Evaluation of the anthropogenic influx of metal and metalloid contaminants into the Moulay Bousselham lagoon, Morocco, using chemometric methods coupled to geographical information systems

Superficial and cored sediment samples from the Moulay Bousselham lagoon and sub-watershed were analyzed for Al, Fe, Cu, Zn, Pb, Mn, Ni, Cr, As, Hg, and Cd. The temporal and spatial distributions of the main contamination sources of heavy metals were identified and described using chemometric and geographic information system (GIS) methods. Sediments from coastal lagoons near urban and agricultural areas are commonly contaminated with heavy metals, and the concentrations found in surface sediments are significantly higher than those from 50–100 years ago. The concentrations of these elements decrease sharply with depth in the sediment column, and the elements are preferentially enriched in the <2-μm-sized fraction of the sediment. The zones of enhanced risk of heavy metals were detected by means of GIS-based geostatistical modeling. According to sediment pollution indices and statistical analysis, heavy metals (Pb, Cu, Ni, Zn, Cr, and Hg) that pose a risk have become largely enriched in the lagoon sediments during the recent period of agricultural intensification.     

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).     

Influence of solution acidity and CaCl2 concentration on the removal of heavy metals from metal-contaminated rice soils

Soil washing is considered a useful technique for remediating metal-contaminated soils. This study examined the release edges of Cd, Zn, Ni, Cr, Cu or Pb in two contaminated rice soils from central Taiwan. The concentrations exceeding the trigger levels established by the regulatory agency of Taiwan were Cu, Zn, Ni and Cr for the Ho-Mei soil and Pb for the Nan-Tou soil. Successive extractions with HCl ranging from 0 to 0.2 M showed increased release of the heavy metals with declining pH, and the threshold pH value below which a sharp increase in the releases of the heavy metals was highest for Cd, Zn, and Ni (pH 4.6 to 4.9), intermediate for Pb and Cu (3.1 to 3.8) and lowest for Fe (2.1), Al (2.2) and Cr (1.7) for the soils. The low response slope of Ni and Cr particularly for the rice soils make soil washing with the acid up to the highest concentration used ineffective to reduce their concentrations to below trigger levels. Although soil washing with 0.1 M HCl was moderately effective in reducing Cu, Pb, Zn and Cd, which brought pH of the soils to 1.1+/-0.1 (S.D.), the concurrent release of large quantities of Fe and Al make this remediation technique undesirable for the rice soils containing high clay. Successive washings with 0.01 M HCl could be considered an alternative as the dissolution of Fe and Al was minimal, and between 46 to 64% of Cd, Zn, and Cu for the Ho-Mei soil and 45% of Pb in the Na-Tou soil were extracted after four successive extractions with this dilute acid solution. The efficacy of Cd extraction improved if CaCl2 was added to the acid solution. The correlation analysis revealed that Cr extracted was highly correlated (P < 0.001) with Fe extracted, whereas the Cu, Ni, Zn, Cd or Pb extracted was better correlated (P < 0.001) with Al than with Fe extracted. It is possible that the past seasonal soil flooding and drainage in the soils for rice production was conducive to incorporating Cr within the structure of Fe oxide, thereby making them extremely insoluble even in 0.2 M HCl solution. The formation of solid solution of Ni with Al oxide was also possible, making it far less extractable than Cd, Zn, Cu, or Pb with the acid concentrations used.     

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.     

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.     

Heavy metals in sediments,soils, and aquatic plants from a secondary anabranch of the three gorges reservoir region,China

We investigated the occurrence of cadmium (Cd), copper (Cu), chromium (Cr), nickel (Ni), lead (Pb), Znic (Zn), iron (Fe), manganese (Mn), and magnesium (Mg) in sediments, as well as in related soils and aquatic plants in the Liangtan River, a typical secondary anabranch of the Yangtze River in the Three Gorges Reservoir Region (TGRR) of China. We found that sediments accumulated more metals than soils and aquatic plants. Concentrations of the nine metals in sediments and soils followed the same sequence, while their concentrations in aquatic plants followed a different sequence. Potential adverse effects of contaminated sediments on benthic fauna were evaluated, and the results showed that the toxic effect on benthic organisms followed the sequence Zn?>?Ni?>?Cr?>?Cu?>?Cd?>?Pb. The potential ecological risk index analysis indicated that Cd in sediments had considerable ecological risk, whereas Cr, Cu, Zn, Ni, and Pb had low ecological risk. The potential ecological risk index (RI) of the heavy metals in sediments of the Liangtan River was 174.9, indicating moderate ecological risk. The transfer factor trend of metals for aquatic plants showed that Cd and Ni had the most and least accumulation, respectively. For Cu, Cd, Mg, Pb, and Cr, a significant positive correlation of the metal concentrations was observed between sediments and soils, but no correlations (excluding Cr) were detected between sediments and aquatic plants. Our study indicated that anthropogenic input may be the primary source of metal contamination in the Liangtan River, and that Zn and Cd pollution in the Liangtan River should be further explored.     

Evaluation of diffusive gradients in thin film (DGT) samplers for measuring contaminants in the Antarctic marine environment

This work has been the first application of DGT samplers for measuring metals in water and sediment porewater in the Antarctic environment, and whilst DGT water sampling was restricted to quantification of Cd, Fe and Ni, preconcentration using Empore chelating disks provided results for an additional nine elements (Sn, Pb, Al, Cr, Mn, Co, Cu, Zn, As). Although higher concentrations were measured for some metals (Cd, Ni, Pb) using the Empore technique, most likely due to particulate-bound or colloidal species becoming entrapped in the Empore chelating disks, heavy metal concentrations in the impacted Brown Bay were found to be comparable with the non-impacted O'Brien Bay. Sediment porewater sampling using DGT also indicated little difference between Brown Bay and O'Brien Bay for many metals (Cd, Al, Cr, Co, Ni, Cu), however, greater amounts of Pb, Mn, Fe and As were accumulated in DGT probes deployed in Brown Bay compared with O'Brien Bay, and a higher accumulation of Sn was observed in Brown Bay inner than any of the other three sites sampled. Comparison of DGT derived porewater concentrations with actual porewater concentrations showed limited resupply of Cd, Pb, Al, Cr, Mn, Co, Ni, Cu, Zn and As from the solid phase to porewater, with these metals appearing to be strongly bound to the sediment, however, resupply of Fe and Sn was apparent. Based upon our observations here, we suggest that Sn, and to a lesser extent Pb, are critical contaminants.     

A comparative study on metal sorption by brown seaweed

This study compared the sorption of Ag, Cd, Co, Cd, Mn, Ni, Pb and Zn by a Ca-treated Sargassum biomass at pH 5.0, under low and high ionic strength (IS) conditions. The sorption isotherms of As [As(V)] and Cr [Cr(III) and Cr(VI)] were also determined at low IS. The isotherm data for the eight cationic metals and Cr(III) were well fitted by Langmuir equations. Generally, the maximum metal uptake (Umax) followed: Cr(III) > Pb approximately Cu > Ag approximately Zn approximately Cd > Ni approximately Mn approximately Co > Cr(VI) > As(V) at low IS and Pb > Cu > Co > Mn approximately Cd > Zn approximately Ag > Ni at high IS. As(V) did not bind to the seaweed at pH 5.0. The results indicated that sorption of Pb was not affected by the increasing IS, though the percentage of free Pb ions in the water was greatly reduced as predicted by the speciation model. High IS lowered Umax by 10-36% (except Co and Pb), and lowered the affinity constant of the metal by 33-91% for all cationic metals, as compared to low IS. Moreover, the removal efficiency of the cationic metals and Cr decreased exponentially with initial metal concentrations and was lower at high IS. Ion-exchange was the mechanism responsible for the cationic metal sorption onto the seaweed, and Na ion interfered with the cationic metal binding through electrostatic interaction. In conclusion, this study showed the differential binding capacity of the Sargassm biomass for different metals and oxidation states and the differential effects of IS. According to the present results, Sargassum may be considered a good biosorbent for cationic metals (especially Pb) in both low and high-salt containing wastewater.     

Non-destructive pollution exposure assessment in the European hedgehog (Erinaceus europaeus): II. Hair and spines as indicators of endogenous metal and As concentrations

The role of hair and spines of the European hedgehog as non-destructive monitoring tools of metal (Ag, Al, Cd, Co, Cr, Cu, Fe, Ni, Pb, Zn) and As pollution in terrestrial ecosystems was investigated. Our results showed that mean pollution levels of a random sample of hedgehogs in Flanders are low to moderate. Yet, individual hedgehogs may be at risk for metal toxicity. Tissue distribution analyses (hair, spines, liver, kidney, muscle and fat tissue) indicated that metals and As may reach considerable concentrations in external tissues, such as hair and spines. Positive relationships were observed between concentrations in hair and those in liver, kidney and muscle for Al, Co, Cr, Cu, and Pb (0.43 < r < 0.85). Spine concentrations were positively related to liver, kidney and muscle concentrations for Cd, Co, Cr, Cu and Pb (0.37 < r < 0.62). Hair Ag, As, Fe and Zn and spine Ag, Al, As and Fe were related to metal concentrations in one or two of the investigated internal tissues (0.31 < r < 0.45). The regression models presented here may be used to predict metal and As concentrations in internal tissues of hedgehogs when concentrations in hair or spines are available. The present study demonstrated the possibility of using hair and spines for non-destructive monitoring of metal and As pollution in hedgehogs.     

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.     

Seasonal variation and background levels of heavy metals in two green seaweeds

Seasonal variation in the contents of different metals (Al, Cr, Cu, Fe, Mn, Ni and Zn) in two genera of macroalgae, Ulva and Enteromorpha was studied at 22 sites on the northwest coast of Spain. The seasonal variation in the different metals followed a similar pattern in both seaweeds and appeared to be caused by dilution during the period of maximum growth and concentration during periods of slow growth. Fluvial inputs of Al, Fe and Mn in autumn and winter appeared to accentuate the latter effect: the concentrations of these three metals in both macroalgae and of Cr in Enteromorpha were highest at those sites most influenced by inputs from rivers. The background levels of Cr, Cu, Ni and Zn in the algae in summer and winter were established.     

Metal accumulation in the greentail prawn, Metapenaeus bennettae, in Sydney and Port Hacking estuaries, Australia

Metal concentrations of the inshore greentail prawn, Metapenaeus bennettae, and surface sediments from locations within Sydney estuary and Port Hacking (Australia) were assessed for bioaccumulation and contamination. The current study aimed to assess metal concentrations in prawn tissue (tail muscle, exoskeleton, hepatopancreas and gills), relate whole body prawn tissue metal concentrations to sediment metal concentrations and animal size, as well as assess prawn consumption as a risk to human health. Metal concentrations were highest in sediment and prawns from contaminated locations (Iron Cove, Hen and Chicken Bay and Lane Cove) in Sydney estuary compared with the reference estuary (Port Hacking). Concentrations in sediments varied considerably between sites and between metals (As, Cd, Cr, Cu, Ni, Pb and Zn), and although concentrations exceeded Interim Sediment Quality Guideline-Low values, metals (As, Cd, Cr, Cu, Ni, Pb and Zn) were below Australian National Health and Medical Research Council human consumption guidelines in prawn tail muscle tissue. Metal concentrations in prawn tail muscle tissue were significantly different (p?≤?0.05) amongst locations for Pb, Zn and Cd, and metal concentrations were generally highest in gills tissue, followed by the hepatopancreas, exoskeleton and tail muscle. The exoskeleton contained the highest Sr concentration; the hepatopancreas contained the highest As, