MELIMEX,an experimental heavy metal pollution study: Chemical speciation and biological availability of copper in lake water

The chemical speciation of dissolved copper was investigated in waters from the limno-corrals of the MELIMEX project and compared with speciation data from other Swiss lakes. Copper is complexed primarily by organic ligands having molecular sizes between 10⁴ and 10³ daltons. The mean concentration of the ligands is approximately 5×10⁻⁷ mole/mg DOC. The conditional stability constants (pH=8.8) are about 10¹¹. An increased metal load did not induce an increase of binding ligands. A comparison of calculated Cu²⁺ concentration with corresponding copper contents in the biomass leads to the conclusion that organic ligands and pH are the most important factors in deciding the biological availability of copper. However the sorption capacity of the biomass depends as well on the variety of plankton species.     

Nutrient,heavy metal and organic pollutant composition of suspended and bed sediments in the Rhone River

The environmental quality of the Rhone River (Switzerland-France) has been assessed with a geochemical survey of the pollutants bound to suspended sediments. Ten samples were collected between Lake Geneva and the Mediterranean Sea in Nobember 1989 by continuous flow centrifugation and analysed for grain size distribution, carbonate, organic C, N, forms of particulate P, trace metals, and organic compounds (chlorobenzenes, organochlorine pesticides, PCBs, and PAHs). Four bed sediment samples were also studied for comparative purposes. The suspended solids provide lower variance by parameter than the bed sediments and are clearly most suitable for synoptic monitoring.The Upper Rhone River carries a glacial derived sediment with a low nutrient content, the stretch from Geneva to Lyon provides a sediment dominated by carbonate, and in the Lower Rhone the organic matter and phosphorus are relatively increased, mainly due to wastewater effluents and to an industrial P source. High concentrations of metals and organic micropollutants downstream of Lyon indicate a multiple contamination in the Lower Rhone, whereas more specific inputs are located downstream of Geneva and Arles.The comparison with data from other polluted major systems, the Rhine, the Niagara and the Detroit rivers, shows on overall similarity confirming that the Rhone quality is degraded downstream of Lyon. The levels of particular concern are for Hg, DDT metabolites which reveal a recent release in the basin, PCBs with a likely high chlorine content, and PAHs.The statistical evaluation of the compositional variables indicates a limited number of well defined associations, suggesting that the contamination of the suspended sediments results from the combination of numerous and intermittent point and diffuse sources in the Rhone River basin.     

典型小型水库表层沉积物重金属分布特征及生态风险

以典型乡镇水库通济桥水库表层沉积物为研究对象,在分析其中As、Cd、Cr、Cu、Hg、Ni、Pb和Zn等有毒、有害重金属分布特征的基础上,分析重金属来源,评价重金属污染程度及其潜在生态危害.结果表明:通济桥水库表层沉积物中,上述8种重金属均存在一定程度的污染,坝前和入库区污染物蓄积更为明显.其中,Hg和Cd的污染范围较广、污染程度较严重.受重金属Hg和Cd的影响,水库表层沉积物存在中等程度的重金属生态危害风险,其中坝前区域已处于强风险等级.为保障水库水体水质安全,防范重金属污染应提到当前水库管理工作的重要位置.     

Biosorption of heavy metals in polluted water,using different waste fruit cortex

The biosorption capacity of different cortex fruit wastes including banana (Musa paradisiaca), lemon (Citrus limonum) and orange (Citrus sinensis) peel were evaluated. In order to perform these experiments, grinded dried cortexes were used as package in 100 mm high, 10 mm i.d. columns. The grinded material was powdered in a mortar and passed through a screen in order to get two different particle sizes, 2 and 1 mm, for all powders. To estimate the biosorption capabilities of the tested materials, different heavy metals were passed through the columns and the elution filtrate reloaded different times to increase the retention of metals. The heavy metals used were prepared as synthetic samples at 10 mg/L of Pb(NO₃)₂, Cd(NO₃)₂, and Cu(NO₃)₂·6H₂O using primary standards. In preliminary experiments using banana cortex, it was found that material with 1 mm of particle size showed higher retention capability (up to12%) than the material with 2 mm of particle size. Considering these results, 1 mm particle size material was used in further experiments with the other waste materials. It was found that for Pb and Cu removal, lemon and orange cortex showed better biosorption capability when compared with banana cortex (up to 15% less for Pb and 48% less for Cu). For Cd, banana cortex showed better biosorption capability 57% (67.2 mg/g of cortex) more than orange (28.8 mg/g of cortex), and 82% more than lemon (12 mg/g of cortex). Reload of the columns with the filtrate after passing through the column improved the removal capability of all the materials tested from 10% to 50% depending on the cortex and metal tested.     

