关性分析及线性回归方程的模拟,研究了土壤中重金属的形态分布特征及其生物有效性。统计分析结果表明：土壤中Cr、Cu、Pb、Zn各形态含量的分配顺序为：残渣态〉有机物结合态〉铁锰氧化物结合态〉碳酸盐结合态〉可交换态,而Cd各形态含量的分配顺序为：铁锰氧化物结合态〉残渣态〉碳酸盐结合态〉有机物结合态〉可交换态。若以活性态（非残渣态含量）而论,Cd的活性最高,Cr的活性最低。除Cr外,各元素全量与各活性形态之间的关系较为密切。土壤中全Cd含量与4种活性形态Cd含量间的相关性均达极显著水平;Cu、Zn全量分别与其铁锰氧化物和有机物结合态含量,Pb全量分别与其可交换态和铁锰氧化物含量间的相关系数达显著或极显著水平。用卫生部颁布的食品中重金属限量卫生标准评价稻麦籽粒重金属累积情况,其结果表明,小麦籽粒（旱作）中的Cd、Cr、Cu、Pb分别超标14.71%、8.70%、6.50%和17.40%,而水稻籽粒（水作）仅有Pb和Cd含量超标10.90%和8.70%。不同形态重金属对水稻和小麦籽粒中重金属累积的影响效应不同,从多元线性回归方程的回归系数来看：稻一麦籽粒中Cd含量受到土壤中各活性形态Cd含量的影响。除铁锰氧化态Cd和有机物结合态Cd含量分别对小麦和水稻籽粒中Cd的累积表现出负效应外,其余均为正效应。可交换态Cu含量对稻-麦籽粒Cu累积的效应最大,其次受碳酸盐结合态Cu含量的影响。稻一麦籽粒Pb含量的累积受土壤各活性态Pb含量影响效应的差异不甚明显。稻-麦籽粒Zn含量与土壤各活性态Zn含量间无显著线性关系。     

Chemical speciation and bioavailability of lead and cadmium in an aquatic system polluted by sewage discharges

Abstract

A physico-chemical scheme encompassing anodic stripping voltammetry (ASV) as an analytical tool, and ultraviolet irradiation techniques, has been applied to determine the species of lead and cadmium in sewage polluted and unpolluted fresh-waters of a major perennial river located downstream of a metropolitan city in India. The physico-chemical and bioavailable species that have been identified and quantified include ASV-labile (bioavailable), particulate bound, total dissolved, non-labile or bound and organically bound metal. For precise and rapid assessment of the toxic bioavailable fraction, the ASV technique has been proposed as an analytical tool.

The river stretch, divided into reference, impact and recovery zones, has been monitored for any alteration in the distribution and partitioning of Pb and Cd amongst various physico-chemical forms. An attempt has been made to assess the impact of effluent discharge upon the receiving river by correlating concentrations of various metal-species with reference to the properties of the stream and drainage basin. Speciation analysis revealed complete association of Cd with particulates and a significant proportion of Pb in labile form, downstream of effluent outfall, thus an immediate toxic impact on the aquatic system may be posed.     

Trace metal bioavailability in municipal solid waste and sewage sludge composts

A sequential extraction procedure was employed to determine the soil fractions, and assess plant availability of Cr, Cu, Ni, Pb and Zn in a Glynwood silt loam amended with five rates (0, 30, 60, 120 and 240 metric tons/ha) of composted municipal solid waste (CMSW) or composted sewage sludge (CSS) cropped to oats (Avena sativa). The application of the composts tended to shift the solid phase forms of the metals away from those extractable with HNO₃ to those extractable with NaOH and EDTA. The more labile fractions (KNO₃ and H₂O extracts) of the metals typically decreased with application of CMSW and CSS. Crop dry matter increased at the 30 and 60 MT/ha CMSW rates by 142 and 152%, respectively, after which yields declined to below control values. Yields at all rates of CSS declined. The CMSW and CSS had an insignificant effect on concentrations of Cr and Pb in oat tissue, but tissue levels of Cu, Ni and Zn increased with increased rate of compost application.     

