A study of metal and metalloid contaminant availability in Antarctic marine sediments

Previous studies of impacted sites near Casey Station, Antarctica, have revealed elevated concentrations of metals and metalloids, particularly Cd, Cu, Fe, Pb, Sn and Zn in marine sediments. However, attempts to understand the availability and mobility of contaminant elements have not provided a true understanding of speciation. The current work shows, for the first time, that sediments in Brown Bay, an embayment adjacent to the Thala Valley waste disposal site, have elevated concentrations of sulfide, well in excess of that required to bind contaminant metals such as Cd, Cu, Pb and Zn. Furthermore, sediment characterisation using the BCR sequential extraction scheme has shown metal partitioning consistent with sulfides being the controlling factor in metal availability, thus explaining the low porewater concentrations of these metals. The speciation of Sn in Brown Bay, however, is still unclear with the BCR sequential extraction scheme partitioning Sn predominantly into the residual fraction despite Sn being readily extracted by dilute HCl.     

Relationship between heavy metals concentrations in egret species,their environment and food chain differences from two Headworks of Pakistan

Concentration of ten metals (Cd, Cr, Co, Cu, Fe, Li, Mn, Ni, Pb and Zn) were analyzed in the egg contents, prey and soil samples of little egret (Egretta garzetta) and cattle egret (Bubulcus ibis) from two Headworks to determine habitat and species-specific differences; to assess the importance of prey and habitat contamination as an exposure source for heavy metals. Concentration of Cu, Mn, Cr and Pb in egg contents, Fe, Co, Cu, Mn, Zn in prey and Fe, Co, Cu, Ni, Li in surface soils were significantly different (P < 0.05). Mean metal concentrations of Cr, Pb and Cd were relatively higher in little egret whereas Cu and Mn were higher in the egg contents of cattle egret. The mean concentrations of Cu, Mn and Zn were higher in prey samples of cattle egrets and Cr, Cd and Pb in prey samples of little egrets. In soil samples collected from little egret heronries metal concentrations were higher except Cu and Ni. Correlation Analysis and Hierarchical Agglomerative Cluster Analysis (HACA) identified relatively similar associations of metals and their source identification. Metals such as Fe, Cu, Mn, and Li were related with geochemical origin from parent rock material as well as anthropogenic input whereas Cr, Cd, Pb, Ni, Co and Zn were associated mostly with anthropogenic activities. The study suggested that eggs are useful bio-monitor of local heavy metal contamination.     

Level,source identification,and risk analysis of heavy metal in surface sediments from river-lake ecosystems in the Poyang Lake,China

Environmental Science and Pollution Research - The concentrations, sources, and risks of heavy metals (Fe, Al, Mn, Cr, Co, Ni, Cu, Zn, As, Cd, W, Pb, and Tl) in sediments in five river-lake...     

Distribution and coassociations of trace elements in soft tissue and byssus of Mytilus galloprovincialis relative to the surrounding seawater and suspended matter of the southern part of the Korean Peninsula

The concentrations of Cd, Co, Cu, Cr, Fe, Hg, Mn, Ni, Pb, Sn, Ti and Zn were analyzed by AAS, ICP MS and AFS in soft tissues and byssal threads of Mytilus galloprovincialis from Masan Bay and Ulsan Bay, Korea. Spatial variations in metal concentrations were found. The levels of Cd, Pb, Hg, Cu, Zn, Co and Mn were very high in the mussels from Ulsan Bay (Sts. U1, U2) and comparable with elevated concentrations of these elements in Mytilus sp. reported to date for other geographical areas. Seasonal differences in some metal concentrations were also observed. These variations may be caused by factors such as: a large difference in seawater temperature, food supply for the mussel population and/or freshwater runoff of particulate metal to the coastal water and weight changes brought about by gonadal development and the release of sexual products. Pb, Cu, Zn, Co, Ni, Fe and Mn were more enriched in byssal threads than in the soft tissues, hence the byssus seems to be more sensitive in reflecting the availabilities of trace metals in the ambient waters. Concentrations of trace metals varied with respect to the size of mussels and season, depending on many factors like sexual development, and seawater temperature, etc. The levels of some trace metals in seawater, especially in suspended matter were correlated significantly with those in soft tissues and byssal threads. There were spatial variations in metal concentrations in the soft tissue and byssus attributed to different sources of trace elements located near the sampling sites. There were significant relationships between concentrations of some metals (Cd, Cu, Pb, and Zn) in mussel soft tissues and byssal threads and suspended matter. This suggests that M. galloprovincialis can be used as a sensitive biomonitor for the availabilities of trace elements in the coastal waters off Korea.     

Geochemical evidences of the anthropogenic alteration of trace metal composition of the sediments of Chiricahueto marsh (SE Gulf of California)

Seven sediment cores (60-80 cm) were collected at Chiricahueto marsh, a salt marsh influenced by agrochemical, domestic and industrial effluents. The concentrations of Ag, Al, Cd, Co, Cu, Fe, Li, Mn, Pb, V and Zn were studied in the solid phase at each 1-cm section. The profiles of Ag, Cd, Cu, Mn, Ni, Pb and Zn showed a slight recent pollution in the site with enrichment and anthropogenic factors higher than unity; and correlation analysis indicated a direct association with organic carbon. Al, Co, Cr, Fe, Li, and V concentration profiles displayed a negative correlation with organic C and positive with mud content and no consistent enrichment at surface. Based on the principal component analysis and correlation analysis, two principal groups of metals were identified. The first group includes Al, Co, Cr, Fe and Li, that are derived predominantly from the weathering of parent materials in the local bedrock; and the second group include most of the metals, which were relatively enriched at surficial sediments, that are produced mainly by anthropogenic activities such as agriculture (Cd, Cu and Zn), sewage effluents (Ag, Cd, Cu, Ni, Pb and Zn) and in lesser extent atmospheric deposition (Cd and Pb).     

The influence of body size, condition index and tidal exposure on the variability in metal bioaccumulation in Mytilus edulis

Mussels are commonly used to monitor metal pollution despite high inter-individual variability in tissue concentrations. In this study, influences of body size, condition index and tidal height on concentrations of As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn were investigated. Body weight was inversely related to metal concentrations and for Cd, Mn, Pb and Zn the regression was affected by tidal height. Except for As, Fe and Mn metal concentrations were inversely related to physiological status though no differences between essential and non-essential metals were obvious. After correcting for body size, tidal height was related positively to As, Cd and Zn, negatively related to Cu, Fe and Mn while Co, Cr, Ni and Pb were independent of tidal height. The study recommends stringent measures during sampling for biomonitoring or metal concentrations at each location must be normalized to a common body size, CI and tidal height.     

Metal concentrations and mobility in marine sediment and groundwater in coastal reclamation areas: a case study in Shenzhen, China

The concentrations of metals in the buried marine sediment and groundwater were differently affected by land reclamation. Nine metals (V, Cr, Mn, Co, Ni, Cu, Zn, Cd and Pb) in sediment and coastal groundwater from reclamation areas in Shenzhen were examined. The gradually decreased concentrations (V, Cr, Mn, Ni, Cu, Zn) in sediment and relatively higher concentrations (V, Cr, Mn, Co, Ni, Cu and Cd) in groundwater within reclamation areas were observed. The increase of V, Cr, Mn, Ni, Cu and Cd concentrations in groundwater within reclamation areas subsequently after land reclamation should be resulted from the mobilization of these metals accumulated in the sediment. These metals appear to be easily mobilized from solid phase to solution phase after reclamation. The physico-chemical changes such as reduction in pH and salinity in water environment induced by land reclamation appear to be responsible for metal mobility in the sediment-groundwater system.     

Trace metal speciation and fluxes within a major French wastewater treatment plant: impact of the successive treatments stages

Seven metals (Cd, Co, Cr, Cu, Fe, Ni and Pb) were monitored at the Seine-Aval wastewater treatment plant during 6 sampling campaigns in April 2004. Particulate and dissolved metals have been measured in 24 h composite samples at each treatment stage (primary settling, secondary activated sludge and tertiary flocculation by FeCl₃). In addition, the diffusive gradient in thin film technique (DGT) was used to determine the dissolved inert and labile metal fraction. Although all treatment stages were able to decrease particulate metals concentrations in wastewater, most dissolved metals concentrations were mainly affected during primary settling. This unexpected result was attributed to tertiary sludge filtrate recirculation. Metals added via the FeCl₃ reagent at the tertiary treatment were shown to lower the overall Cr removal from wastewater and to enrich Ni in effluents. The plant operating conditions (recirculation and reagent addition) appear therefore as important as treatment processes for the metals removal. Total metal fluxes were highly decreased by the whole treatment plant for Cd, Cr, Cu and Pb and to a lesser extend for Co and Ni. However, the labile metal fluxes were poorly decreased for Cu (18%), not significantly decreased for Ni and increased for Fe. The labile fraction of Cd, Co and Cr was not detectable at any stage of the plant. Discharged labile fluxes, at least for Ni, were potentially significant compared to the labile metal fluxes in the river measured downstream the plant. Treated urban wastewater discharges should be carefully considered as a possible source of bioavailable trace metals.     

Distribution of elements in needles of Pinus massoniana (Lamb.) was uneven and affected by needle age

Macronutrients (P, S, K, Na, Mg, Ca), heavy metals (Fe, Zn, Mn, Cu, Pb, Cr, Ni, Cd) and Al concentrations as well as values of Ca/Al in the tip, middle, base sections and sheaths of current year and previous year needles of Pinus massoniana from Xiqiao Mountain were analyzed and the distribution patterns of those elements were compared. The results indicated that many elements were unevenly distributed among the different components of needles. Possible deficiency of P, K, Ca, Mn and Al toxicity occurred in needles under air pollution. Heavy metals may threaten the health of Masson pine. Needle sheaths were good places to look for particulate pollutants, in this case including Fe, Cu, Zn, Pb, Cr, Cd and Al.     

应用地质累积指数评价抚顺市PM10中元素的污染

2006-2007年采暖季、风沙季和非采暖季分别在抚顺市的6个采样点采集PM10样品,用等离子体原子发射光谱(ICP-AES)法测定样品中Ti、Al、Mn、Mg、Ca、Na、K、Cu、Zn、As、Pb、Cr、Ni、Co、Cd、Fe、V等17种元素的含量,并用地质累积指数对其污染状况进行初步评价。结果表明:(1)从PM10中元素在不同采样点的含量看,抚顺市PM10中Ti、Mn、Mg、Cu、Zn、Pb、Cr、Ni、Co这9种元素在各采样点间的差别较大;Al、Ca、Na、K、As、Cd、Fe、V这8种元素差别较小。(2)从PM10中元素在不同采样季的含量看,抚顺市PM10中Mn、Mg含量的季间差别较大,其余15种元素季间差别较小。(3)Zn、Cd污染较重;Ti、Al、Mg、Ca、Na、K、As、Fe和V污染较轻;其他6种元素在6个采样点和3个采样季污染程度差别较大。(4)水库采样点各元素污染级别均不是最高;新华采样点PM10中Cu、Zn、Pb、Cr、Ni、Co、Cd污染级别均较高。(5)3个采样季PM10中Cd、Zn污染均较重,属于重度或严重污染;在采暖季PM10中Cu、Pb、Cr的地质累积指数较风沙季、非采暖季大;在非采暖季PM10中Mn、Co受到的污染比采暖季和风沙季稍严重。     

Distribution of elements in needles of Pinus massoniana (Lamb.) was uneven and affected by needle age

Macronutrients (P, S, K, Na, Mg, Ca), heavy metals (Fe, Zn, Mn, Cu, Pb, Cr, Ni, Cd,) and Al concentrations as well as values of Ca/Al in the tip, middle and base sections, and sheaths of current year and previous year needles of Pinus massoniana from Xiqiao Mountain were analyzed and the distribution patterns of those elements were compared. The results indicated that many elements were unevenly distributed among the different components of needles. Possible deficiency of P, K, Ca, Mn and Al toxicity occurred in needles under air pollution. Heavy metals may threaten the health of Masson pine. Needle sheaths were good places to look for particulate pollutants, in this case including Fe, Cu, Zn, Pb, Cr, Cd and Al.     