Observation of excess heavy metal concentrations in water resources to infer surface water influences on shallow groundwater: a typical example of the Porsuk River (Eskisehir-Turkey)

Water Resources - The Eskisehir province is well-known due to its industrial and agricultural activities, which are a threat for the aquatic environment. Hence, monitoring of water quality in the...     

首钢工业区土壤剖面重金属含量及其结合态的磁指示作用的研究

对取自首都钢铁厂附近的土壤样芯进行了重金属含量、形态分析和的磁学测量.探讨了利用磁参数追踪和指示重金属污染和有机结合态和铁锰氧化结合态重金属的可行性.结果表明:土壤样芯中Cu、Pb、Zn、Fe和Mn的含量与χ、SIRM和ARM存在着十分相似的垂向变化特征,且相关关系显著(0.98>R>0.86).进一步对磁化率和Cu、Pb、Zn、Fe和Mn各结合态进行相关分析表明:五种元素的有机结合态与铁锰结合态和磁化率呈显著相关关系(0.98>R>0.56),而交换态和残渣态重金属与磁化率基本不存在相关关系.反映了磁性矿物和和重金属在赋存状态的本质联系.表明了磁性测量可作为工业区土壤重金属污染及有机结合态与铁锰结合态重金属记录信息提取的辅助手段.     

Remediation studies of trace metals in natural and treated water using surface modified biopolymer nanofibers

In this study, remediation results of trace metals in natural water and treated water using three functionalized nanofiber mats of cellulose and chitosan are reported. The nanofiber materials, packed in mini-columns, were employed for the remediation of five toxic trace metals (Cd, Pb, Cu, Cr and Ni) from natural water samples. Trace metals in real water samples were undetectable as the concentrations were lower than the instrument’s detection limits of 0.27 × 10⁻³ (Cd) and 4.2 × 10⁻² (Pb) μg mL⁻¹, respectively. However, after percolation through the functionalised biosorbents in cartridges, detectability of the metal ions was enhanced. The starting volume of the natural water sample was 100 mL, which was passed through a column containing the nanofibers sorbent and the retained metals eluted with 5 mL of 2.0 M nitric acid. The eluate was analyzed for metals concentrations. An enrichment factor of 20 for the metals was realized as a result of the pre-concentration procedure applied to handle the determination of the metals at trace levels. The order of remediation of the studied metals using the nanofibers was as follows: chitosan/PAM-g-furan-2,5-dione < cellulose-g-furan-2,5-dione < cellulose-g-oxolane-2,5-dione. The modified biopolymer nanofibers were able to adsorb trace metals from the river water and treated water, thereby confirming their capability of water purification. These materials are proposed as useful tools and innovative approach for improving the quality of drinking for those consumers in small scale households.     

我国城市水源水库水质风险成因及对策

我国城市水源中约40%为湖泊或水库,且大部分为水库,因此水源水库的水质状况对我国城市安全极其关键。本文综述了我国水源水库水质问题研究进展,分析了22个代表性水源水库的周年水质状况。结果发现,当前我国城市水源水库水质风险类型主要是异味问题、藻类水华、铁锰超标、有机质偏高、营养盐超标等。引发水源水库水质问题的主要原因包括流域开发强度过大、库底淤积及内源释放、生态系统结构失衡、气候与水文异常变化等。针对上述主要问题,提出了构建在线水质监测预警体系、控制流域土地开发强度、构建面源拦截及流域净化系统、疏浚底泥、优化生态系统结构、实施应急曝气与控藻工程、完善流域生态保护法律法规等多种水源水库水质安全保障技术措施。鉴于水源水库水质及水生态对暴雨、高温热浪等极端气象响应敏感而复杂,在当前极端天气事件频发、强度不断增加的气候背景下,还应加强水库生态学基础研究,以深入理解水源水库水质对气候变化的响应机制,提高水库水安全保障科技支撑能力,满足我国城市高质量发展的水资源需求。     

The potential use of fairy prions (Pachyptila turtur) as monitors of heavy metal levels in Tasmanian waters

The purpose of the present study was to examine the potential use of the fairy prion to monitor contamination in the marine food chain following ocean dumping of industrial waste in S.E. Tasmania. Factors considered that can complicate interpretation of heavy metal levels detected include age, sex, seasonal, and other ecological aspects of the indicator species chosen. Unlike some other species of seabirds, the influence of sex and season on metal levels was unimportant. Copper, zinc, cadmium, and lead were tested in the liver and muscle tissue of fairy prions. In this preliminary study, cadmium levels were found to be significantly higher statistically in fairy prions closest to a potential source of pollution compared to levels from distant locations. This trend was not found in other metals investigated. However, it is suggested that this species would provide a useful future means of monitoring heavy metal levels.     

Leaf biochemical parameters in Avicennia marina (Forsk.) Vierh as potential biomarkers of heavy metal stress in estuarine ecosystems

Sediment loadings and leaf accumulation of the heavy metals copper (Cu), lead (Pb) and zinc (Zn) with accompanying changes in leaf chlorophylls' (a + b), carotenoids and the antioxidant enzyme peroxidase were examined in the grey mangrove Avicennia marina (Forsk.) Vierh, in order to determine the applicability of these parameters as biomarkers of heavy metal stress under field conditions. Copper was found to show limited accumulation to leaf tissue, following a linear relationship at lower sediment concentrations, with saturation at higher sediment Cu concentrations. Copper accumulation relationships to leaf tissue were maintained temporally, and increases in sediment Cu, salinity, and decreases in sediment pH and Zn contributed to the accumulation of Cu to leaf tissue. Lead showed a significant relationship between sediment and leaf Pb levels, but accumulation was minimal. Accumulation relationships for Pb were not maintained temporally, and high sediment Pb, low pH and organic content increased bioavailability and accumulation of Pb. Zinc was the most mobile of all metals and was accumulated to the greatest quantities in leaf tissue in a dose-dependant relationship. Some temporal variation in Zn accumulation occurred, and higher sediment pH, organic content Zn and Pb promoted leaf Zn accumulation. Leaf Cu and Zn showed the strongest relationship with peroxidase activity and to a lesser degree Pb. Zinc was the only accumulated metal to show relationship maintenance with peroxidase activity over time. It was found that peroxidase activity best reflects the total phytotoxic effect from the combined metal stress of all three accumulated leaf metals. The only significant photopigment relationship evidenced was that of leaf Zn with the chlorophyll a/b ratio, but was not maintained temporally. Peroxidase activity may be an appropriate biomarker for Zn or total metal accumulation in leaf tissue, and the chlorophyll a/b ratio a suitable biomarker of Zn accumulation though requires temporal monitoring under field conditions.     

Spatial and temporal variations of heavy metal contamination in sediments of a mangrove swamp in Hong Kong

Spatial and temporal variations of heavy metal contamination in sediments of a small mangrove stand in Hong Kong were examined by laying two transects perpendicular across the shore. Surface sediment samples were taken along the two transects running landward to seaward at intervals of 5 or 10 m during December 1989, and March, July and September 1990. Total concentrations of Cu, Zn, Mn and Pb did not show any specific trend along each transect, although the maximum concentration of heavy metals tended to occur at the landward edge. There was a high level of variability among locations within each transect; for instance, the Cu concentrations fluctuated from 1 to 42 μg g⁻¹. Certain sites contained exceptionally high levels of total metals. Total concentrations of Cu, Zn, Mn and Pb as high as 42, 150, 640 and 650 μg g⁻¹, respectively, were recorded, implying contaminated sediment. A comparison of the two transects indicated that the sediments of Transect B seemed to contain higher total Zn but lower Cu and Mn concentrations than those of Transect A. Most of the heavy metals accumulated in the sediments were not extractable with ammonium acetate and no Cu or Pb was detected in these extracts. The concentrations of extractable Zn and Mn were low, less than 10% of the total metal concentration in the sediment, and appeared to decrease from the landward to seaward samples. For both total and extractable metals, there were significant seasonal fluctuations for both transects, but no specific trends could be identified. These spatial and temporal variations suggest that the scale and representativeness of sampling require careful planning, and a single sample might not give a satisfactory evaluation of the levels of heavy metal contamination in mangrove ecosystems.     

An approach to analyses of periphytic ciliate colonization for monitoring water quality using a modified artificial substrate in Korean coastal waters

Structural and functional parameters of periphytic ciliate communities were studied for monitoring water quality in Korean coastal waters during April 2007. The PFES (polyurethane foam enveloped slide) system, a modified glass slide method, was used to analyze periphytic ciliate colonization in marine ecosystems. A total of 27 ciliate species were identified using living observation and silver impregnation method with this system. Although the ciliate colonizations had similar species composition, they represented considerable differences in both structural and functional parameters between the PFES system and the conventional slide system. The species diversity, evenness and the colonization rate (G) were distinctly higher, but the time for reaching 90% equilibrium species number (T_90%) was shorter in the PFES system than those on the naked slides. Results suggest that the PFES system is more effective than the conventional slide method for periphytic ciliate colonization with high species diversity, evenness, and colonization rate in marine ecosystems.     

