Modelling the concentrations of dissolved contaminants (Cd,Cu, Ni,Pb, Zn) in floodplain soils

Central European floodplain soils are often contaminated with potentially toxic metals. The prediction of their aqueous concentrations is a prerequisite for an assessment of environmental concerns. We tested the aqueous concentrations of cadmium (Cd), copper (Cu), nickel (Ni), lead (Pb) and zinc (Zn) derived from multi-surface adsorption modelling (on hydrous iron, aluminum and manganese oxides, clay and soil organic matter) against those analyzed in situ in the soil solution of four horizons of floodplain soils at the Elbe River, Germany. The input data for the reactive metals were derived from a seven-step sequential extraction scheme or from extraction with 0.43 M nitric acid (HNO₃) and evaluated in four modelling scenarios. In all scenarios, measured and modelled concentrations were positively related, except partially for Pb. Close reproduction of the measured data was obtained using measured data of accompanying cations and anions together with amounts of reactive metals from both the sequential extraction or from 0.43 M HNO₃ extraction, except for Cu, which was often strongly overestimated, and partially Cd. We recommend extraction with 0.43 M HNO₃ to quantify reactive metals in soil because the modelling results were metal-specific with better or equal results using the single extractant, the application of which is also less laborious. Approximations of ion concentrations and water contents yielded similar results. Modelled solid-phase speciation of metals varied with pH and differed from that from sequential extraction. Multi-surface modelling may be an effective tool to predict both aqueous concentrations and solid-phase speciation of metals in soil.     

Exposure assessment of heavy metals (Cd,Hg, and Pb) by the intake of local foods from Zhejiang,China

Considering the environmental pollution, food safety is of great concern to the consumers. The present study was conducted to assess the health risk of cadmium (Cd), mercury (Hg), and lead (Pb) through the dietary intake in Zhejiang, China. Eight hundred and sixty two food samples including aquatic products, meat, vegetables, milk and dairy products, and cereal grains were analyzed. Only 2.44 % (Cd), 1.39 % (Hg), and 1.51 % (Pb) of the samples exceeded the maximum allowable concentration set by Chinese Ministry of Health. The average dietary intakes of Cd, Hg, and Pb were estimated to be 0.26, 0.14, and 0.55 μg/kg bw/day, respectively. Compared with the reference doses, the mean exposure of Cd, Hg, and Pb was all less than the tolerable intake value. Only at the 95th percentile level, Cd and Hg exposure exceeded the values of tolerable intakes by 40 and 277 %, respectively. It indicates that there is low health risk to the dietary exposure of Cd, Hg, and Pb for general people in Zhejiang province, China.     

Modelling the potential mobility of Cd,Cu, Ni,Pb and Zn in Mollic Fluvisols

European floodplain soils are frequently contaminated with potentially toxic inorganic substances. We used a multi-surface model to estimate the aqueous concentrations of Cd, Cu, Ni, Pb and Zn in three Mollic Fluvisols from the Central Elbe River (Germany). The model considered complexation in solution and interactions with soil organic matter (SOM), a clay mineral and hydrous Al, Fe and Mn oxides. The amounts of reactive metals were derived from extraction with 0.43 M HNO₃. Modelling was carried out as a function of pH (soil pH ± 1.4) because it varies in floodplain soils owing to redox processes that consume or release protons. The fraction of reactive metals, which were dissolved according to the modelling, was predominantly <1%. Depending on soil properties, especially pH and contents of SOM and minerals of the clay fraction, the modelled concentrations partially exceeded the trigger values for the soil–groundwater pathway of the German soil legislation. This differentiation by soil properties was given for Ni, Pb and Zn. On the other hand, Cd was more mobile, i.e., the trigger values were mostly exceeded. Copper represented the opposite, as the modelling did not predict exceeding the trigger values in any horizon. Except for Pb and partially Zn (where oxides were more important), SOM was the most important adsorbent for metals. However, given the special composition and dynamics of SOM in mollic horizons, we suggest further quantitative and qualitative investigations on SOM and on its interaction with metals to improve the prediction of contaminant dynamics.     