Marine sponges with contrasting life histories can be complementary biomonitors of heavy metal pollution in coastal ecosystems

In this study, we compared the usefulness of a long-living sponge (Hymeniacidon heliophila, Class Demospongiae) and a short-living one (Paraleucilla magna, Class Calcarea) as biomonitors of metallic pollution. The concentrations of 16 heavy metals were analyzed in both species along a gradient of decreasing pollution from the heavily polluted Guanabara Bay to the less impacted coastal islands in Rio de Janeiro, SE Brazil (SW Atlantic). The levels of most elements analyzed were higher in H. heliophila (Al, Co, Cr, Cu, Fe, Mn, Ni, Hg, Ni, and Sn) and P. magna (Ni, Cu, Mn, Al, Ti, Fe, Pb, Co, Cr, Zn, and V) collected from the heavily polluted bay when compared with the cleanest sites. Hymeniacidon heliophila accumulates 11 elements more efficiently than P. magna. This difference may be related to their skeleton composition, histological organization, symbiont bacteria and especially to their life cycle. Both species can be used as a biomonitors of metallic pollution, but while Hymeniacidon heliophila was more effective in concentrating most metals, Paraleucilla magna is more indicated to detect recent pollutant discharges due to its shorter life cycle. We suggest that the complementary use of species with contrasting life histories can be an effective monitoring strategy of heavy metals in coastal environments.     

Heavy metal surveys in Nordic lakes; concentrations, geographic patterns and relation to critical limits

In the autumn of 1995, coordinated national lake surveys were conducted in the Nordic countries, including Russian Kola. The 11 metals (Pb, Cd, As, Zn, Cu, Ni, Co, Fe, Mn, Cr, V) investigated in nearly 3000 lakes have generally low concentrations and distinct geographical patterns. Direct and indirect influence of long-range transported air pollution is the major important factor for distribution of Pb, Cd, Zn and to a certain degree Co. Total organic carbon (TOC) concentrations in lakes are important for Fe and Mn but also to a certain degree for As, Cr and V. Bedrock geology is the major controlling factor for Cu and Ni, with the exception of areas around the smelters in the Kola peninsula, where the Cu and Ni concentrations in lakes are very high due to local airborne pollution. Bedrock and surficial geology is also an important factor for controlling the concentrations of As, Co, Cr and V. The results indicate that heavy metal pollution in lakes is a minor ecological problem on a regional scale in the Nordic countries.     

The intestinal parasite Pomphorhynchus laevis (Acanthocephala) from barbel as a bioindicator for metal pollution in the Danube River near Budapest, Hungary

Concentrations of As, Al, Ag, Ba, Bi, Cd, Co, Cr, Cu, Fe, Ga, Mg, Mn, Ni, Pb, Sb, Sn, Sr, Tl, V and Zn were analyzed by inductively coupled mass spectrometry (ICP-MS) in the intestinal helminth Pomphorhynchus laevis and its host Barbus barbus. The fish were caught in the Danube river downstream of the city of Budapest (Hungary). Ten out of twenty one elements analyzed were found at higher concentrations in the acanthocephalan than in different tissues (muscle, intestine, liver and kidney) of barbel. Considering the fish tissues, most of the elements were present at highest concentrations in liver, followed by kidney, intestine and muscle. Spearman correlation analyses indicate that there is competition for metals between the parasites and the host. The negative relationships between parasite number and metal levels in organs of the barbel support this hypothesis. The bioconcentration factors for Ag, As, Ba, Bi, Cu, Ga, Mn, Pb, Sr, Tl, and Zn showed that the parasites concentrated metals to a higher degree than the fish tissues. They accumulated the metals As, Cd, Cu, Fe, Ni, Pb, Sr and Zn even better than established bioindicators such as the mussel Dreissena polymorpha as revealed by data from the literature. The results presented here emphasize that acanthocephalans of fish are very useful as sentinels for metal pollution in aquatic ecosystems. Ratio of metal concentrations in the parasites and the host tissues provide additional information. Not including acanthocephalans in accumulation bioindication studies with fishes (as still customarily done) may lead to false results.     

Heavy metals incidence in the application of inorganic fertilizers and pesticides to rice farming soils

The concentrations of Cd, Co, Cu, Ni, Pb, Zn, Fe and Mn in different inorganic fertilizers (urea, calcium superphosphate, iron sulphate and copper sulphate) and in pesticides (two herbicides and one fungicide) are evaluated together with the contribution of these metals in soils from their use. The study was made in rice farming areas to the north of Albufera Natural Park (Valencia, Spain). The results obtained show that superphosphate is the fertilizer that contains the highest concentrations of Cd, Co, Cu and Zn as impurities. Copper sulphate and iron sulphate have the most significant concentrations of Pb, and are the only fertilizers in which Ni was detected. The three pesticides analysed show similar Cd contents and the highest levels of Fe, Mn, Zn, Pb and Ni are found in the herbicides. The most significant additions of heavy metals as impurities that soil receives from agricultural practices, are Mn, Zn, Co and Pb. Three contamination indexes have been applied to provide a basis for comparison of potential heavy metal toxicity. These results denote the potential toxicity of heavy metals in the studied soils.     

Trace element contamination of Norwegian Lake sediments

Concentrations of Sb, Hg, Bi, Cd, Mo, As, Co, Ni, Cr, Cu, V, Pb and Zn in surface and preindustrial sediments from 210 lakes in Norway were used for studying modern atmospheric depositions of these elements. Surface sediments had considerably higher concentrations of Sb, Hg, Bi, Cd, As, Pb than preindustrial sediments. The differences decreased with latitude and altitude. A multivariate analysis including the trace elements and the major constituents (organic matter, Si, Al, Fe and Mn) of surface sediments suggested the following relationships: Sb, Hg, Bi, As, and Pb formed a group with strong associations to organic matter. Ni, Cr and Cu formed a second group, weakly associated to the inorganic sediment fraction (Si and Al). Zn and Cd formed a third group with weak associations to organic matter. Co was associated to Mn, whereas Mo and V showed no important covariations with any other trace elements or major components.     

Mobility of heavy metals from polluted sediments of a semi-enclosed basin: in situ benthic chamber experiments in Taranto’s Mar Piccolo (Ionian Sea,Southern Italy)

In situ benthic flux experiments were conducted at two stations in the Mar Piccolo of Taranto (Italy), one of the most industrialised and contaminated coastal areas of the Mediterranean. Sediments of the two stations are notably different in their trace metal content, with a station closer to a Navy harbour showing higher mean concentrations of almost all investigated metals (Al, As, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, V and Zn). Conversely, both stations are characterised by significant Hg contamination, compared to the local baseline. Results of a sequential extraction scheme on surface sediments suggest a relatively scarce mobility of the examined metals (Zn > Ni > Cr > As > Cu > Pb). A Hg-specific extraction procedure showed that most of the element (93.1 %) occurs in a fraction comprising Hg bound to Fe/Mn oxi-hydroxides. Reduction of these oxides may affect Hg remobilisation and redistribution. Porewater profiles of dissolved trace metals were quite similar in the two sites, although significant differences could be observed for Al, Cu, Fe and Hg. The highest diffusive fluxes were observed for As, Fe and Mn. Mobility rates of several trace elements (Al, As, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, V and Zn) were directly measured at the sediment–water interface. Results from benthic in situ incubation experiments showed increasing dissolved metal concentrations with time, resulting in higher fluxes for Cu, Fe, Hg, V and Zn in the most contaminated site. Conversely, fluxes of Mn, Ni and Pb were comparable between the two stations. The estimated flux of Hg (97 μg m^?2 day^?1) was the highest observed among similar experiments conducted in other highly contaminated Mediterranean coastal environments. Benthic fluxes could be partially explained by considering rates of organic matter remineralisation, dissolution of Fe/Mn oxy-hydroxides and metal speciation in sediments. Seasonal and spatial variation of biogeochemical parameters can influence metal remobilisation in the Mar Piccolo area. In particular, metals could be promptly remobilised as a consequence of oxygen depletion, posing a serious concern for the widespread fishing and mussel farming activities in the area.     

