Potentially toxic metals in ombrotrophic peat along a 400 km English-Scottish transect

Four samples of ombrotrophic peat were collected from each of 10 upland locations in a transect from the southern Pennines to the Highland Boundary Fault, a total distance of ca. 400 km. Bulk compositions and other properties were determined. Total contents of Al and heavy metals (Ni, Cu, Zn, Cd, Pb) were determined following digestion with hydrofluoric acid, and concentrations of metals extractable with dilute nitric acid were also measured. Supernatants obtained from aqueous extractions of the peat samples were analysed for pH, major cations and anions, dissolved organic carbon and dissolved metals, and concentrations of free metal ions (Al(3+), Ni(2+), etc.) were estimated by applying a chemical speciation model. Both total and HNO(3)-extractable metal concentrations varied along the transect, the highest values being found at locations close to industrial and former mining areas. The HNO(3)-extractable soil metal contents of Ni, Cu and Cd were appreciably lower than lowest-observed-effect-concentrations (LOEC) for toxicity towards microorganisms in acid, organic rich soils. However, the contents of Zn at two locations, and of Pb at five locations exceeded LOECs, suggesting that they may be exerting toxic effects in the peats. Soil solution concentrations of free heavy metal ions (Cu(2+), Zn(2+), Cd(2+), Pb(2+)) were substantially lower than LOECs for toxicity towards vascular plants, whereas concentrations of Al(3+) were near to toxic levels at two locations.     

Involvement of siderophores in the reduction of metal-induced inhibition of auxin synthesis in Streptomyces spp

Unlike synthetic metal chelators, microbe-assisted phytoremediation provides plants with natural metal-solubilizing chelators which do not constitute a potential source of environmental pollution. Concurrently with microbial chelators, plant growth promotion can be enhanced through bacterially-produced phytohormones. In this work, the simultaneous production of siderophores and auxins by Streptomyces was studied to gain insight for future application in plant growth and phytoremediation in a metal-contaminated soil. Standard auxin and siderophore detection assays indicated that all of the investigated Streptomyces strains can produce these metabolites simultaneously. However, Al(3+), Cd(2+), Cu(2+), Fe(3+) and Ni(2+), or a combination of Fe(3+) and Cd(2+), and Fe(3+) and Ni(2+) affected auxin production negatively, as revealed by spectrophotometry and gas chromatography-mass spectrometry. This effect was more dramatic in a siderophore-deficient mutant. In contrast, except for Fe, all the metals stimulated siderophore production. Mass spectrometry showed that siderophore and auxin-containing supernatants from a representative Streptomyces species contain three different hydroxamate siderophores, revealing the individual binding responses of these siderophores to Cd(2+) and Ni(2+), and thus, showing their auxin-stimulating effects. We conclude that siderophores promote auxin synthesis in the presence of Al(3+), Cd(2+), Cu(2+) and Ni(2+) by chelating these metals. Chelation makes the metals less able to inhibit the synthesis of auxins, and potentially increases the plant growth-promoting effects of auxins, which in turn enhances the phytoremediation potential of plants.     

Detection and localization of aluminum and heavy metals in ectomycorrhizal Norway spruce seedlings

Norway spruce seedlings colonized with Hebeloma crustuliniforme were grown in growth pouches. After formation of ectomycorrhizas, the seedlings were exposed to Al or the heavy metals Cd, Cu, Ni, or Zn at various concentrations for 5 weeks to estimate the detection limits of metals with X-ray microanalysis in the cryo-scanning electron microscope. When the lowest metal concentrations (1 mM Al(3+), 0.1 mM Cd(2+), 0.2 mM Cu(2+), 0.5 mM Ni(2+), 2 mM Zn(2+)) were applied, only Al and Zn were detected at low X-ray counts in the ectomycorrhizas. After application of 10-fold higher metal concentrations, distinct metal accumulation patterns were observed. Cd was detected predominantly in the Hartig net, Al and Ni in the Hartig net and in the cell walls of the cortex, and Zn in the Hartig net, the cortical cell walls and the fungal mantle. Cu was not detected at all. By combining X-ray microanalysis with absolute metal concentrations found in the roots, the estimated detection limits of X-ray microanalysis were: Al> or =0.86 mg g(-1), Cd> or =0.26 mg g(-1), Ni> or =1.30 mg g(-1), and Zn> or =0.54 mg g(-1), whereas Cu was not detectable even at root concentrations of 0.47 mg g(-1). Treatments with the highest metal concentrations showed high X-ray counts of metals in cells of the stele but reduced concentrations of the macronutrients K, Mg, and P in roots, indicating a possible disturbance of root and ectomycorrhizal function.     

Development of a biotic ligand model (BLM) predicting nickel toxicity to barley (Hordeum vulgare)

A biotic ligand model (BLM) was developed to predict nickel toxicity, affecting root growth of barley (Hordeum vulgare), in nutrient solutions. The extent to which Ca(2+), Mg(2+), Na(+), K(+) ions and pH each influenced nickel toxicity was determined. Higher activities of Mg(2+) linearly increased the 4d EC50 Ni (2+) , while Ca(2+), Na(+), K(+) and H(+) activities did not significantly influence Ni(2+) toxicity. Stability constants for the binding of Ni(2+) and Mg(2+) to the biotic ligand were obtained: logK(NiBL)=5.27 and logK(MgBL)=3.47. Further, it was calculated that on average 57% of the biotic ligand sites needed to be occupied by nickel to induce 50% root growth inhibition. Auto-validation of the BLM indicated that predicted EC50s differed from the observed EC50s by a factor of less than 2, indicating that the BLM concept may also be used to predict metal toxicity to terrestrial plants.     

An engineered plant that accumulates higher levels of heavy metals than Thlaspi caerulescens, with yields of 100 times more biomass in mine soils

Nicotiana glauca transformed with TaPCS1 was tested for its application in phytoremediation. When plantlets were grown in mine soils containing Cu, Zn, and Pb (42, 2600, and 1500 mg kg(-1)) the plant showed high levels of accumulation especially of Zn and Pb. Adult plants growing in mine soils containing different heavy metal concentrations showed a greater accumulation as well as an extension to a wider range of elements, including Cd, Ni and B. The overexpressed gene confers up to 9 and 36 times more Cd and Pb accumulation in the shoots under hydroponic conditions, and a 3- and 6-fold increase in mining soils. When the hyperaccumulator Thlaspi caerulescens was compared, the results were higher values of heavy metal and Boron accumulation, with a yield of 100 times more biomass. Thlaspi was unable to survive in mining soils containing either a level higher than 11000 mg kg(-1) of Pb and 4500 mg kg(-1) of Zn, while engineered plants yielded an average of 0.5 kg per plant.     

In vitro effect of agriculture pollutants and their joint action on Pseudokirchneriella subcapitata acid phosphatase

Acid phosphatase plays important roles in algae metabolism such as availability and recycling of inorganic phosphate, autophagic digestive processes and fertilization. Chemicals released into the environment from agriculture activities may impair algae phosphatase activity. The aim of this work was to evaluate the in vitro effect of twenty-four organic compounds and six metals used as pesticides, or present as contaminants in sewage sludge, on the acid phosphatase activity extracted from Pseudokirchneriella subcapitata. Results demonstrated that only the linear surfactant alkyl benzenesulphonate (LAS) and the heavy metals Hg(2+), Al(3+) and Cu(2+) markedly altered (50%) the enzyme activity. Join action inhibition studies indicated that Hg(2+) was more potent inhibitor than Al(3+) or LAS, and that the Hg(2+)+Al(3+) and Hg(2+)+LAS mixtures have, respectively, additive and slight antagonism effects. Copper, which demonstrated an activator effect when preincubated with the enzyme, behaved as a slight antagonist for the inhibitor effect of Hg(2+).     

Impacts of pH and ammonia on the leaching of Cu(II) and Cd(II) from coal fly ash

Many coal-fired power plants are implementing ammonia-based technologies to reduce NO(x) emissions. Excess ammonia in the flue gas often deposits on the coal fly ash. Ammonia can form complexes with many heavy metals and change the leaching characteristics of these metals. This research tends to develop a fundamental understanding of the ammonia impact on the leaching of some heavy metals, exemplified by Cu(II) and Cd(II), under different pH conditions. Batch results indicated that the adsorption is the main mechanism controlling Cu(II) and Cd(II) leaching, and high concentrations of ammonia (>5,000 mg/l) can increase the release of Cu(II) and Cd(II) in the alkaline pH range. Based on the chemical reactions among fly ash, ammonia, and heavy metal ion, a mathematical model was developed to quantify effects of pH and ammonia on metal adsorption. The adsorption constants (logK) of Cu(2+), Cu(OH)(+), Cu(OH)(2), and Cu(NH(3))(m)(2+) for the fly ash under investigation were respectively 6.0, 7.7, 9.6, and 2.9. For Cd(II), these constants were respectively 4.3, 6.9, 8.8, and 2.6. Metal speciation calculations indicated that the formation of less adsorbable metal-ammonia complexes decreased metal adsorption, therefore enhanced metal leaching.     

Heavy metal pollution in sediments of the Pasvik River drainage

The purpose of this paper is to study the regional impacts of heavy metals (Ni, Cu, Co, Zn, Cd, Pb, Hg) on the watershed of the Pasvik River. On the basis of sediment investigations at 27 stations of the watershed, background concentrations of the heavy metals, vertical distribution of heavy metals in sediments, heavy metal concentrations in surface sediments, contamination degree, and risk index were determined. The atmospheric emissions of Ni, Cu, Co, Zn, Cd and Hg from the smelters and waste waters from tailing dams and mines of the Pechenganickel Company are likely to be the main sources of increasing concentrations observed in recent sediments of the lower river reaches. Lead showed a different pattern from the other heavy metals--increasing Pb concentrations in the upper sediment layers towards the Norwegian side.     

Sorption studies of heavy metal ions on a novel chelating resin and its application in the stripping of mercury (II)

A chelating resin containing a stable thiol group was synthesised, using polystyrene as the starting material. The resin is stable towards conc. HCl, 0.1M HNO(3) and 0.1M NaOH. The resin shows affinity towards Ag(+), Hg(2+), Bi(3+), Pb(2+), Cu(2+), Zn(2+) and Cd(2+). Extraction of these metal ions as a function of pH, kinetics of exchange and breakthrough capacities is evaluated. The selectivity of the resin for the metal ions is in the order Ag(+) > Hg2+ > Cu2+ > Pb2+ > Cd2+ > Zn2+. The equilibrium constants for exchange and kinetics of exchange are favourable for the recovery of mercury from lean sources. Application of the resin in the stripping of mercury from chlor-alkali plant affluent, and in the enrichment of mercury from seawater, have been investigated. Mercury sorbed resin can be regenerated using 5% thiourea in 0.1M HCl.     

Heavy metal ion influence on the photosynthetic growth of Rhodobacter sphaeroides

The potential of purple non-sulphur bacteria for bioremediation was assessed by investigating the ability of Rhodobacter sphaeroides strain R26.1 to grow photosynthetically in heavy metal contaminated environments. Bacterial cultures were carried out in artificially polluted media, enriched with the transition metal ions Hg2+, Cu2+, Fe2+, Ni2+, Co2+, MoO4(2-), and CrO4(2-) in millimolar concentration range. For each investigated ion the effect on growth parameters was evaluated. The analysis of concentration-effect curves revealed a differentiated response, indicating that diverse mechanisms of tolerance and/or resistance are involved. Adaptation or selection procedures were not applied, leading to assess intrinsic abilities of coping with these contaminants. The microorganism proved to be highly tolerant to heavy metal exposure, especially towards Co2+, Fe2+ and MoO4(2-). In addition Ni2+ and Co2+ were found to decrease the cellular content of light harvesting complexes. A characteristic behavior was observed with mercuric ions, which produced a significant increase of the lag-phase.     

Variation of heavy metals within and among feathers of birds of prey: effects of molt and external contamination

In this study we examined the effect of external contamination on the heavy metal (Ag, Al, As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb and Zn) concentration in feathers. We compared the heavy metal content among the 10 primary wing feathers of sparrowhawks (Accipiter nisus), little owls (Athene nocta) and barn owls (Tyto alba) and the variation within the outermost tail feather of sparrowhawks and tawny owls (Strix aluco). The concentration of Hg was significantly higher in feathers molted first, suggesting that levels in feathers reflect levels in the blood during formation. For some other elements (Al, Co, Ni, Pb, Zn) on the other hand, there are strong indications that external contamination may have an important impact on the levels detected in the feathers. This should be taken into account in future monitoring studies.     

大洋锰结核在环境污染治理方面的应用

大洋锰结核能够有效分解转化气体污染物(如CO、CH、VOC、NOx、SO2);能够吸附水体中的Cu、CO、Ni、Mn、Zn、Cr、Hg、Pb、As等重金属阳离子和PO4^3-、SeO3^2-等阴离子;可做生物固定化载体除去水体中的有机污染物。大洋锰结核具有良好的环境矿物学属性,是一种理想的环境矿物材料,为环境治理提供了新的方向。     

Study on the photocatalytic degradation of glyphosate by TiO(2) photocatalyst

In this paper, the photocatalytic degradation of glyphosate selected as the deputy of organic pollutant in aqueous solution with TiO(2) powder as a photocatalyst has been studied. The effects of various parameters, such as the amount of the photocatalyst, illumination time, initial pH value, electron acceptors, metal ions, and anions on the photocatalytic degradation of glyphosate were investigated. From the studies, the best condition for the effect of the parameters on the photocatalytic degradation of glyphosate was obtained. The results show that the optimum amount of the photocatalyst used is 6.0 g l(-1) for the photocatalytic reactions. The photodegradation efficiency of glyphosate increases with the increase of the illumination time. With the addition of Fe(3+), Cu(2+), H(2)O(2), K(2)S(2)O(8) or KBrO(3), the photocatalytic degradation of glyphosate is accelerated. However, with the addition of Na(+), K(+), Mg(2+), Ca(2+), Zn(2+), Co(2+) and Ni(2+), or with the addition of trace amounts of Cl(-), Br(-), SO(4)(2-), there are no obvious effects on the reactions. Acidic or alkaline mediums are favorable for the photocatalytic degradation of glyphosate. The possible roles of the additives on the reactions and the possible mechanisms of effect were discussed.     

Multiscale analysis of heavy metal contents in Spanish agricultural topsoils

This study characterized and mapped the spatial variability patterns of seven topsoil heavy metals (Cr, Ni, Pb, Cu, Zn, Hg and Cd) within the Ebro river basin (9.3 million ha) by Multivariate Factorial Kriging. The variograms and cross-variograms of heavy metal concentrations showed the presence of multiscale variation that was modeled using three variogram models with ranges of 20km (short-range), 100km (medium-range) and 225km (long-range). Our results indicate that the heavy metal concentration is influenced by bedrock composition and dynamics at all the spatial scales, while human activities have a notorious effect only at the short- and medium-range scale of variation. Sources of Cu, Pb and Zn (and secondary Cd) are associated with agricultural practices (at the short-range scale of variation), whereas Hg variation at the short- and medium-range scale of variation is related to atmospheric deposition.     

Bioindication of heavy metals in the town Wrocław (Poland) with evergreen plants

In this paper the results are reported of a study on the concentration of macroelements (N, P, K, Ca, Mg, S and Fe) and heavy metals (Ni, Cr, Co, V, Zn, Mn, Pb, Cd, Cu, Hg, Ba and Sr) in soil and in three species of the evergreen plants Ilex aquifolium, Mahonia aquifolium and Rhododendron catawbiense. These plants are collected in the Botanical Garden of the Polish town Wrocław (which is exposed to atmospheric exhausts of heavy traffic, chemical factories, metal smelters and a heat and power plant partly alimented with lignite and coals) and in two presumed unpolluted reference (background) sites, one in Poland (the Dendrological Garden in Wojslawice near Niemcza, south from Wrocław) and the other in The Netherlands (the Botanical Garden of the University of Nijmegen).Analyses of both soil and plant samples point to the pollution of the Wrocław Botanical Garden by Ni, Cr, Co, Cd via the atmosphere and pollution by Zn, Pb and Hg probably via atmosphere and soil. Especially pollution with Hg via soil is supported by a significant positive correlation between Hg content in soil and in all the examined species of which Ilex aquifolium seemed to be the best monitor of soil pollution with this element.     

Source identification and risk assessment of heavy metal contaminations in urban soils of Changsha,a mine-impacted city in Southern China

The urban soils suffered seriously from heavy metal pollutions with rapid industrialization and urbanization in China. In this study, 54 urban soil samples were collected from Changsha, a mine-impacted city located in Southern China. The concentrations of heavy metals (As, Cd, Co, Cu, Mn, Ni, Pb, and Zn) were determined by ICP-MS. The pollution sources of heavy metals were discriminated and identified by the combination of multivariate statistical and geostatistical methods. Four main sources were identified according to the results of hierarchical cluster analysis (HCA), principal component analysis (PCA), and spatial distribution patterns. Co and Mn were primarily derived from soil parent material. Cu, Pb, and Zn with significant positive relationships were associated with mining activities and traffic emissions. Cd and Ni might be affected by commercial activities and industrial discharges. As isolated into a single group was considered to have correlation with coal combustion and waste incineration. Risk assessment of heavy metals in urban soils indicated an overall moderate potential ecological risk in the urban region of Changsha.     

Pre-concentration and separation of heavy metal ions by chemically modified waste paper gel

Iminodiacetic acid was immobilized on waste paper by chemical modification in order to develop a new type of adsorption gel for heavy metal ions. Adsorption behavior of the gel was investigated for a number of metal ions, specifically Cu(II), Pb(II), Fe(III), Ni(II), Cd(II), and Co(II) at acidic pH. From batch adsorption tests, the order of selectivity was found to be as follows: Cu(II)  Fe(III) > Pb(II) > Ni(II)  Co(II) > Cd(II). Column tests were carried out for pairs of metal ions to understand the separation and pre-concentration behavior of the gel. It was found that mutual separation of Ni(II) from Co(II) and that of Pb(II) from Cd(II) can be achieved at pH 3. Similarly, selective separation of Cu(II) from Cu(II)–Fe(III) and Cu(II)–Pb(II) mixtures at pH 1.5 and 2, respectively, was observed by using this new adsorption gel. In all cases, almost complete recovery of the adsorbed metal was confirmed by elution tests with HCl.     

西湖沉积物中元素分布特征研究

分析测定了西湖沉积物（２０ｍ钻探样品）不同层次中Ｆｅ、Ａｌ、Ｃａ、Ｍｇ、Ｔｉ、Ｍｎ、Ｃｕ、Ｚｎ、Ｃｄ、Ｎｉ、Ｈｇ、Ｃｒ、Ａｓ、Ｃｏ、Ｖ等１５种元素的含量，并根据元素的分布特征探讨了西湖沉积物的形成发展及重金属污染状况。     

Impact of industrial and mine drainage wastes on the heavy metal distribution in the drainage basin and estuary of the Sado River (Portugal)

This paper presents results from a survey of the heavy metal distribution in sediments in the drainage basin and estuary of the Sado River (Portugal). In the drainage basin, heavy metals originate mostly from pyrite outcrop erosion and mining activities (Cd, Zn, Cu and locally Hg, Pg), and also from crust erosion (Sn, Ni, Ti, Zr). These sources are not correlated with the particulate organic carbon (POC) and so the metals are thought to be in inorganic forms in this area. Anthropogenic heavy metal sources (urban and industrial) are found in the lower estuary (Sn, Cd, Hg, Zn, Pb and Cu) along with high POC concentrations. In this zone, these metals are thought to be strongly adsorbed onto organic particles. Furthermore, organo-metallic species are likely to be present, as demonstrated in the case of Sn, since methyl- and butyl-tin species were detected in sediments from this area. This suggests the need for the detection of organo-metallic species to understand the heavy metal geochemical cycles. No long-term changes in metal concentrations are found in sediment cores, except in the middle estuary (Zn, Cu) due to the development of mining activities on an industrial scale in the 1860s.     

Studies on the effects of some organic pollutants on the heavy metal transport in an Indian soil

The translocation of some heavy metals, such as Hg, Cd, Cu, Co, Ni and Zn, as affected by organic pollutants, i.e. methanol, ethanol, propanol, formaldehyde, acetaldehyde, benzaldehyde, acetone, ethyl methyl ketone and cyclo-hexanone, was studied in an Indian red soil using soil thin layer chromatography. It was observed that an increase in the concentration of organic compounds in developer enhances the heavy metal mobility, except in the case of Cu and Hg which show a decreasing trend. The results are discussed in relation to the physico-chemical characteristics of the soil and adsorption/desorption phenomena.