Assessment of individual and combined toxicities of three heavy metals (Cu,Cd and Hg) by using Tigriopus fulvus

The toxicities of copper, cadmium, and mercury ions and their binary and ternary mixtures were studied using the copepods Tigriopus fulvus. The LC50 values measured after 48 h exposure to single metal solutions revealed a toxicities rank as follows: CdT. fulvus. The combined effect of the metals was found to be antagonistic for Cu?Cd, Hg?Cd, and Cu?Cd?Hg, additive for Hg?Cu.     

Effect of heavy metals (Hg and Zn) on the growth and phosphate solubilising activity in halophilic phosphobacteria isolated from Manakudi mangrove

The diversity of phosphobacteria in Manakudi mangrove ecosystem of Tamil Nadu was carried out in root and rhizosphere soil samples. The counts of phosphobacteria were found higher in root samples than in soil samples particularly in Hymenachene acutigluma. The abundance of phosphobacterial diversity in Manakudi mangrove showed high degree of positive correlation with the content of phosphate in rhizosphere soil of all the mangrove and associated plant species. Nine phosphobacterial species belonging to 7 genera were reported from Manakudi mangrove ecosystem. All the identified bacterial species are sensitive to both the heavy metals (mercury and zinc) in terms of growth and physiology even at lower concentrations. The content of protein and total sugars were increased by the higher concentrations of heavy metals whereas decreased trend was noticed in lower concentrations of heavy metals.     

Levels of heavy metals (Zn,Cu, Cd,and Pb) in mudskippers (Periophthalmodon schlosseri) and sediments collected from intertidal areas at Morib and Remis,Peninsular Malaysia

The concentrations of Zn, Cu, Cd, and Pb were determined in different tissues of mudskipper fishes Periophthalmodon schlosseri caught at two selected locations (Morib and Remis) of the intertidal mudflat area of Selangor state, West Coast of Peninsular Malaysia and in surface sediment samples. Metal concentrations in the mudskipper tissue and in the sediment samples tended to vary significantly (p < 0.05) between the two locations. Higher metal concentrations (except for Zn) were mostly found in the tissues of mudskippers from Remis. For sediment samples, significantly (p < 0.05) higher metal concentrations of all metals were also found at Remis. Generally, metal distribution between different tissues of mudskipper varied with scales being highly accumulative of Zn, Cd, and Pb, while for Cu, the highest mean concentrations were found in the liver. The lowest mean concentrations of Zn, Cu, and Cd were found in the muscles except for Pb, which was lowest in the liver. This study suggests that mudskippers can be potential biomonitoring organisms for heavy metal bioavailability and contamination of intertidal coastal mudflats. The concentrations of Cd and Pb were slightly above the acceptable limits of Malaysian and European food safety guidelines.     

Use of different soft tissues of Perna viridis a s biomonitors of bioavailability and contamination by heavy metals (Cd,Cu, Fe,Pb, Ni,and Zn) in a semi-enclosed intertidal water,the Johore Straits

Green-lipped mussels, Perna viridis, were collected from the eastern and western parts of the Johore Straits in September 2004 and January 2005. Based on the heavy metal concentrations in the different soft tissues (gonad, foot, mantle, gills, muscle, and remaining soft tissues) of these mussel samples, the eastern part of the Johore Straits (which is divided into two portions by a causeway), recorded higher levels of bioavailability and contamination by Cd, Cu, Fe, Ni, and Zn when compared to the western part, while Kg. Pasir Puteh in the eastern part was found to record the highest bioavailability and contamination by heavy metals. The use of different soft tissues of P. viridis as biomonitors of bioavailability and contamination by Cd, Cu, Fe, Pb, Ni, and Zn in the semi-enclosed Johore Straits is proposed, since erroneous results due to spawning and the problem of defecation before dissection could be overcome. Hence, a more accurate interpretation of the bioavailability and contamination by heavy metals in coastal waters could be obtained. To our knowledge, this is the most detailed study on the bioavailability and contamination of heavy metals in the Johore Straits on the Malaysian side of the waterway carried out by using the different soft tissues and metal distribution based on the Mussel Watch approach.     

Tissue distribution of Cd,Cu, Zn,Ni, Cr,Pb and Hg in striated heron,Butorides striatus (Aves: Ardeidae), in a fluvial ecosystem

In this study, the striated heron (Butorides striatus), a species that reproduces in the Middle Paraná River floodplain, was examined for lead, cadmium, chromium, zinc, nickel, mercury and copper concentrations, using liver, kidney, muscle, vertebra and feathers. The results showed low exposure to chromium because all tissue samples had concentrations below the limit of detection. Similar results were obtained for nickel and lead, with the exception of vertebra. This might be associated with either long-term exposure to these metals, or it may be that both nesting and wintering areas are non-polluted. Zinc and copper, both essential metals, were found in all tissues and their concentrations were within the ranges reported in the literature. Mercury was also found in all tissues, but at very low concentrations and even at concentrations below those that produce negative effects in several species of birds (e.g. reproductive success, food intake). Studies of this type are needed to interpret the role of organisms within environments impacted by different human activities.     

Trace metals in mussels (Mytilus edulis) from southwest Iceland

The temperate population of the tropical anemonefish Amphiprion clarkii has a seasonality of reproduction, larval settlement and growth. There was a considerable difference in size (15–47 mm) among 0-year olds in December, after the season of larval settlement and growth. This difference could be attributed mainly to a difference in the duration of the first growing season spent after settlement and a social inhibition of growth of the subordinate late settlers by frequent attacks by the dominant early settlers. The growth equation which was used to describe the growth of tagged individuals estimated that an anemonefish would get an opportunity to spawn within four of five years after settlement. Breeding adult pairs occupied almost all sea anemones essential to breeding within a 50×50 m study area, and all 17 new adults that matured from non-breeding juveniles to breeding adults between June 1983 and August 1985 were found in the territories from which either or both of the mated adults had disappeared. The new adults were large juveniles who had resided near those vacant territories before. These results suggest that the onset of breeding by an individual is not only determined by his age, but also by his ranking in the dominance hierarchy. Therefore, the difference in size among 0-year olds in December might give rise to the difference in age of the earliest breeding and might be a factor in making a female apply more reproductive effort at the beginning of the season.     

Effects of three low-molecular-weight organic acids (LMWOAs) and pH on the mobilization of arsenic and heavy metals (Cu, Pb, and Zn) from mine tailings

Natural organic acids may play an important role in influencing the mobility of toxic contaminants in the environment. The mobilization of arsenic (As) and heavy metals from an oxidized Pb–Zn mine tailings sample in the presence of three low-molecular-weight organic acids, aspartic acid, cysteine, and succinic acid, was investigated at a mass ratio of 10 mg organic additive/g mine tailings in this study. The effect of pH was also evaluated. The mine tailings sample, containing elevated levels of As (2,180 mg/kg), copper (Cu, 1,100 mg/kg), lead (Pb, 12,860 mg/kg), and zinc (Zn, 5,075 mg/kg), was collected from Bathurst, New Brunswick, Canada. It was found that the organic additives inhibited As and heavy metal mobilization under acidic conditions (at pH 3 or 5), but enhanced it under neutral to alkaline conditions (at pH above 7) through forming aqueous organic complexes. At pH 11, As, Cu, Pb, and Zn were mobilized mostly by the organic additives, 45, 46, 1,660, and 128 mg/kg by aspartic acid, 31, 28, 1,040, and 112 mg/kg by succinic acid, and 53, 38, 2,020, and 150 mg/kg by cysteine, respectively, whereas those by distilled water were 6, 16, 260, and 52 mg/kg, respectively. It was also found that the mobilization of As and the heavy metals was closely correlated, and both were closely correlated to Fe mobilization. Arsenic mobilization by the three LMWOAs was found to be consistent with the order of the stability of Fe–, Cu–, Pb–, and Zn–organic ligand complexes. The organic acids might be used potentially in the natural attenuation and remediation of As and heavy metal–contaminated sites.     

Population health risk via dietary exposure to trace elements (Cu,Zn, Pb,Cd, Hg,and As) in Qiqihar,Northeastern China

The estimated daily intakes (EDIs) of six trace elements (Cu, Zn, Pb, Cd, Hg, and As) in vegetables (leafy vegetable, i.e., bok choy, fruit vegetables, i.e., cucumber and tomato, and other categories, i.e., mushroom, kidney bean, and potato), cereals (rice and wheat flour), and meats (pork, mutton, and beef) most commonly consumed by adult inhabitants of Qiqihar, Northeastern China, were determined to assess the health status of local people. The average EDIs of Cu, Zn, Pb, Cd, Hg, and As were with 20.77 μg (kg bw)^?1 day^?1 of Cu, 288 μg (kg bw)^?1 day^?1 of Zn, 2.01 μg (kg bw)^?1 day^?1 of Pb, 0.41 μg (kg bw)^?1 day^?1 of Cd, 0.01 μg (kg bw)^?1 day^?1 of Hg, and 0.52 μg (kg bw)^?1 day^?1 of As, respectively, which are below the daily allowance recommended by FAO/WHO. However, the maximum EDIs of Pb and Cd were 4.56 μg (kg bw)^?1 day^?1 and 1.68 μg (kg bw)^?1 day^?1, respectively, which are above the recommended levels [i.e., 3.58 μg (kg bw)^?1 day^?1 for Pb and 1.0 μg (kg bw)^?1 day^?1 for Cd] by FAO/WHO. This finding indicates that the potential health risk induced by daily ingestion of Pb and Cd for the local residents should receive a significant concern. Similarly, we detected elevated Pb and Cd concentrations, i.e., with average of 13.58 and 0.60 mg kg^?1 dw, respectively, in the adult scalp hairs. Consumption of rice, potato, bok choy, and wheat flour contributed to 75 and 82% of Pb and Cd daily intake from foodstuffs. Nevertheless, human scalp hair is inappropriate biological material for determination of the nutritional status of trace elements in this region.     

Biomonitoring of heavy metal (Cd,Cu, Pb,and Zn) concentrations in the west intertidal area of Peninsular Malaysia by using Nerita lineata

Snails, Nerita lineata, were collected from 15 sites along the west intertidal area of Peninsular Malaysia from December 2005 until April 2006. The concentrations of heavy metals (Cd, Cu, Pb, and Zn) were determined in the total soft tissues, operculums, and shells of the snails. Different patterns of heavy metal distributions were found in the different tissues (shell, operculums, and soft tissues) as well as spatial variations of heavy metal concentrations in the snails. This shows that the distribution of metals in the shells and the total soft tissues of N. lineata were not similar which could be due to different rates of metal accumulation, excretion, and sequestration. Since N. lineata is abundant on the rocky shores, below jetties and mangrove trees along the west intertidal area of Peninsular Malaysia and accumulate heavy metals, the snails are therefore potential biomonitors of heavy metal contamination for the west intertidal area of Peninsular Malaysia.     

干旱区绿洲土壤镉、铅、锌、镍的形态转化

以我国西北干旱区绿洲土壤为供试土壤,采用Tessier形态连续浸提方法,研究了土壤中Cd、Pb、Zn、Ni单一胁迫下的形态分布及再分配趋势.试验结果表明,原状土壤中Cd的主要赋存形态为铁锰氧化态,Pb、Zn、Ni则以残渣态为主;外源可溶性重金属进入土壤后,Cd、Pb、Zn、Ni的主要赋存形态和形态分布特征均发生显著改变,各形态的响应程度因元素而异;重金属的活性均有不同程度的提高,Cd的活性最大;重金属的形态分布是不稳定的,尤以Zn、Pb为甚,尽管会随着时间和作物的影响继续向着稳定的方向转化,但过程是缓慢的.因此,重金属污染对土壤环境的影响是持久的.     

