Test of experimental set-ups for electrodialytic removal of Cu, Zn, Pb and Cd from different contaminated harbour sediments

Electrodialytic removal of heavy metals from different harbour sediments was investigated. Electrodialytic remediation experiments in laboratory scale were made with calcareous and non-calcareous harbour sediments. Two different experimental set-ups were used for the study, one with stirring of the sediment slurry, the other without stirring. The removal of heavy metals was highest in the non-calcareous sediment, where 94% Cd, 91% Zn and 73% Cu were removed after 24 days. The highest removal obtained for the calcareous sediment was 81% Cd, 76% Zn, 75% Pb and 53% Cu after 21 days, with stirred sediment slurry. Electrodialytic experiments without stirring of calcareous sediment gave high removals (84% Zn, 58% Pb and 48% Cu), but there were problems with precipitations in the sediment, which limited the removal. The stirred experiments gave the highest removals of heavy metals and the voltage was the most stable in these experiments, and thus, the stirred set-up is the best choice for experimental set-up. The order in which the heavy metals were removed from the harbour sediments was Cd>Zn>Pb>Cu.     

Distribution of Cd,Pb, Zn and Cu and their chemical speciations in soils from a peri-smelter area in northeast China

An exploratory study on soil contamination of heavy metals was carried out surrounding Huludao zinc smelter in Liaoning province, China. The distribution of total heavy metals and their chemical speciations were investigated. The correlations between heavy metal speciations and soil pH values in corresponding sites were also analyzed. In general, Cd, Zn, Pb, Cu and As presented a significant contamination in the area near the smelter, comparied with Environmental Quality Standards for Soils in China. The geoaccumulation index showed the degree of contamination: Cd > Zn > Pb > Cu > As. There was no obvious pollution of Cr and Ni in the studied area. The speciation analysis showed that the dominant fraction of Cd and Zn was the acid soluble fraction, and the second was the residual fraction. Pb was mostly associated with the residual fraction, which constituted more than 50% of total concentration in all samples. Cu in residual fraction accounted for a high percentage (40–80%) of total concentration, and the proportion of Cu in the oxidizable fraction is higher than that of other metals. The distribution pattern of Pb and Zn was obviously affected by soil pH. It seemed that Pb and Zn content in acid solution fraction increased with increasing soil pH values, while Cd content in acid soluble fraction accounted for more proportion in neutral and alkaline groups than acidic one. The fraction distribution patterns of Cu in three pH groups were very similar and independent of soil pH values. And the residual fraction of Cu took a predominant part (50%) of the total content.     

Phosphorus status and sorption characteristics of some calcareous soils of Hamadan,western Iran

Phosphorus (P) application in excess of plant requirement may result in contamination of drinking water and eutrophication of surface water bodies. The phosphorous buffer capacity (PBC) of soil is important in plant nutrition and is an important soil property in the determination of the P release potential of soils. Phosphorus sorption greatly affects both plant nutrition and environmental pollution. For better and accurate P fertilizer recommendations, it is necessary to quantify P sorption. This study was conducted to investigate available P and P sorption by calcareous soils in a semi-arid region of Hamadan, western Iran. The soil samples were mainly from cultivated land. Olsen’s biocarbonate extractable P (Olsen P) varied among soils and ranged from 10 to 80 mg kg⁻¹ with a mean of 36 mg kg⁻¹. Half of the soils had an Olsen P > 40 mg kg⁻¹ and >70% of them had a concentration >20 mg kg⁻¹, whereas the critical concentration for most crops is <15 mg P kg⁻¹. Greater average Olsen P in soils occurred under garlic (56 mg kg⁻¹) and potato (44 kg kg⁻¹) fields than in dry-land wheat farming (24 mg kg⁻¹), pasture (30 mg kg⁻¹), and wheat (24 mg P kg⁻¹) fields. A marked increase in fertilizer P rates applied to agricultural soils has caused P to be accumulated in the surface soil. Phosphate sorption curves were well fitted to the Freundlich equation. The standard P requirement (SPR) of soils, defined as the amount of P sorbed at an equilibrium concentration of 0.2 mg l⁻¹ ranged from 4 to 102 mg kg⁻¹. Phosphorus buffer capacity was relatively high and varied from 16 to 123 l kg⁻¹ with an average of 58 l kg⁻¹. In areas of intensive crop production, continual P applications as P fertilizer and farmyard manure have been used at levels exceeding crop requirements. Surface soil accumulations of P are high enough that loss of P in surface runoff and a high risk for P transfer into groundwater have become priority management concerns.     