Grit ingestion as a source of metal exposure in the spruce grouse, Dendragapus canadensis

The objective of this study was to determine if ingestion of grit was a source of metal exposure to the spruce grouse, Dendragapus canadensis. A secondary objective was to assess whether grit could provide a supplemental source of essential minerals to their diet. Ca, P, Mg, S, Zn, Cu, Ni, Co, Cr, Fe, Mn, Al, Pb and Cd of liver (adult, yearling, chicks), crop and gizzard contents (adults) were determined for grouse collected from a relatively pristine boreal forest region of north-central Ontario, Canada. With the exception of Cd liver, concentrations were independent of age [one-way analysis of variance (ANOVA); p>0.004). Zn liver concentrations tended to be greater in adults than yearlings and chicks (one-way ANOVA; p=0.02). Liver concentrations of Cd increased with age (r=0.99; p<0.001). The contribution of crop items to total gizzard elemental content was element specific; crop contents contributed 90-100% of Mn and Zn, 70% for P and Ca, 60% for Pb, 50% for S, and 0-25% for Cu, Mg, Ni, Al, Fe, Co, Cr and Cd to the total elemental concentration of gizzard contents (crop plus grit). Incorporation of grit by grouse could, therefore, constitute an important source of essential macro-(Ca, P, Mg, S) and trace elements (Cu, Fe) but not for Mn or Zn. However, in addition to providing nutrients to the bird, ingestion of grit results in exposure to toxic trace metals such as Cd which in turn is accumulating in the liver. Research directed at determining grit turnover time, and hence metal exposure rates, in bird species which ingest grit to aid in food digestion is required. The toxicological significance of Cd exposure to grit-ingesting birds needs attention.     

Heavy metal monitoring of marine algae from the Turkish Coast of the Black Sea, 1998-2000

Concentrations of Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn were determined in macroalgae samples collected from the Turkish Coast of the Black Sea. Certain algae species were chosen among the green, brown and red algae species at Sile and Sinop sampling stations from 1998 to 2000. In general, as regards the influence of the collection sites on the whole metal accumulation, Sinop is considered to be more polluted than Sile. The concentrations of the heavy metals in Cystoseira barbata algae are compared with previous studies in the same stations. The results showed that all metal levels have gradually decreased during past years. At the same time, Cd, Co, Cr, Cu, Fe, Ni and Pb levels in the present study are lower than in Bosphorus and Marmara Sea algae. However, Mn and Zn concentrations are higher than Bosphorus but lower than at Marmara. According to these findings the heavy metal pollution decreased in Turkish Coast of the Black Sea during the years investigated.     

Status of metal levels and their potential sources of contamination in Southeast Asian rivers

To assess the concentration and status of metal contaminants in four major Southeast Asian river systems, water were collected from the Tonle Sap–Bassac Rivers (Cambodia), Citarum River (Indonesia), lower Chao Phraya River (Thailand), and Saigon River (Vietnam) in both dry and wet seasons. The target elements were Be, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Mo, Ag, Cd, Ba, Tl, and Pb and the concentrations exceeded the background metal concentrations by 1- to 88-fold. This distinctly indicates enrichment by human urban area activities. The results of a normalization technique used to distinguish natural from enriched metal concentrations confirmed contamination by Al, Cd, Co, Mn, Ni, Pb, and Zn. Cluster analysis revealed the probable source of metals contamination in most sampling sites on all rivers studied to be anthropogenic, including industrial, commercial, and residential activities. Stable lead isotopes analyses applied to track the sources and pathways of anthropogenic lead furthermore confirmed that anthropogenic sources of metal contaminated these rivers. Discharges of wastewater from both industrial and household activities were major contributors of Pb into the rivers. Non-point sources, especially road runoff and street dust, also contributed contamination from Pb and other metals.