EDTA and citric acid mediated phytoextraction of Zn, Cu, Pb and Cd through marigold (Tagetes erecta)

Phytoextraction is an emerging cost-effective solution for remediation of contaminated soils which involves the removal of toxins, especially heavy metals and metalloids, by the roots of the plants with subsequent transport to aerial plant organs. The aim of the present investigation is to study the effects of EDTA and citric acid on accumulation potential of marigold (Tagetes erecta) to Zn, Cu, Pb, and Cd and also to evaluate the impacts of these chelators (EDTA and citric acid) in combination with all the four heavy metals on the growth of marigold. The plants were grown in pots and treated with Zn (7.3 mg l(-1)), Cu (7.5 mg I(-1)), Pb (3.7 mg l(-1)) and Cd (0.2 mg l(-1)) alone and in combination with different doses of EDTA i.e., 10, 20 and 30 mg l(-1). All the three doses of EDTA i.e., 10, 20 and 30 mg l(-1) significantly increased the accumulation of Zn, Cu, Pb and Cd by roots, stems and leaves as compared to control treatments. The 30 mg l(-1) concentration of citric acid showed reduced accumulation of these metals by root, stem and leaves as compared to lower doses i.e., 10 and 20 mg l(-1). Among the four heavy metals, Zn accumulated in the great amount (526.34 mg kg(-1) DW) followed by Cu (443.14 mg kg(-1) DW), Pb (393.16 mg kg(-1) DW) and Cd (333.62 mg kg(-1) DW) in leaves with 30 mg l(-1) EDTA treatment. The highest concentration of EDTA and citric acid (30 mg l(-1)) caused significant reduction in growth of marigold in terms of plant height, fresh weight of plant, total chlorophyll, carbohydrate content and protein content. Thus EDTA and citric acid efficiently increased the phytoextractability of marigold which can be used to remediate the soil contaminated with these metals.     

Effect of Cd on accumulation and loss of 210Po in the mussel Mytilus edulis

As a result of ²¹⁰Po's previously identified association with sulphur-rich proteins, metallothioneins could have a significant effect on the behaviour and fate of ²¹⁰Po in molluscs. Starved control and cadmium-exposed mussels, Mytilus edulis, were fed ²¹⁰Po-labelled algae (Isochrysis galbana) for 5 d and then allowed to depurate in clean sea water. Cadmium-exposed M. edulis accumulated less ²¹⁰Po in the digestive gland and the remainder of the tissue than control mussels, although this was due to a decrease in tissue weight. More than 40% of ²¹⁰Po was identified as being associated with high molecular weight and heat-treated cytosol proteins in M. edulis. Mussels in a starved state are known to recycle as much as 90% of their amino acids. It is proposed that ²¹⁰Po associated with these and other proteins is recycled, explaining why no significant loss of ²¹⁰Po was observed from the remainder of the tissue in either control or Cd-exposed mussels. Cadmium-induced metallothioneins had no effect on the distribution of ²¹⁰Po in M. edulis; <5% associated with the cytosolic fraction was considered to principally contain metallothioneins. It is suggested that ²¹⁰Po's apparent relationship with metallothioneins is coincidental rather than connected with its role in the regulation of metals. Received: 30 March 1998 / Accepted: 3 August 1998     

Extraction of Co,Ni, Cu,Zn and Cd ions using 2-aminophenylaminopropylpolysiloxane

Insoluble porous solid functionalized ligand system bearing 2-aminophenylaminopropyl chelating ligand of the general formula P–(CH₂)₃NH–(C₆H₄)–NH₂ was prepared via the sol–gel process, where P represents [Si–O] _n polysiloxane network. First, the 2-aminophenylaminopropylsilane agent was prepared by substitution reaction between 3-chloropropyltrimethoxysilane and 1,2-phenylenediamine, followed by hydrolytic polycondensation between 2-aminophenylaminopropylsilane agent and tetraethylorthosilicate(TEOS). The immobilized 2-aminophenylaminopropylpolysiloxane P–(CH₂)₃NH–(C₆H₄)–NH₂(P–AphA) was characterized by ¹³C NMR, XPS, and FTIR. The results showed that 1,2-phenylenediamine groups were introduced onto polysiloxane network. The functionalized ligand system exhibits 90–100% metal uptake capacity for all metal ions except Cd²⁺. The elemental analysis data and the metal uptake capacities of the immobilized ligand system suggest that over than 90% ligand sites were involved in coordination with metal ions except that of cadmium forming 1:1 metal to ligand ratio complexes.     

Linear alkylbenzene sulphonates (LAS) and bioaccumulation of heavy metals (Cu and Pb) in Ruditapes philippinarum

The effect of linear alkylbenzene sulphonate (LAS) on copper and lead bioaccumulation in Ruditapes philippinarum was studied. The in vitro and in vivo effect of LAS on acid and alkaline phosphatase activities was also examined. For lead, significant differences (P<0.01) were observed between organisms exposed to lead and to the mixture of LAS and lead. In the case of copper, these differences were only significant in the digestive gland (P<0.05). In vitro acid phosphatase was inhibited by LAS and the mixture of LAS with copper showed the effect of decreasing the enzymatic activity. Nevertheless, in vivo no significant differences in the digestive gland and gills (P < 0.05) were observed.     

Geo-accumulation index and contamination factors of heavy metals (Zn and Pb) in urban river sediment

The aim of the present study was to appraise the levels of heavy metal contamination (Zn and Pb) in sediment of the Langat River (Selangor, Malaysia). Samples were collected randomly from 15 sampling stations located along the Langat River. The parameters measured were pH, redox potential, salinity, electrical conductivity, loss of ignition, cation exchanges capacity (Na, Mg, Ca, K), and metal ions (Zn and Pb). The geo-accumulation index (I _geo) and contamination factor (C _f) were applied to determine and classify the magnitude of heavy metal pollution in this urban river sediment. Results revealed that the I _geo of Pb indicated unpolluted to moderately polluted sediment at most of the sampling stations, whereas Zn was considered to be within background concentration. The I _geo results were refined by the C _f values, which showed Pb with very high C _f at 12 stations. Zinc, on the other hand, had low to moderate C _f values. These findings indicated that the sediment of the Langat River is severely polluted with Pb. The Zn concentration at most sampling points was well below most sediment quality guidelines. However, 40% of the sampling points were found to have a Pb concentration higher than the consensus-based probable effect concentration of 128 mg/kg (concentrations above this value are likely to cause harmful effects). This result not only highlights the severity of Pb pollution in the sediment of the Langat River, but also the potential risk it poses to the environment.     

Effect of Chlorination on the Gill Lipids of the Mussel Mytilus edulis (L)

Experiments are described which involve the chlorination of standard solutions of lipids and populations of the mussel, Mytilus edulis (L). The object was to test the hypothesis that chlorine will bind to unsaturated lipids. Evidence is presented that chlorine and aqueous chlorinated species rapidly and readily form addition compounds with unsaturated lipids in vivo as well as in vitro. The relevance of these findings to possible environmental effects of chlorination is discussed.     

Effect of suspended bottom material on growth and energetics in Mytilus edulis

The influence of suspended, natural silt (0 to 20 mg l^-1) in addition to unicellular algal cells (Phaeodactylum tricornutum) (o to 20.000 cells ml^-1) on clearance, growth and energetics in Mytilus edulis has been studied. Clearance increased by 32 to 43% by the addition of 5 mg silt l^-1 as compared to clearance in a pure algal suspension. Ingestion and growth rate increased with algal concentration, and growth rate was further increased by 30 to 70% by the addition of 5 mg silt l^-1. A growth rate comparable to maximum natural growth rates was reached only at the highest algal concentration in the presence of 5 mg siltl^-1. Assimilation efficiency of P. tricornutum decreased from 77% at 5,000 cells ml^-1 to 52% at 20,000 cells ml^-1. In the experiments with silt added, some 20 to 30% of the assimilated organic matter originated from the suspended bottom material. Net growth efficiency increased with growth rate at a decelerating rate, approaching a maximum of about 70%. It is concluded that suspended bottom material, which is always present in M. edulis' natural habitats, serves as an additional food source, and that M. edulis depends on suspended bottom material to exploit fully its clearance potential, and to reach the maximum growth rates observed in nature.