北京城区土壤中Hg、Pb、Cd、Cu及Zn化学形态及环境效应

为弄清北京城区土壤中Hg、Pb、Cd、Cu及Zn五种重金属元素的化学形态分布特征,系统采集了126件城区表层土壤样品,采用连续提取法对重金属元素各化学形态含量进行了测定。结果表明:土壤中土壤中Hg、Pb、Cd、Cu、Zn含量差异显著。Hg元素以残渣态和强有机结合态为主,Cd元素离子交换态、碳酸盐结合态、残渣态、铁锰氧化物结合态含量较高,Pb、Cu、Zn元素以残渣态、铁锰氧化物结合态为主。Hg元素的有效态含量最低(不足1%),现情况下不会对环境造成污染;Cd元素的有效态含量最高(40%),生物有效性和潜在生态危害性较大,运用植物修复技术对其治理为经济有效的方法;Pb、Cu、Zn有效态含量较低(约10%),生物有效性和潜在生态危害性均有限。各元素形态与全量之间相关程度虽有差别,但基本呈正相关关系。     

Competitive adsorption of Cd,Cu, Pb and Zn by different soils of Eastern China

Simultaneous competitive adsorption behavior of Cd, Cu, Pb and Zn onto nine soils with a wide physical–chemical characteristics from Eastern China was measured in batch experiments to assess the mobility and retention of these metals in soils. In the competitive adsorption system, adsorption isotherms for these metals on the soils exhibited significant differences in shape and in the amount adsorbed. As the applied concentration increased, Cu and Pb adsorption increased, while Cd and Zn adsorption decreased. Competition among heavy metals is very strong in acid soils with lower capacity to adsorb metal cations. Distribution coefficients (K _dmedium) for each metal and soil were calculated. The highest K _dmedium value was found for Pb and followed by Cu. However, low K _dmedium values were shown for Zn and Cd. On the basis of the K _dmedium values, the selectivity sequence of the metal adsorption is Pb > Cu > Zn > Cd and Pb > Cu > Cd > Zn. The adsorption sequence of nine soils was deduced from the joint distribution coefficients (K _dΣmedium). This indicated that acid soils with low pH value had lower adsorption capacity for heavy metals, resulting in much higher risk of heavy metal pollution. The sum of adsorbed heavy metals on the soils could well described using the Langmuir equation. The maximum adsorption capacity (Q _m) of soils ranged from 32.57 to 90.09 mmol kg⁻¹. Highly significant positive correlations were found between the K _dΣmedium and Q _m of the metals and pH value and cation exchange capacity (CEC) of soil, suggesting that soil pH and CEC were key factors controlling the solubility and mobility of the metals in soils.     

Geochemistry characterization of groundwater in an agricultural area of Razan,Hamadan, Iran

This study was conducted to evaluate factors regulating groundwater quality in an area with agriculture as main use. Thirty groundwater samples have been collected from Razan area (Hamadan, Iran) for hydrochemical investigations to understand the sources of dissolved ions and assess the chemical quality of the groundwater. The chemical compositions of the groundwater are dominated by Na⁺, Ca²⁺, HCO₃ ⁻, Cl⁻ and SO₄ ²⁻, which have been derived largely from natural chemical weathering of carbonate, gypsum and anthropogenic activities of fertilizer’s source. The production of SO₄ ²⁻ has multiple origins, mainly from dissolution of sulphate minerals, oxidation of sulphide minerals and anthropogenic sources. The major anthropogenic components in the groundwater include Na⁺, Cl⁻, SO₄ ²⁻ and NO₃ ⁻, with Cl⁻ and NO₃ ⁻ being the main contributors to groundwater pollution in Razan area.     

Chemical characteristics of groundwater in parts of mountainous region, Alvand, Hamadan, Iran

Eighty-seven groundwater samples have been collected from a mountainous region (Alvand, Iran) for hydrochemical investigations to understand the sources of dissolved ions and assess the chemical quality of the groundwater. Most water quality parameters are within World Health Organization acceptable limits set for drinking water. The least mineralized water is found closest to the main recharge zones and the salinity of water increased towards the north of the basin. The most prevalent water type is Ca–HCO₃ followed by water types Ca–NO₃, Ca–Cl, Ca–SO₄ and Mg–HCO₃. The Ca–NO₃ water type is associated with high nitrate pollution. Agricultural and industrial activities were associated with elevated level of NO₃⁻. Mineral dissolution/weathering of evaporites dominates the major element hydrochemistry of the area. Chemical properties of groundwater in Alvand region are controlled both by natural geochemical processes and anthropogenic activities.     

Potential hyperaccumulation of Pb, Zn, Cu and Cd in endurant plants distributed in an old smeltery, northeast China

The absorption and accumulation of Pb, Zn, Cu and Cd in some endurant weed plant species that survived in an old smeltery in Liaoning, China, were systematically investigated. Potential hyperaccumulative characteristics of these species were also discussed. The results showed that metal accumulation in plants differed with species, tissues and metals. Endurant weed plants growing in this contaminated site exhibited high metal adaptability. Both the metal exclusion and detoxification tolerance strategies were involved in the species studied. Seven species for Pb and four species for Cd were satisfied for the concentration time level standard for hyperaccumulator. Considering translocation factor (TF) values, one species for Pb, seven species for Zn, two species for Cu and five species for Cd possessed the characteristic of hyperaccumulator. Particularly, Abutilon theophrasti Medic, exhibited strong accumulative ability to four heavy metals. Although enrichment coefficients of all samples were lesser than 1 and the absolute concentrations didn’t reach the standard, species mentioned above were primarily believed to be potential hyperaccumulators.     

无高氯酸常压酸溶-ICP-MS法同时测定土壤中的As、Cd、Pb、Cr、Zn、Cu、Ni

采用无高氯酸常压酸溶分解土壤样品,利用等离子体质谱法可以1次溶矿测定As、Cd、Pb、Cr、Zn、Cu、Ni 7个重金属元素,具有较高的分析效率、较好的分析质量、较低的分析成本。实验表明,试样溶液中氯的含量对分析元素信号有较大影响。采用硝酸-氢氟酸-硫酸-过氧化氢分解样品以避免引入氯离子,从而能有效避免Cr、As元素在样品分解过程中的损失和氯离子产生的质谱干扰。Cd的测定需采用干扰校正公式扣除Sn的干扰。对于As元素,若试样溶液中不含或仅含微量的氯离子,采用标准模式测定即可得到理想的分析结果,否则必须采用CCT模式进行测定。除As以外的其他元素不论在标准模式或CCT模式下均能得到理想的分析结果。     

Trace metals (Cd,Pb, Cu,Zn and Ni) in sediment of the submarine pit Dragon ear (Soline Bay,Rogoznica, Croatia)

Vertical profiles of trace metal (Cd, Pb, Zn, Cu, Ni) concentrations, organic matter content, carbonate content and granulometric composition were determined in two sediment cores from the submarine pit Dragon Ear (Middle Adriatic). Concentrations of the analyzed metals (Cd: 0.06–0.12 mg kg⁻¹, Pb: 28.5–67.3 mg kg⁻¹, Zn: 17.0-65.4 mg kg⁻¹, Cu: 21.1–51.9 mg kg⁻¹, Ni: 27.8–40.2 mg kg⁻¹) were in usual range for Adriatic carbonate marine sediments. Nevertheless, concentrations of Cu, Zn, and especially Pb in the upper layer of sediments (top 12 cm) were higher than in bottom layer, while Cd and Ni concentration profiles were uniform. Regression analysis and principal component analysis were used to interpret distribution of trace metals, organic matter and carbonate content in sediment cores. Results of both analysis showed that concentrations of all trace metals in the core below the entrance to the pit were significantly positively correlated with organic matter and negatively correlated with carbonate, while in the core more distant from the entrance only Pb showed significant positive correlation with organic matter. Obtained results indicated that, except for lead which was enriched in surface sediment, in the time of sampling (before the building of the nautical marina) investigated area belonged to unpolluted areas.     

Mineral deposits and Cu–Zn–As dispersion–contamination in stream sediments from the semiarid Coquimbo Region,Chile

This paper presents Cu–Zn–As geochemical data from stream sediment surveys carried out in the three main watersheds of the Coquimbo Region of Chile. This mountainous semiarid realm occupies an area of 40,656 km² between 29° and 32°S. Given that the area has a long historical record of mining activities, important environmental disturbances were expected. However, despite the detection of three major geochemical anomalies for Cu, Zn, or As, only one can be unmistakably linked to the development of mining–metal recovery procedures (Andacollo–Panulcillo). An investigation of the other two anomalies (Elqui and Hurtado) reveals three major causes that fully or partially account for them: (1) the type of ore deposit and associated hydrothermal alteration; (2) the regional structural setting (intensity of fracturing); and (3) climate–landscape. Cu–Au–As epithermal deposits/prospects along the so-called El Indio belt are here regarded as the sources of both the Elqui and Hurtado anomalies. The strong advanced argillic alteration present in some of the epithermal deposits/prospects of the El Indio belt may have induced the loss of the buffering capacity of rocks, and therefore favoured metal dispersion during later oxidation–leaching of sulphides. This applies to the Elqui and Hurtado anomalies. Conversely, given that the potassic, propylitic and phyllic alterations do not affect the buffering capacity of rocks, only minor metal dispersion is observed in relation to the Los Pelambres porphyry copper deposit. Besides, the epithermal belt is located within a highly fractured Andean domain (3,000–4,000 m of altitude), which may have conditioned the fast unroofing of ore deposits, contributed to enhanced circulation of meteoric waters, and eventually, to strong oxidation, and leaching of metals. Metal dispersion is aggravated during rainy years in response to strong El Niño episodes.     

Assessment of Zn, Cu, Pb and Ni contamination in wetland soils and plants in the Lake Victoria basin

The impact of waste disposal on trace metal contamination was investigated in eleven wetlands in the Lake Victoria Basin. Samples of soil, water and plants were analysed for total Zn, Cu, Pb and Ni concentrations using flame atomic absorption spectrophotometry. The trace metal concentrations in soil were the highest in Katanga wetland with the highest mean concentrations of 387.5±86.5 mg/kg Zn, 171.5±36.2 mg/kg Pb, 51.20±6.69 mg/kg Cu and 21.33±2.23 mg/kg Ni compared to the lowest levels observed at Butabika (30.7±3.2 mg/kg Zn, 15.3±1.7 mg/kg Pb, 12.77±1.35 mg/kg Cu and 6.97±1.49 mg/kg Ni). Katanga receives waste from multiple industrial sources including a major referral city hospital while Butabika is a former solid waste dumpsite. Wetland soil near a copper smelter had a Cu concentration of 5936.3±56.2 mg/kg. Trace metal concentrations in industrial effluents were above international limits for irrigation water with the highest concentrations of 357,000 μg/L Cu and 1480 μg/L Zn at a Cu smelter and 5600 μg/L Pb at a battery assembling facility compared to the lowest of 50 μg/L Cu and 50 μg/L Zn in water discharged from Wakaliga dumpsite. Uptake of trace metals from soil differed from plant to plant and site to site. Higher levels of trace metals accumulated in the root rather than in the rhizome and the least amount was in the leaf. The study identifies industry as a potential source of trace metal contamination of water and the environment pent-up need for policy intervention in industrial waste management.     

The adsorption of Cu,Pb, Zn,and Cd on goethite from major ion seawater

The adsorption of Cu, Pb, Zn, and Cd on goethite (αFeOOH) from NaNO₃ solutions and from major ion seawater was compared to assess the effect of the major ions of seawater (Na, Mg, Ca, K, Cl, and SO₄) on the adsorption behavior of the metals. Magnesium and sulphate are the principal seawater ions which enhance or inhibit adsorption relative to the inert system. Their effect, as determined from the site-binding model of Davis et al. (1978), was a combination of changing the electrostatic conditions at the interface and decreasing the available binding sites.The basic differences between the experimental system of major ion seawater and natural seawater were examined. It was concluded that: 1) although the experimental metal concentrations in major ion seawater were higher than those found in natural seawater, estimates of the binding energy of Cu, Zn, and Cd with αFeOOH for natural seawater concentrations could be made from the data, 2) Cu, Pb, Zn, and Cd showed little or no competition for surface sites on goethite, and 3) the presence of carbonate, phosphate, and silicate had little or no effect on the adsorption of Zn and Cd on goethite.     

Status of anthropogenically induced metal pollution in the Kanpur-Unnao industrial region of the Ganga Plain, India

 The Ganga Plain is one of the most densely populated regions and one of the largest groundwater repositories of the Earth. For several decades, the drainage basin of the Ganga Plain has been used for the disposal of domestic and industrial wastes which has adversely affected the quality of water, sediments and agricultural soils of the plain. The concentrations of Al, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Sn, Zn and organic carbon were determined in river sediments and soils of the Ganga Plain in the Kanpur-Unnao industrial region in 1994 and 1995 (pre-monsoon period of April–May). High contents (maximum values) of C-org (12.0 wt. %), Cr (3.40 wt. %), Sn (1.92 wt. %), Zn (4000 mg/kg), Pb (646 mg/kg), Cu (408 mg/kg), Ni (502 mg/kg) and Cd (9.8 mg/kg) in sediments (<20 μm fraction); and C-org (5.9 wt. %), Cr (2.16 wt. %), Sn (1.21 wt %), Zn (975 mg/kg) and Ni (482 mg/kg) in soils (<20 μm) in the pre-monsoon period of 1994 were found. From 1994 to 1995 the contents of Fe and Sn in sediments increase whereas those of C-org, Cd, Cu, Ni and Zn decrease. Considering the analytical errors, Al, Co, Cr, Mn and Pb do not show any change in their concentrations. In soils, the contents of Cd, Fe and Sn increase whereas those of Ni decrease from 1994 to 1995. Aluminium, Co, Cr, Cu, Mn, Pb and Zn do not show any change in their concentrations from 1994 to 1995. About 90% of the contents of Cd, Cr and Sn; 50–75% of C-org, Cu and Zn; and 25% of Co, Ni and Pb in sediments are derived from the anthropogenic input in relation to the natural background values, whereas in soils this is the case for about 90% of Cr and Sn; about 75% of Cd; and about 25% of C-org, Cu, Ni and Zn. The sediments of the study area show enrichment factors of 23.6 for Cr, 14.7 for Cd, 12.2 for Sn, 3.6 for C-org, 3.2 for Zn, 2.6 for Cu and 1.6 for Ni. The soils are enriched with factors of 10.7 for Cr, 9.0 for Sn, 3.6 for Cd, 1.8 for Ni and 1.5 for Cu and Zn, respectively. Received: 3 March 1998 · Accepted: 15 June 1998     

Geochemical fractionation of Ni,Cu and Pb in the deep sea sediments from the Central Indian Ocean Basin: An insight into the mechanism of metal enrichment in sediment

Metal speciation study in combination with major element chemistry of deep sea sediments provided possible metal enrichment pathways in sediments collected from environmentally different locations of Central Indian Ocean Basin (CIB). Metal speciation study suggests that Fe–Mn oxyhydroxide phase was the major binding phase for Ni, Cu and Pb in the sediments. The second highest concentrations of all these metals were present within the structure of the sediments. Easily reducible oxide phase (within the Fe–Mn oxyhydroxide binding phases) was the major host for all the three metals in the studied sediments. Major element chemistry of these sediments revealed that there was an increased tendency of Cu and Ni to get incorporated into the deep sea sediment via the non-terrigenous Mn-oxyhydroxide fraction, whereas, Pb gets incorporated mostly via amorphous Fe-hydroxides into the sediment from the CIB. This is the first attempt to provide an insight into the mechanism of metal enrichment in sediment that host vast manganese nodule.     