Use of fluorescein as a ground water tracer in brackish water aquifers

A drift and pumpback experiment was conducted in a brackish water sandfill. The sandfill was reclaimed from the sea in the eastern part of Singapore and contains sands with low organic and clay/silt contents. The high salinity in the ground water precludes the use of chloride and bromide as tracers in such an environment, and a field experiment was conducted to assess the viability of using fluorescein as a tracer in brackish water aquifers. Nitrate was used as a second tracer to serve as a check. Initial laboratory studies showed that fluorescence was unaffected over the range of electrical conductivity and pH of the ground water. Results from the field experiment show that fluorescein appears to behave conservatively.     

Investigation of recreational boats as a source of copper at anchorage sites using time-integrated diffusive gradients in thin film and sediment measurements

Antifouling paints on small to medium recreational vessels were first recognized as an important source of pollution in the 1970s. One of the principle biocides in these paints is Cu. Results from a field program in the Gold Coast Broadwater, Queensland, demonstrate a clear correlation between recreational boat numbers at anchorage sites and water column Cu concentrations, for both time-integrated 24 h DGT measurements (n=14, r=0.815, p<0.001) and measurements on composite 0.45 mum-filtered grab samples (n=14, r=0.698, p<0.01) collected every 4 h over 24 h. At boat numbers above 30 the 0.45 microm-filterable Cu concentrations were mostly above the relevant guideline value (1.3 microgl(-1)) but the DGT-reactive Cu concentrations were well below this value at all boat numbers studied. For three-day DGT deployments in Moreton Bay, Queensland, correlations between Cu levels and vessel numbers were not observed, possibly because of uncertain estimates of boat numbers. However, using a multi-factorial ANOVA, DGT-reactive Cu concentrations showed a significant effect for 'sites with vessels vs. sites without vessels' (alpha=0.10, p=0.077) and for 'sampling period' (non-holiday weekdays, weekends, holiday weekdays, holiday weekends) at alpha=0.10, p=0.02. Cu levels in sediments at the same sites were strongly influenced by fraction of clay (<63 microm) material but also by whether the samples were collected at an anchorage or control site. Results from this study further support the view that Cu emissions from antifouling paints may become an important source in waters with high boat numbers and should be taken into account when designing management instruments for coastal waterways.     

Dating of soil layers in a young floodplain using iron oxide crystallinity

Dating of fluvial deposits is essential for a more quantitative understanding of landscape evolution and soil development in floodplain environments. We collected soil layers in defined depth intervals down to 60 cm along a substrate age gradient in a floodplain of the Danube River near Vienna, Austria. Depth profiles of fallout ¹³⁷Cs were used to assess short-term sedimentation, and optically stimulated luminescence (OSL) dating was used to attribute sediment deposits to time periods between the early last millennium BC and the 18th century AD. In the studied soils, the ratio of oxalate- to dithionite-extractable iron (Fe_o/Fe_d), which indicates the degree of iron oxide crystallinity, progressively decreased from ratios greater than 0.5 to values less than 0.2 with increasing soil age and proved to be a reliable indicator of soil maturity. We linked the observed Fe_o/Fe_d ratios to the radiometric and OSL ages in a chronofunction, which allows to approximately date soil layers that lack an independent age control. The soil ages calculated with this chronofunction accurately reflected their geomorphological position, resulted in consistent age trends with depth, and highlighted the active morphodynamics of the studied floodplain. The chronofunction was further validated by dating a soil profile near the studied chronosequence that contained an archaeological find dated to the La Tène period (5th to 1st century BC).     

