Speciation of heavy metals in sediments from the Scheldt estuary,Belgium

A simple three-step sequential extraction procedure was applied to study the speciation of heavy metals in sediment from Scheldt estuary, and their relationship to sediment grain size and organic matter content. The sedimentary metal content was fractionated into carbonate and exchangeable, metals bound to organic matter and residual fractions. Sedimentary total metal content was also determined using an industrial microwave (ETHOS 900) HF/HNO₃ extraction method. The extracts were analysed for metals using inductively coupled plasma atomic emission spectrometry. The bioavailable fraction (exchangeable and metals bound to organic matter) comprised less than the other forms. Residue metals were the dominant form of metals in almost all studied sites. The average total metal content for the studied sites decreased in the order Fe>Cr>Cu>Co>Zn>Pb>Cd. Based on average values for the studied sites, the highest bioavailable metals in sediments were Cd (38%) from Westkapelle, Zn (17%) from Yerseke, Co (12%) from Domburg, Cr (9%) from Vlissingen, Fe and Pb each (2%) from Yerseke, and Cu (1%) from Domburg. Metal recovery was good, with<10% difference between the total metal recovered through the extractant steps and the total metal determined using HF/HNO₃ extract.     

Heavy metals and soil microbes

Heavy metal pollution is a global issue due to health risks associated with metal contamination. Although many metals are essential for life, they can be harmful to man, animal, plant and microorganisms at toxic levels. Occurrence of heavy metals in soil is mainly attributed to natural weathering of metal-rich parent material and anthropogenic activities such as industrial, mining, agricultural activities. Here we review the effect of soil microbes on the biosorption and bioavailability of heavy metals; the mechanisms of heavy metals sequestration by plant and microbes; and the effects of pollution on soil microbial diversity and activities. The major points are: anthropogenic activities constitute the major source of heavy metals in the environment. Soil chemistry is the major determinant of metal solubility, movement and availability in the soil. High levels of heavy metals in living tissues cause severe organ impairment, neurological disorders and eventual death. Elevated levels of heavy metals in soils decrease microbial population, diversity and activities. Nonetheless, certain soil microbes tolerate and use heavy metals in their systems; as such they are used for bioremediation of polluted soils. Soil microbes can be used for remediation of contaminated soils either directly or by making heavy metals bioavailable in the rhizosphere of plants. Such plants can accumulate 100 mg g^?1 Cd and As; 1000 mg g^?1 Co, Cu, Cr, Ni and 10,000 mg g^?1 Pb, Mn and Ni; and translocate metals to harvestable parts. Microbial activity changes soil physical properties such as soil structure and biochemical properties such as pH, soil redox state, soil enzymes that influence the solubility and bioavailability of heavy metals. The concept of ecological dose (ED₅₀) and lethal concentration (LC₅₀) was developed in response to the need to easily quantify the influence of pollutants on microbial-mediated ecological processes in various ecosystems.     

Biokinetic modeling of heavy metals in earthworms

Studies concerning bioaccumulation kinetics and bioconcentration factor (BCF) of heavy metals like zinc (Zn), lead (Pb), chromium (Cr), cadmium (Cd), and copper (Cu) in earthworm Eudrilus eugeniae tissues including integument, gizzard, clitellum, and head region were undertaken. Calculated BCF, predicted K _ow, and predicted K _oc showed a significant correlation between heavy metals in different earthworm tissues, in substrate spiked with heavy metals. The regression coefficient (r ²) between heavy metal uptake concentration and exposure time varied between 0.73 and 0.99, indicating significant correlation. The K _oc was a maximum of 13.9016 in case of Cu and integument at an exposure time of 100 days and a minimum of 0.1114 in case of Cr with respect to head at the same exposure time. Earthworms accumulated heavy metals following chronic exposure to municipal solid waste containing heavy metals. BCF and uptake rate kinetics of heavy metals were calculated and showed increased values in head tissue followed by integument.     

Heavy metals in three commercially valuable cyprinids in the river Panjkora,district Lower Dir,Khyber Pakhtunkhwa,Pakistan

This study was conducted in river Panjkora (Khall, upstream; Timergara, downstream) and its tributary (Konhaye stream, reference site) at district Lower Dir. The study was aimed to assess heavy metal load in gills, liver, kidneys, and muscles of three fish species, namely Schizothorax esocinus, Racoma labiata, and Crossocheilus diplocheilus. The heavy metals, including nickel, cadmium, lead, copper, zinc, chromium, iron, and manganese were determined using an atomic absorption spect-rophotometer. Nickel and cadmium were not detected in any of the collected specimens at all sampling sites. Concentration of the detected metals varied significantly depending upon fish species and tissue type. Crossocheilus diplocheilus showed higher accumulated concentration of heavy metals while R. labiata contained the least. Schizothorax esocinus and R. labiata displayed significant differences in their concentrations of metals. The order of accumulation of heavy metals in different tissues was liver>kidneys>muscles>gills. Data demonstrated that heavy metal levels in the studied species were within permissible limits and thus, apparently suitable for human consumption. Currently, the river contains a sewage burden, and continued heavy pollution may ultimately lead to serious problems in the future.     

Accumulation of some metals in Morinda lucida from Nigeria

Transfer coefficients of the four metals As, Cd, Hg, and Pb were determined in the leaves and barks of Morinda lucida collected in Nigeria, with the view to quantify relative differences in the bioavailability of the metals to these parts of the plant. Samples were acid digested and the levels of the metals in the digestates were determined using an atomic absorption spectrophotometer. Certain properties of the soils, i.e., pH, clay fraction, electrical conductivity, cation exchange capacity, and organic matter, were also determined. The latter influence the bioavailability of the metals. All parameters correlated with the concentrations of the metals in soils. Transfer coefficient values recorded for Cd and Pb in various tissues of M. lucida Benth were within the expected ranges, while those of As and Hg showed elevated topsoil concentrations of metals. The order of bioavailability of the metals and their bioaccumulation in the tissues of M. lucida Benth was Hg > Cd > As > Pb. Stem barks of the plant showed the least bioaccumulation of all four metals and hence are most suitable for therapeutic purposes. Vegetative parts of M. lucida Benth used for therapeutic purposes should be sourced at sites that will give low transfer coefficient in order to reduce human exposure to toxicity associated with ingestion of heavy metals.     

污染土壤中有机质结合态重金属的研究

用物理与化学相结合的方法研究了2个污染土壤剖面中有机质结合重金属（Cd、Cu、Pb和Zn）的分布，把有机质相结合态重金属分为颗粒状有机质（POM）结合的重金属和与细土腐殖质结合的重金属。结果表明，土壤POM对重金属有明品的富集作用，其中〉2mmPOM重金属Cd、Cu、Pb和Zn的富集系数分别在1．4～3．2、2．5～2．6、2．8—3．9和3．0～3．9之间；而0．05～2mmPOM重金属Cd、Cu、Pb和Zn的富集系数分别在2．7～7．8、3．2～6．4、3．2～9．3和3．2～5．6之间，0．05～2mmPOM组分中重金属的平均富集高于〉2mmPOM组分。POM中重金属的富集程度与土壤重金属的积累呈正相关。有机质结合态重金属占土壤重金属总最的比例随土壤有机质积累而增高，表土层约40％以上的重金属以有机质结合态存在。     

Uncommon heavy metals,metalloids and their plant toxicity: a review

Heavy metals still represent a group of dangerous pollutants, to which close attention is paid. Many heavy metals are essential as important constituents of pigments and enzymes, mainly zinc, nickel and copper. However, all metals, especially cadmium, lead, mercury and copper, are toxic at high concentration because of disrupting enzyme functions, replacing essential metals in pigments or producing reactive oxygen species. The toxicity of less common heavy metals and metalloids, such as thallium, arsenic, chromium, antimony, selenium and bismuth, has been investigated. Here, we review the phytotoxicity of thallium, chromium, antimony, selenium, bismuth, and other rare heavy metals and metalloids such as tellurium, germanium, gallium, scandium, gold, platinum group metals (palladium, platinum and rhodium), technetium, tungsten, uranium, thorium, and rare earth elements yttrium and lanthanum, and the 14 lanthanides cerium, dysprosium, erbium, europium, gadolinium, holmium, lutetium, neodymium, promethium, praseodymium, samarium, terbium, thulium and ytterbium.     