Space,sympatry and speciation

Sympatric speciation remains controversial. ‘Sympatry’ originally meant “in the same geographical area”. Recently, evolutionists have redefined ‘sympatric speciation’ non‐spatially to require panmixia (m = 0.5) between a pair of demes before onset of reproductive isolation. Although panmixia is a suitable starting point in models of speciation, it is not a useful definition of sympatry in natural populations, because it becomes virtually impossible to find or demonstrate sympatry in nature. The newer, non‐spatial definition fails to address the classical debate about whether natural selection within a geographic overlap regularly causes speciation in nature, or whether complete geographic isolation is usually required. We therefore propose a more precise spatial definition by incorporating the population genetics of dispersal (or ‘cruising range’). Sympatric speciation is considerably more likely under this spatial definition than under the demic definition, because distance itself has a powerful structuring effect, even over small spatial scales comparable to dispersal. Ecological adaptation in two‐dimensional space often acts as a ‘magic trait’ that causes pleiotropic reductions of gene flow. We provide examples from our own research.     

Endosymbiosis,cell evolution,and speciation

In 1905, the Russian biologist C. Mereschkowsky postulated that plastids (e.g., chloroplasts) are the evolutionary descendants of endosymbiotic cyanobacteria-like organisms. In 1927, I. Wallin explicitly postulated that mitochondria likewise evolved from once free-living bacteria. Here, we summarize the history of these endosymbiotic concepts to their modern-day derivative, the “serial endosymbiosis theory”, which collectively expound on the origin of eukaryotic cell organelles (plastids, mitochondria) and subsequent endosymbiotic events. Additionally, we review recent hypotheses about the origin of the nucleus. Model systems for the study of “endosymbiosis in action” are also described, and the hypothesis that symbiogenesis may contribute to the generation of new species is critically assessed with special reference to the secondary and tertiary endosymbiosis (macroevolution) of unicellular eukaryotic algae.     

Modeling speciation effects on biodegradation in mixed metal/chelate systems

A new model, CCBATCH, comprehensively couples microbially catalyzed reactions to aqueous geochemistry. The effect of aqueous speciation on biodegradation reactions and the effect of biological reactions on the concentration of chemical species (e.g. H₂CO₃, NH ₄ ⁺ , O₂) are explicitly included in CCBATCH, allowing systematic investigation of kinetically controlled biological reactions. Bulk-phase chemical speciation reactions including acid/base and complexation are modeled as thermodynamically controlled, while biological reactions are modeled as kinetically controlled. A dual-Monod kinetic formulation for biological degradation reactions is coupled with stoichiometry for the degradation reaction to predict the rate of change of all biological and chemical species affected by the biological reactions. The capability of CCBATCH to capture pH and speciation effects on biological reactions is demonstrated by a series of modeling examples for the citrate/Fe(III) system. pH controls the concentration of potentially biologically available forms of citrate. When the percentage of the degradable substrate is low due to complexation or acid/base speciation, degradation rates may be slow despite high concentrations of substrate Complexation reactions that sequester substratein non-degradable forms may prevent degradation or stopdegradation reactions prior to complete substrate utilization. The capability of CCBATCH to couple aqueous speciation changes to biodegradation reaction kinetics and stoichiometry allows prediction of these key behaviors in mixed metal/chelate systems.     

Heavy metal contamination of a mixed waste compost: Metal speciation and fate

The aims of this study were to assess changes in heavy metal availability in two contrasting feedstocks during aerobic composting, and the availability of said metals in the finished composts. A high C-to-N ratio mixed biodegradable municipal solid waste (MSW) feedstock was successfully composted on its own and in combination with green waste. Changes in heavy metal speciation throughout the composting process were studied using the modified BCR sequential extraction protocol. It was found that total Cu, Pb and Zn concentrations increased over time due to the progressive mineralization of the compost feedstock. Metals were fractionated differently within the two feedstocks, although only Cu showed significant redistribution (mostly to the oxidisable fraction) over the 5 month composting period. The MSW-derived composts performed comparably with other commercially-available composts in a series of plant growth trials. Plant metal accumulation was not influenced by the heavy metals present in the MSW-derived compost implying that they are not plant available. It is recommended that these relatively low value/quality composts may be used for remediation of acidic heavy metal contaminated sites.