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.     

Schwermetalle in Regenwürmern Baden-Württembergs

Goal and Scope

Since 1984 the Environmental Protection Agency (LfU) of the State of Baden-Wuerttemberg has been investigating the heavy metal burden of earthworms from representative long-term forest observation plots. These investigations are aimed at elucidating and assessing adverse effects of pollutants on the soil biocenosis.

Methods

At first only lead and cadmium were measured in the worms; in repetitive measurements over the years further metals or metalloid elements such as aluminum, arsenic, chromium, cobalt, copper, manganese, mercury, nickel, thallium, vanadium, and zinc were added to the agenda.

Results and Conclusion

The frequency distribution of the metals in the earthworms was characterized statistically. For the first time state-wide background values, normal values and threshold values were established for all the elements measured. A comparable study with a similar range of parameters is known neither nationally nor internationally. Time trend studies have been available for lead and cadmium since 1985/86, and for zinc since 1987. The studies show a steady decrease of the heavy metals on a state-wide average and especially in the ‘Odenwald’ and ‘Black Forest’ hills with their formerly highly polluted earthworm habitats. Today, the level of these metals in the earthworms is low with few exceptions. This holds true for other heavy metals as well.

Recommendations and Perspectives

The state-wide decreasing very low heavy metal burden of forest observation plots far from known emission sources can be considered a success of air pollution abatement measures. Because of the ongoing atmospheric deposition of heavy metals, regular observation should continue in order to estimate time trends and to recommend the reduction of emissions when precautionary values (part 2) are exceeded.     

Schwermetalle in Regenwürmern Baden-Württembergs

Goal and Scope

The heavy metal burden of the soil and of earthworms from representative long-term forest observation plots has been measured since 1984 as one component of the media-embracing environmental monitoring network of the State of Baden-Wuerttemberg. These investigations are aimed at elucidating and assessing adverse effects of pollutants on the soil biocenosis

Methods

So-called characteristic curves for the metals Cd, Cu, Ni, Pb, and Zn were developed for the assessment. Earthworm toxicity data and background values in soil served as criteria. This procedure facilitates a comparative assessment of different pollutants. The mobility of the metals, which greatly influences their bioavailability and toxicity, was taken into account for the effects assessment.

Results and Conclusion

Besides inventorying the heavy metals (Part 1), the question of threshold values for toxic reactions as well as for accumulation was raised. The metal concentrations were assessed in the soil with regard to its habitat function. The ecotoxicological assessment revealed that the heavy metal burden of the investigated plots lies within the background- or precautionary range, well below the screening value established here to indicate the effect threshold in earthworms. This result means that a pollution of the forest observation plots with the metals cadmium, copper, lead, nickel, and zinc is low or absent. Only the distribution of the lead content is centered slightly above background (but clearly below the toxicity threshold). This slight lead burden of the soil of the observation plots can be explained by emissions from motor vehicles. Investigations at sites that are contaminated with either chromium or copper or cadmium showed that an accumulation of these metals in the body of the worms can be observed only above a threshold concentration of several hundred micrograms of mobile metal per kilogram in the upper layer of the soil.

Recommendations and Perspectives

The hitherto unknown threshold values for the accumulation in the body of the earthworm should be statistically validated and extended to other elements. Further research is needed in order to build a well founded basis for the ecotoxicological assessment of soil pollution. Acute and chronic earthworm effect thresholds are neither available yet for arsenic, cobalt, and mercury nor for some other elements occurring less frequently as soil pollutants. Background values depending on the kind of rock have been measured so far for total chromium only. They are lacking for the more toxic chromium (VI) which is a frequent soil pollutant but naturally occurs in traces only.     

Heavy metal action on transintegumentary absorption of glycine in two annelid species

Absorption of ¹⁴C-glycine from ambient sea water across the body surface of the oligochaete Enchytraeus albidus Henle was, after 6 h preincubation, significantly reduced in the presence of 0.1 to 0.15 ppm mercury, 0.25 ppm copper, 1.5 ppm silver, and 2 ppm cadmium. Addition of heavy metal salts reduced maximum uptake rates (V _max ), without affecting transport constants (K _t ). Influx of ¹⁴C-glycine remained unchanged in the presence of up to 10 ppm aluminium, chromium, iron, lead, molybdenum, vanadium, and zinc. Effects of up to 150 ppm nickel, manganese, cobalt and selenium were negligible. Inhibition of glycine absorption by mercury and cadmium in the polychaete Nereis diversicolor Müller is almost identical with results presented for E. albidus. Transintegumentary solute absorption in soft-bodied marine invertebrates obviously represents a suitable biological function for studies on heavy metal toxicity. The close relationship between rates of heavy metal absorption, inhibition of transintegumentary glycine uptake, and acute toxicity is discussed.     

Heavy metals in surface water and stream sediments in Jamaica

The levels of heavy metals in water and stream sediments in Jamaica are presented and compared to levels in soils and environmental standards. Heavy metals (cadmium, chromium, copper, mercury, nickel, lead and zinc) appear to be less of a problem to Jamaica's freshwater environment than might be expected given the concentrations in soils. This can be explained by taking into account the dynamics of the Jamaican water environment and the relative absence of anthropogenic sources. The dynamics of the freshwater system on the other hand, could pass any environmental threat to the coastal environment. Because the stream sediments are relatively coarse and contain little organic material the bio-availability of micropollutants such as heavy metals from the sediments can be expected to be relatively high.     

The toxicity of heavy metals to embryos of the American oyster Crassostrea virginica

The acute toxicity of 11 heavy metals to embryos of the American oyster Crassostrea virginica was studied and the concentrations at which 50% of the embryos did not develop were determined. The most toxic metals and their LC₅₀ values were mercury (0.0056 ppm), silver (0.0058 ppm), copper (0.103 ppm) and zinc (0.31 ppm). Those metals that were not as toxic and their LC₅₀ values were nickel (1.18 ppm), lead (2.45 ppm) and cadmium (3.80 ppm). Those metals that were relatively non-toxic and their LC₅₀ values were arsenic (7.5 ppm), chromium (10.3 ppm) and manganese (16.0 ppm). Aluminum was non-toxic at 7.5 ppm, the highest concentration tested.     

澳门城市垃圾焚烧底灰的重金属淋溶及其遗传毒性评价

应用美国国家环境保护局推荐的毒性特性溶出程序(toxicitycharacteristicleachingprocedure,TCLP),以及ICP-MS和ICP-AES技术研究了澳门城市垃圾焚烧底灰中重金属的淋溶,并结合蚕豆根尖微核试验评价了其潜在的生态与健康风险.结果显示,该底灰淋溶出来的重金属元素:铝(Al)、锰(Mn)、钴(Co)和汞(Hg)的浓度低于0.01mg·L-1,铁(Fe)、铜(Cu)和钼(Mo)的浓度低于0.1mg·L-1,而铬(Cr)、锌(Zn)、硒(Se)、锶(Sr)、钡(Ba)和铯(Cs)的浓度在0.11mg·L-1￣2.19mg·L-1之间.需要注意的是淋溶液中铅(Pb)的浓度异常高,最高可达19.06mg·L-1,超过了美国相关标准的上限(5mg·L-1);对比不同条件下底灰中重金属的淋溶情况,表明溶解作用和淋溶液的pH值是影响其淋溶的2个重要因素.蚕豆根尖微核试验显示各淋溶液处理组根尖细胞微核率明显升高,与阴性对照组相比具有显著性差异(p<0.05),表明各淋溶液具有遗传毒性;随着淋溶液中重金属浓度的增加,蚕豆根尖细胞所表现出来的毒性效应增强,表明重金属是淋溶液具有遗传毒性的重要原因.     

Spatial Variations of Heavy Metals in the East China Sea Continental Shelf Surface Sediments

Surface sediments collected from continental shelf of the East China Sea were analyzed for heavy metals (iron, manganese, copper, zinc, lead, cadmium), carbonate, organic carbon contents, and grain sizes. the range of concentrations observed were iron: 0.3-1.3 wt%, manganese: 2.3-14 μmole/g, copper: 7.1-184 μmole/g, zinc: 0.16-0.77μmiole/g, lead: 15-98 μmole/g, cadmium: 0.17-3.9 μmole/g, carbonate: 3.6-87 wt%, sand: 10-100%, silt: 0-70% and clay: 0-50%.

A zonal distribution pattern of the heavy metals was found in the East China Sea Continental shelf sediments. High concentrations of most heavy metals, organic carbon and fine-grained sediments were observed in the inner shelf zone, especially those near the discharge of the Yangtze River. Concentrations of these heavy metals decreased from the inner shelf to the shelf break region. High concentrations of metals were also found in sediments near Taiwan. Iron concentrations decreased north-east of the central shelf region. High concentrations of cadmium were found in the shelf break region where biogenic carbonate is predominant. This study showed that biogenic carbonate in the East China Sea shelf break region and the terrigenous sediments from the Yangtze River and island of Taiwan were the major sources of heavy metals. Heavy metal concentrations were strongly influenced by the content of the coarse-grained quartz sand present in the sediments.     

Spatial Variations of Heavy Metals in the East China Sea Continental Shelf Surface Sediments

Surface sediments collected from continental shelf of the East China Sea were analyzed for heavy metals (iron, manganese, copper, zinc, lead, cadmium), carbonate, organic carbon contents, and grain sizes. the range of concentrations observed were iron: 0.3-1.3 wt%, manganese: 2.3-14 μmole/g, copper: 7.1-184 μmole/g, zinc: 0.16-0.77μmiole/g, lead: 15-98 μmole/g, cadmium: 0.17-3.9 μmole/g, carbonate: 3.6-87 wt%, sand: 10-100%, silt: 0-70% and clay: 0-50%.

A zonal distribution pattern of the heavy metals was found in the East China Sea Continental shelf sediments. High concentrations of most heavy metals, organic carbon and fine-grained sediments were observed in the inner shelf zone, especially those near the discharge of the Yangtze River. Concentrations of these heavy metals decreased from the inner shelf to the shelf break region. High concentrations of metals were also found in sediments near Taiwan. Iron concentrations decreased north-east of the central shelf region. High concentrations of cadmium were found in the shelf break region where biogenic carbonate is predominant. This study showed that biogenic carbonate in the East China Sea shelf break region and the terrigenous sediments from the Yangtze River and island of Taiwan were the major sources of heavy metals. Heavy metal concentrations were strongly influenced by the content of the coarse-grained quartz sand present in the sediments.     

Sources,spatial variation,and speciation of heavy metals in sediments of the Tamagawa River in Central Japan

Sediments of the Tamagawa River in central Japan were studied to explain the spatial variation, to identify the sources of heavy metals, and to evaluate the anthropogenic influence on these pollutants in the river. Sediment samples were collected from 20 sites along the river (five upstream, four midstream, and 11 downstream). Heavy metal concentrations, viz. chromium, nickel, copper, zinc, lead, cadmium, and molybdenum, in the samples were measured using inductively coupled plasma-mass spectroscopy. The chemical speciations of heavy metals in the sediments were identified by the widely used five-step Hall method. Lead isotopes were analyzed to identify what portion is contributed by anthropogenic sources. The total heavy metal concentrations were compared with global averages for continental crust (shale) and average values for Japanese river sediments. The mean heavy metal concentrations were higher in downstream sediments than in upstream and midstream samples, and the concentrations in the silt samples were higher than those in the sand samples. Speciation results demonstrate that, for chromium and nickel, the residual fractions were dominant. These findings imply that the influence of anthropogenic chromium and nickel contamination is negligible, while copper, zinc, and lead were mostly extracted in the non-residual fraction (metals in adsorbed/exchangeable/carbonate forms or bound to amorphous Fe oxyhydroxides, crystalline Fe oxides, or organic matter), indicating that these elements have high chemical mobility. The proportion of lead (Pb) isotopes in the downstream silt samples indicates that Pb accumulation is primarily derived from anthropogenic sources.     

深圳市农林土壤重金属累积现状及风险评价研究（Heavy Metal Accumulation Characters and Risk Assessment in the Soil of Agriculture and Forest of Shenzhen Area）

为探讨深圳市农林土壤重金属的污染现状,系统采集了深圳市菜地、果园、林地和荒地4种土地利用的52个土壤样品,测定了Cu、Pb、Cd、Zn、Cr、Ni6种重金属的全量,对深圳市农林土壤重金属20余年来的累积状况进行了分析并进行了初步的风险评价.结果发现,深圳农林土壤均存在不同程度的重金属累积,总体而言,Cu、Pb、Zn、Cr和Ni的累积较轻,Zn的最大含量尚未超过其80年代末背景值的最大值;Cd的累积最为严重,其最大含量已为背景最大值的16倍.以GB15618-1995为标准,对深圳农林土壤的重金属风险进行评价后发现,Cu的污染最轻,仅20%的菜地土壤超过国家一级标准,Pb50%超过国家一级标准,但尚未超过二级标准;Zn、Cr和Ni均有一定比例的样点超过二级标准,最少4%,最高50%,但未有超过三级标准的样点;Cd的风险最大,不仅有大量超过一、二级标准的样点,而且超过三级标准的样点也占有一定的比例(菜地、果园、林地和荒地土壤中Cd含量超过三级标准的比例分别为10%、23%、29%和50%).深圳农林土壤中的Cd污染应该引起相关部门的重视.     

Sources, spatial variation, and speciation of heavy metals in sediments of the Tamagawa River in Central Japan

Sediments of the Tamagawa River in central Japan were studied to explain the spatial variation, to identify the sources of heavy metals, and to evaluate the anthropogenic influence on these pollutants in the river. Sediment samples were collected from 20 sites along the river (five upstream, four midstream, and 11 downstream). Heavy metal concentrations, viz. chromium, nickel, copper, zinc, lead, cadmium, and molybdenum, in the samples were measured using inductively coupled plasma-mass spectroscopy. The chemical speciations of heavy metals in the sediments were identified by the widely used five-step Hall method. Lead isotopes were analyzed to identify what portion is contributed by anthropogenic sources. The total heavy metal concentrations were compared with global averages for continental crust (shale) and average values for Japanese river sediments. The mean heavy metal concentrations were higher in downstream sediments than in upstream and midstream samples, and the concentrations in the silt samples were higher than those in the sand samples. Speciation results demonstrate that, for chromium and nickel, the residual fractions were dominant. These findings imply that the influence of anthropogenic chromium and nickel contamination is negligible, while copper, zinc, and lead were mostly extracted in the non-residual fraction (metals in adsorbed/exchangeable/carbonate forms or bound to amorphous Fe oxyhydroxides, crystalline Fe oxides, or organic matter), indicating that these elements have high chemical mobility. The proportion of lead (Pb) isotopes in the downstream silt samples indicates that Pb accumulation is primarily derived from anthropogenic sources.     

Hair burning and liming in tanneries is a source of pollution by arsenic,lead, zinc,manganese and iron

Heavy metals in the environment may be toxic for human and animals. Tanneries are a source of pollution by heavy metals. There is little information on heavy metals pollution in tanneries, especially on metals produced by the process of hair burning and liming. Liming is the first stage of chemical treatment where animal hair or wool is removed with sodium sulphide and calcium oxide. Here we studied cow, goat, buffalo and sheep hair, conventional liming agents and liming wastewaters from several sources. Samples were acid-digested and aliquots were analysed by atomic absorption spectroscopy following APHA standard method to measure concentrations of arsenic, lead, cadmium, zinc, manganese and iron. Results show that the range of metal contents in hair or wool and liming agents are 1.3–8.2 mg/kg for arsenic, 0.02–21.8 mg/kg for lead, 17.7–121.0 mg/kg for manganese, 7.3–141.1 mg/kg for zinc and 119.6–10613.8 mg/kg for iron. Liming wastewaters contain 1.9–5.6 µg/L arsenic, 0.03–6.05 µg/L lead, 38.6–139.0 µg/L manganese, 144.0–171.5 µg/L zinc and 399.5–1069.0 µg/L iron. Cadmium was below detection limits. This is the first investigation that reveals that hair burning liming operation is a potential source of heavy metals in the environment.     

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.     

Concentrations of cadmium,manganese, copper,zinc, and lead in the tissues of the oyster (Crassostrea iredalei) obtained from Setiu Lagoon,Terengganu, Malaysia

Heavy metals pollution in aquatic environments is a major problem contributing to human health issues. The study of these pollutants through bioindicators such as the oyster Crassostrea iredalei is important for (1) determining the levels and sources and (2) regulating the quantity of pollutants. The concentrations of cadmium (Cd), manganese (Mn), copper (Cu), zinc (Zn), and lead (Pb) in tissues of C. iredalei, sediment and surrounding water was measured, and data was analyzed to determine the relationship between sampling periods and between oyster tissue, sediment, and water. The highest concentration of metals in oyster tissue was Zn, followed by Cu, Mn, Cd, and Pb. Concentrations of Cd, Cu, and Zn exceeded the maximum level allowed according to the Malaysian Food Act of 1983, which is equivalent to the WHO recommended levels of heavy metals in organisms used for consumption. The highest metal concentration in sediment was Mn followed by Zn, Pb, Cu, and Cd. Concentrations of heavy metals in surrounding water were Zn, Pb, Cu, Mn, and Cd. There was no correlation between metal concentration in oyster tissue and in sediment for all five metals.     