Low uptakes of Cd,Cu, and Zn in Dugesia japonica,a freshwater planarian with higher tolerance to metals

Although a freshwater planarian is proposed as a potential model for studying toxicities of environmental pollutants, they are less sensitive to metal exposures, compared to other freshwater invertebrates. We hypothesised that the metal uptake is low in treated planarians, which may lead to their higher tolerance to metals. The acute toxicities of Cu and Zn to Dugesia japonica were determined. The 24- and 48-h median lethal concentrations were 4.50 and 3.46?mg?L^?1, respectively, for Cu, and 41.97 and 37.79?mg?L^?1, respectively, for Zn. Accordingly, combining with the data on Cd in our previous study, higher tolerance of planarians to metals was revealed. Also, tissue levels of Cd, Cu, and Zn in treated D. japonica were determined, and their dissolved uptake rate constants (k₁) were calculated. Results showed that bioaccumulations of these metals in D. japonica were, indeed, lower than that in other freshwater invertebrates having higher susceptibilities to these metals.     

Chemical fractionation of metals in core sediments of Orogodo River,southern Nigeria

Sequential chemical extraction of metals (Cu, Ni, Mn, Fe, Pb, Cr, and Zn) from core sediments of the Orogodo River was carried out with a view of providing information on the phase distribution of these metals with respect to depths and seasons. The results indicate that copper was speciated into organic matter/sulfide, Fe–Mn oxides, and residual forms at 0–5?cm depth while at deeper sections copper was predominantly in the residual form. Nickel was speciated mainly into Fe–Mn oxides and residual forms. The average of lead in various particulate phases of the sediment are 0–100% for residual; 0–8% for carbonate; 0–16.2% for exchangeable; 0–10% for organic matter/sulfide form and 22–56% for Fe–Mn oxides bound metals. Manganese was speciated into exchangeable (10–36%) and Fe–Mn oxides bound (10–48%) at the surface layers of 0–20?cm depths and predominantly in the residual form in deeper sections implying partitioning into trioctahydral clay and/or well-defined crystalline oxides. Iron was predominantly in the Fe–Mn oxides and residual fractions, less than 8% in the organic fraction, and 24.4–37.3% in the exchangeable and carbonates fractions at the surface. The percentage contributions of iron in the exchangeable and carbonate fractions decreased to 3.2% at 55–60?cm depth. The amount of chromium in the exchangeable fraction ranged from 0% to 7% for exchangeable; 0–26.5% for organic matter/sulfide bound; 3.8–17.9% for Fe–Mn oxides; and 46.8–100% for residual fraction. The mobility factors of the metals indicated that these metals were relatively mobile at top sections as compared with deeper sections. The overall picture of metal mobility and availability indicates potential contamination risk by Fe, Zn, Mn, and Pb in the Orogodo River sediment system.     

Heavy metals and pesticides in anuran spawn and tadpoles,water, and sediment

High concentrations of metals (cadmium, copper, lead, and zinc) and of lindane were measured in the sediment and in the spawn and tadpoles of Bufo bufo, Rana dalmatina, and Rana ridibunda from two Austrian locations. Residues in spawn suggest maternal transfer. Increase of the metal concentrations from spawn to advanced tadpole stage is explained by the larval microphaguous feeding habits which cause high exposition of the tadpoles to substances concentrating in sediments and suspended particles. Metal and pesticide concentrations in spawn and tadpoles are toxic to various other aquatic organisms and are furthermore considered to be potentially hazardous to the anurans themselves. The results are conform with world‐wide observations of contamination of anuran larvae with heavy metals, and prove the significance of non‐point source chemical exposure due to allochthonous toxicant input by wind load and precipitation.     

Distribution,removal and chemical forms of heavy metals in polluted rice seed

In this paper, the distribution, removal and binding forms of heavy metals in polluted seeds of rice were studied using the methods of histochemistry and biochemistry. The results indicate that the distribution of heavy metals in rice grains was very uneven. The heavy metals in rice grains chiefly exist in association with the parts of high protein. Separation of proteins by Sephadex chromatography and subsequent analysis by atomic absorption spectroscopy revealed that Cd, Pb and As were mainly bound to protein of 54.5 and 5.50 kD molecular weights. During the rice processing, the concentrations of heavy metals in the edible rice decrease greatly, for some heavy metals in these parts of chaff, coarse rice bran and fine rice bran were removed.     

Heavy metals,occurrence and toxicity for plants: a review

Metal contamination issues are becoming increasingly common in India and elsewhere, with many documented cases of metal toxicity in mining industries, foundries, smelters, coal-burning power plants and agriculture. Heavy metals, such as cadmium, copper, lead, chromium and mercury are major environmental pollutants, particularly in areas with high anthropogenic pressure. Heavy metal accumulation in soils is of concern in agricultural production due to the adverse effects on food safety and marketability, crop growth due to phytotoxicity, and environmental health of soil organisms. The influence of plants and their metabolic activities affects the geological and biological redistribution of heavy metals through pollution of the air, water and soil. This article details the range of heavy metals, their occurrence and toxicity for plants. Metal toxicity has high impact and relevance to plants and consequently it affects the ecosystem, where the plants form an integral component. Plants growing in metal-polluted sites exhibit altered metabolism, growth reduction, lower biomass production and metal accumulation. Various physiological and biochemical processes in plants are affected by metals. The contemporary investigations into toxicity and tolerance in metal-stressed plants are prompted by the growing metal pollution in the environment. A few metals, including copper, manganese, cobalt, zinc and chromium are, however, essential to plant metabolism in trace amounts. It is only when metals are present in bioavailable forms and at excessive levels, they have the potential to become toxic to plants. This review focuses mainly on zinc, cadmium, copper, mercury, chromium, lead, arsenic, cobalt, nickel, manganese and iron.     

Geochemical distribution,bioavailability and potential toxicity of some trace metals in a complex micro-tidal estuary,Southwest India

The spatial and temporal variations of some trace metals in the surface sediments of Cochin Estuary were analyzed along with their geochemical associations to identify the possible sources, bioavailability and the health risks posed by them. The dominance of kaolinite and suggested that clay minerals distribution is influenced by sediment sorting. Total metal analysis revealed enrichment for Cd, Pb and Zn due to anthropogenic activities. The speciation analysis established that notwithstanding the large availability, carbonate as well as organic and sulfides bound fractions showed negligible associations with most of the metals. Hydrous Fe–Mn oxides appeared to play a major role in controlling the fate and transport of these metals in the sediments of Cochin Estuary. Lower contribution of the residual fractions for Cd (21%–26%), Pb (<60%) and Zn (24%–42%) indicated an obvious increase of other geochemical fractions. Risk assessment analysis revealed that regardless of total concentration, none of the analyzed metals were at safe levels in the estuary as appreciable percentages were found to be associated with mobile geochemical forms. The speciation study conspicuously established that the metals originating from non-geogenic sources are largely associated with the labile fractions and hence are more detrimental to the aquatic biota.     

Concentration of polyvalent metals by seaweeds in Vostok Bay,Sea of Japan

Spectrophotometric methods were used to measure the contents of the polyvalent metals Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo and Zn in 16 species of red, brown, and green seaweeds and 2 species of higher water plants collected from the intertidal and sublittoral zones of Vostok Bay, Sea of Japan. Some of the species displayed a unique capability for increased accumulation of groups of several metals. We have termed this ability specific group concentration. Thus, Ptilota filicina concentrates Ti, V, Mn, Fe, Ni, Cu, Zn, and Mo; Polysiphonia japonica Ti, V, Mn, Fe, Zn, Mo, and Cr; Rhodomela larix Ti, V, Mn, Fe, Ni, Zn, and Cr; Agarum cribrosum Ti, V, Mn, Fe, Ni, Zn, and Cr; Ulvaria splendens Ti, V, Mn, Fe, Ni, and Cu; Ulva fenestrata Mn, Fe, Ni, and Cu; Enteromorpha prolifera Mn, Co, Zn, Mo, and Cr; codium yessoensis V, Mn, Fe, Ni, and Cr; Zostera asiatica Ti, Mn, Ni, and Mo; Phyllospadix iwatensis Ti, V, Mn, Fe, and Zn. Specific group concentration makes possible a new approach to the study of active transport of polyvalent metals, physiologically significant for live organisms, through cell membranes, and the study of the formation of complex metal compounds inside the cell, i.e., the study of the processes that determine the degree of element concentration. The contents of the metals studied in sea water and the accumulation coefficients were also determined. The variation range is extremely high both for the seaweed species and metals investigated. Maximum coefficients were noted for Mn: 1.8·10⁵; Ti: 4.4·10⁴; Fe: 2.4·10⁴; Cr: 1.2·10⁶.     

猪粪混合堆肥过程中重金属含量的变化

在猪粪混合堆肥中，采用不同的通风方式和填充料，分析该过程中重金属总量和DTPA提取的重金属含量变化。结果表明，通过猪粪混合堆肥，重金属总量不会降低，但重金属生物有效性可降低；在猪粪与木屑混合堆肥中，加入树叶或鸡粪均能显著降低重金属的生物有效性，强制通风 机械翻堆比单一机械翻堆更能降低重金属的生物有效性。     

The dynamics of heavy metals in plant-soil interactions

The effects of soil contamination by heavy metals are studied by a mathematical interaction model, validated by experimental results. The model relates the dynamics of uptake of heavy metals from soil to plants. The model successfully fitted the experimental data and made it possible to predict the threshold values of total mortality. Data are taken from soil with Cd, Cu and Zn treatments for alfalfa, lettuce, radish and Thlaspi caerulescens, measuring the concentrations in the aboveground biomass of plants. At low concentrations, the effects of heavy metals are moderate, and the dynamics seem to be linear. However, increasing concentrations exhibit nonlinear behaviors.     

Concentration of heavy metals in water and chub, Leuciscus cephalus (Linn.) from the river Yildiz, Turkey

The concentration of heavy metals (Cu, Fe and Zn) were determined by atomic absorption spectrophotometry in the river water and the edible muscle tissues of chub, Leuciscus cephalus, from river Yildiz, Turkey, and in the waste water The following results were found in the water of the river Yildiz: Cu 0.03-0.53, Fe 0.91-1.96 and Zn, 053-1.49 microgl(-1), in the waste water Cu 0.20-0.52, Fe 1.22-2.29 and Zn 0.92-1.46 microgl(-1) and in the edible muscle of chub: Cu 1.00-3.79, Fe 7.21-17.04 and Zn 4.12-18.33 microg g(-1) wet weight respectively. Among the heavy metals studied Pb, Cd, Co, Cr, Ni and Mn were not detected in the river water, waste water and chub samples. Heavy metal contents in these samples were evaluated and the highest concentrations of Cu, Fe and Zn were found in the muscle tissue. The levels of the heavy metals were detected in decreasing order as iron> zinc> copper. All the samples contained comparatively lower amounts of metals as suggested by international and national regulatory bodies. Thus, we recommend periodic monitoring of these metals in the fish consumed by local people.     

Chemical speciation and potential ecological risk assessment of heavy metals in volcanic rocks of Southern Qinghai,China

ABSTRACT

Seven volcanic rocks samples were collected from Southern Qinghai to analyze chemical speciation and migration behavior of heavy metals by sequential chemical extraction procedure and column leaching test. The geo-accumulation index, ecological risk index and the risk assessment code were applied to assess the heavy metal pollution and potential environmental effects in this area. Results revealed that the total concentrations of heavy metals did not exceed the background values in soil of this area. Most of the samples produced acid rock drainage. The order of heavy metal migration and transformation sequence in the volcanic rocks of Zhiduo region was Cd?>?Pb?>?As?=?Cu?=?Zn?=?Mn based on the geo-accumulation index and Cd caused heavy pollution, which was also confirmed by the leaching test. Moderate potential ecological risk posed by heavy metals occurred in the study area based on the potential ecological risk index. Cd contributed to most of ecological risk while the remaining heavy metals (except As) exerted medium to high risks to the environment according to the risk assessment code evaluation results. In summary, volcanic rocks possessed potential risks to the surroundings due to potential release of heavy metals. Cd that caused the pollution should be paid special attention.     

Heavy metals in fish species from lotic freshwater ecosystem at Afikpo, Nigeria

A study was conducted between March 2006 and February 2007 to assess the concentration of Fe, Zn, Cu, Mn, Pb, and Cr in the gills and muscles of six fish species (Chrysichthys nigrodigitatus, Clarias anguillaris, Tillapia zillii, Mormyrus rume rume, Mormyrus macrophthalmus and Mormyrus tapirus) from lotic freshwater ecosystem at Afikpo South- East Nigeria using Atomic Absorption Spectrophotometer. In all the fish species studied the concentration of metals in the gills was significantly higher than that of the muscles (p<0.05). While the highest concentration (mg l(-1)) of Fe (702.20 +/- 0.04), Zn (34.40 +/- 0.02), Cu (2.10 +/- 0.01), Mn (4.91 +/- 0.08) Pb (0.50 +/- 0.02) and Cr (1.12 +/- 0.07) were recorded in the gills of C. nigrodigitatus, that in the muscles were recorded in T. zillii (443.20 +/- 0.08, 23.30 +/- 0.06, 1.33 +/- 0.06, 3.09 +/- 0.02, 0.31 +/- 0.01 and 0.66 +/- 0.04 for Fe, Zn, Cu, Mn, Pb and Cr respectively). The lowest concentration of all the heavy metals in the gills was recorded in M. tapirus (309.00 +/- 0.07, 16.45 +/- 0.03, 0.92 +/- 0.04, 2.15 +/- 0.04, 0.21 +/- 0.01 and 0.50 +/- 0.06 mg l(-1)for Fe, Zn, Cu Mn, Pb and Cr respectively) while the lowest in the muscles was recorded in C. anguillaris [Fe (186.00 +/- 0.07), Zn (14.20 +/- 0.08), Cu (0.56 +/- 0.03), Mn (1.30 +/- 0.02), Pb (0.10 +/- 0.01) and Cr (0.28 +/- 0.04)]. The order of heavy metals concentrations in both the gills and muscles was Fe>Zn>Mn>Cu>Cr>Pb. While the concentration of Zn, Cu and Pb both in the muscles and gills of all the six fish species studied were within the WHO and FEPA prescribed limits, that of Fe(except in the muscles), Mn and Cr were above the prescribed limits thus indicating contamination of the fish species by these metals. Fe has the highest bio-concentration factor (BCF) in both tissues while the least was Cu. Periodic monitoring of these metals in both fishes and river to ensure safety is advocated.     

Accumulation of heavy metals in soil and paddy crop (Oryza sativa), irrigated with water of Ramgarh Lake,Gorakhpur, UP,India

Heavy metals, a highly polluting group of constituents known to exert adverse effects, tend to accumulate in living organisms. The objective of this study was to determine the accumulation and translocation of heavy metals in soil and in paddy crop irrigated with lake water compared to soil and paddy crop irrigated with bore-well water. The quantities of heavy metals (Cd, Cr, Cu, Pb, Zn, As, Mn, and Hg) were determined in different parts of rice plants (Oryza sativa). Results revealed that the mean levels of soil Cd, Cr, Pb, Zn, As, Mn, and Hg in experimental soil and in different parts of rice plant (root, straw, and grain) were higher than the control except for Cu. The content of eight toxic metals was significantly higher in root than in aerial parts of the rice (straw and grains). Rice roots were enriched in Cd, As, Hg, and Pb from the soil, while Cr, Cu, Zn, and Mn were hardly taken by the roots. Bioaccumulation factor for Hg was significantly higher than other heavy metals. Metal transfer factors from soil to rice plants were significant for Cd, Cr, Cu, Pb, Zn, As, Mn, and Hg. The concentrations of metals in lake water were found to be within the permissible limit of Indian standard prescribed by Central Pollution Control Board (2000), except for Hg and As, which were higher than the limit of Indian standard. However, the concentrations of heavy metals in soil and rice grains were still below the maximal levels, as stipulated by Indian Prevention of Food Adulteration Act (PFA, 1954) and World Health Organization (WHO, 1993) guidelines.