Effects of organic mineral fertiliser on heavy metal migration and potential carbon sink in soils in a karst region

Heavy metal pollution in karst mountainous area of Guizhou has spread due to the long-term exploitation of mineral resources and the improper disposal of environmentally hazardous waste. Heavy metals are characterised by non-degradation, strong toxicity, and constant accumulation, posing a grave threat to karst mountain fragile soil ecosystem. To reduce the harm caused by heavy metal pollution and damage to agricultural products, research was undertaken on the basis of previous work by simulating pot experiments on pak choi cabbage(Brassica rapa chinensis)planted in Cd-contaminated soil: different amounts of organic mineral fertilisers(OMF) compared with chemical fertiliser(CF) were used and by detecting the amount of heavy metal in the mature vegetable, a better fertilisation strategy was developed. The results showed that the Cd content in vegetables grown with CF was 23.70 mg/kg,while that of vegetables grown with OMF and bacterial inoculant was the lowest at 15.13 mg/kg. This suggests that the use of OMF and microbes in karst areas not only promotes plant growth but also hinders plant absorption of heavy metal ions in the soil. In addition, through the collection of pot leachate, the detection of water chemistrycharacteristics, and the calculation of the calcite saturation index, it was found that the OMF method also induces certain carbon sink effects. The results provide a new way in which rationalise the use of OMFs in karst areas to alleviate soil heavy metal pollution and increase soil carbon sequestration.     

Delineation of heavy metal contamination pathways (seawater,food and sediment) in tropical oysters from New Caledonia using radiotracer techniques

Bioaccumulation of Ag, Cd, Co, Cr and Zn was studied in the oysters Isognomon isognomon and Malleus regula, using highly sensitive radiotracer techniques. Metals were readily bioconcentrated from the dissolved phase. Sediment exposures indicated a low bioavailability of sediment-bound metals (3–5 orders of magnitude lower than dissolved metals). In both seawater and sediment experiments, the two oysters displayed similar bioaccumulation behaviour towards all metals but Ag. Indeed, Ag was much more efficiently incorporated and retained in I. isognomon. Metals ingested with food (phytoplankton) were efficiently assimilated (34–77%) and strongly retained in oyster tissues (T_b½ ⩾ 20 d). Estimation of the relative contribution of each exposure pathway indicated that for both species sediment was the dominant pathway for Co and Cd, whereas food was the major source of Zn. Regarding Ag, seawater was the main source for I. isognomon (86%), whereas sediment was the predominant route for M. regula (92%).     

Photosynthetic pigments and peroxidase activity as indicators of heavy metal stress in the Grey mangrove, Avicennia marina (Forsk.) Vierh

Mangroves have been observed to possess a tolerance to high levels of heavy metals, yet accumulated metals may induce subcellular biochemical changes, which can impact on processes at the organism level. Six month-old seedlings of the grey mangrove, Avicennia marina (Forsk.) Vierh, were exposed to a range of Cu (0-800 micrograms/g), Pb (0-800 micrograms/g) and Zn (0-1000 micrograms/g) concentrations in sediments under laboratory conditions, to determine leaf tissue metal accumulation patterns, effects on photosynthetic pigments (chlorophyll a, chlorophyll b and carotenoids), and the activity of the antioxidant enzyme peroxidase. Limited Cu uptake to leaves was observed at low sediment Cu levels, with saturation and visible toxicity to Cu at sediment levels greater than 400 micrograms/g. Leaf Pb concentrations remained low over a range of Pb sediment concentrations, up to 400 micrograms/g Pb, above which it appeared that unrestricted transport of Pb occurred, although no visible signs of Pb toxicity were observed. Zn was accumulated linearly with sediment zinc concentration, and visible toxicity occurring at the highest concentration, 1000 micrograms/g Zn. Significant increases in peroxidase activity and decreases in photopigments were found with Cu and Zn at concentrations lower than those inducing visible toxicity. Significant increases in peroxidase activity only, were found when plants were exposed to Pb. Positive linear relationships between peroxidase activity and leaf tissue metal concentrations were found for all metals. Significant linear decreases in photosynthetic pigments with increasing leaf tissue metal concentrations were observed with Cu and Zn only. Photosynthetic pigments and peroxidase activity may be applicable as sensitive biological indicators of Cu and Zn stress, and peroxidase activity for Pb stress in A. marina.     

Simulation of spatially-distributed copper pollution in a large river basin using the ECOMAG-HM model

The semi-distributed physically-based model ECOMAG-HM was developed to simulate cycling of heavy metals in large river basins: on the surface, and in soil, groundwater and river water. The model was applied to study the spatial distribution and temporal dynamics of copper concentrations in watercourses of the Nizhnekamskoe Reservoir watershed in Russia. This watershed is characterized by high background concentrations of heavy metals due to wide occurrence of ore deposits and considerable concentrations of ore-parent elements in rocks. The model was found to adequately reproduce the spatial variation of the mean annual copper concentrations at different monitoring points of the river network. The mean annual specific copper washoff, with the surface and subsurface components of river runoff, and the total copper washoff from the watershed into the river network were calculated and mapped. The contributions of natural and anthropogenic factors to river water pollution by copper were evaluated.