Heavy Metals in Tissues of the Norway Lobster Nephrops Norvegicus: Effects of Sex, Size and Season

Concentrations of mercury, cadmium, copper, zinc and iron were determined in the carapace, hepatopancreas, gills, tail muscle, ovary and eggs of 288 Norway lobsters, Nephrops norvegicus, caught in the Clyde Sea area, south of the Isle of Cumbrae, Scotland. Metal levels in males and females were examined separately in relation to size and the season in which the animals were caught.

Cadmium, copper and zinc concentrations were highest in the hepatopancreas whereas mercury and iron concentrations were highest in the gill. Levels of metals showed variations between months, with highest levels tending to occur during molt. Metal levels were influenced by lobster size with pronounced size-related increases in mercury levels in the tail muscle and cadmium levels in the hepatopancreas. Levels of several metals in the various tissues differed between the sexes.     

生物扰动对沉积物中重金属迁移转化影响的研究进展

沉积物是重金属在环境中迁移转化的重要媒介。生物扰动能改变沉积物的物理化学组成,从而影响沉积物中重金属的赋存形态和迁移转化特征。文章介绍了生物扰动的定义和种类,生物扰动的影响因素以及扰动过程中影响污染物释放的主要因素,并综述了近年来生物扰动对沉积物中重金属镉、铜、锌、铅和其他重金属的环境行为影响。     

Assessment of Trace Metals in the Sediments From the Coastal Zone of Alexandria,Egypt

Freshly deposited surface sediments from the Alexandria coastal zone were collected and analysed in 1995 for their trace metal concentrations. Metal concentrations in the sediments vary between sites within a wide range for copper, zinc, iron, lead, chromium and cadmium. the statistical analysis between the metal concentrations and the different constituents (organic carbon, total nitrogen, silt, clay and total iron) showed significant correlations. the enrichment factors for the sediments ranged between 3 and 4-fold for copper, chromium and zinc and reached up to 9-fold for lead and 113-fold for cadmium. the highest index for cadmium and lead may be attributed to the anthropogenic inputs from the surrounding area, where they are highest in lower discharge areas.     

Assessment of Trace Metals in the Sediments From the Coastal Zone of Alexandria, Egypt

Freshly deposited surface sediments from the Alexandria coastal zone were collected and analysed in 1995 for their trace metal concentrations. Metal concentrations in the sediments vary between sites within a wide range for copper, zinc, iron, lead, chromium and cadmium. the statistical analysis between the metal concentrations and the different constituents (organic carbon, total nitrogen, silt, clay and total iron) showed significant correlations. the enrichment factors for the sediments ranged between 3 and 4-fold for copper, chromium and zinc and reached up to 9-fold for lead and 113-fold for cadmium. the highest index for cadmium and lead may be attributed to the anthropogenic inputs from the surrounding area, where they are highest in lower discharge areas.     

Chromosome damage in individuals exposed to heavy metals†

Testing the mutagenic activity of environmental pollutants has become an important area of modern environmental science and prophylactic medicine. The most suitable method for short‐term mutagenicity testing on man, at present, are chromosome studies on somatic cells of exposed individuals. Mutation types analyzed by such studies are of high practical relevance as indicator system of genetic damage induced in man under in vivo conditions. A rather large series of such studies has been dedicated to the action of heavy metals on individuals contacted with these metals under therapeutic, ecological or occupational conditions or by intoxication. Lead, cadmium, chromium, nickel, mercury, zinc and other metals as well as their compounds have been under study. Analyses of that kind, of course, are hampered by difficulties with the distinct estimation of the actual load as well as unclear conditions of exposition, e.g. simultaneous exposition to different metals.

Results obtained till now arouse some suspicion of a direct or indirect mutagenic activity in man by certain chromium and platinum compounds, arsenic, mercury, and combinations of lead with other heavy metals (cadmium, zinc, arsenic, antimony, etc.). Life style, above all smoking habits, well may act comutagenic. In most cases, however, mutagenic activity of metals and metal compounds apparently is clearly superposed by their toxic activity. In specific cases, chromosome studies also may contribute to discover sources of ecological exposition and to monitor occupational load by heavy metals.