GIS-based colour composites and overlays to delineate heavy metal contamination zones in the shallow alluvial aquifers, Ankaleshwar industrial estate, south Gujarat, India

In an attempt to delineate heavy metal contamination precincts and to evaluate the extent and degree of toxic levels, besides their possible sources, 38 water samples from Ankaleshwar Industrial Estate, south Gujarat, India were analyzed. By clutching geochemical analyses and GIS-based colour composites areas depicting anomalously high concentration of heavy metals (Mo, Zn, Pb, Ni, Co, Cd, etc.) in the groundwater were revealed. The multicomponent overlays in grey-scale facilitated in identifying situates of heavy metal ‘hot spots’, and lateral protuberances of the contamination plume around defile stretch of the main stream Amla Khadi flowing through the area. The multiple pollution plumes emerging from other parts of the area further coincide with effluent laden streams and small channels indicating industrial establishments as major sources of groundwater contamination. Influent nature of the streams, accelerated infiltration process, high mass influx and shallow groundwater table are the factors conducive for easy access of heavy metals to the phreatic aquifers affecting over 20 km² area. On the basis of P/U ratios (concentration of metals in polluted water to unpolluted water), geogenic and anthropogenic sources have been identified. Very high levels of technogenic elements present in the ground water raise concerns about possible migration into food crops, as the area is an important horticultural locale and is highly cultivated.     

Spatial variability of topsoil contamination with trace elements in preschools in Vilnius,Lithuania

An investigation of the spatial variability of topsoil contamination level was performed in 49 preschool playgrounds located in Vilnius city and correlated with urban (height and age of the preschools and height of surrounding buildings) and natural (altitude) factors. Composite samples, consisting of 20–30 sub-samples, were collected from 10 cm topsoil layer with a 3–5 m distance from each other. Sieved fraction (< 0.63 mm) was ashed at 400 °C, ground to < 1.0 μm and analysed for the real total concentrations of 22 trace elements (Ag, B, Ba, Co, Cr, Cu, Ga, Li, Mn, Mo, Nb, Ni, Pb, Sc, Sn, Sr, Ti, V, Y, Yb, Zn and Zr) using optical atomic emission spectrophotometry. Information on construction year and height (number of building stories) of preschool and surrounding buildings was acquired from the Centre of Registers of Lithuania. Out of 22 analysed elements, 13 to a greater extent exceeded the background values in several areas and were used to calculate the total contamination index (Z_s13). Out of 49 analysed areas, 21 had moderately hazardous to hazardous levels of contamination as indicated by Z_s13. The main contaminating elements, exceeding the permissible concentrations were Ag, Cu, Mo, Pb, Sn and Zn, the origins of which coincide with city industry and traffic. Topsoil around the newer preschool buildings, despite their location, contained lower concentrations of contaminants, while areas at higher altitudes were more contaminated than those located at lower altitudes. The latter causality is biased, as the city industry, and hence the highest contamination, is in districts located higher above sea level than the remaining studied sites.     

高压微波消解法测定醋酸纤维过滤器采集的微尘粒子中的砷镉钴铬铜铁锰镍铅钒锌

最新的流行病学研究表明,空气中较高浓度的悬浮细颗粒可能对人类的健康有不利的影响。根据该项研究显示,由于心脏病、慢性呼吸问题和肺功能指标恶化而导致死亡率的升高与细尘粒子有关。这些研究结果已经促使欧盟于1999年4月出台了限制空气中二氧化硫、二氧化氮、氧化氮、铅和颗粒物含量的法案（1999/30/EC）,对各项指标包括对可吸入PM10颗粒的浓度提出了新的限制性指标。PM10颗粒是指可以通过预分级器分离采集的气体动力学直径小于10 μm的细颗粒。目前研究的兴趣重点逐步偏向PM2.5这些更细微颗粒物,PM2.5这种颗粒物对健康有明显的不利影响。在欧盟指令2008/50/EC中,对PM10和PM2.5都提出了具体测定要求。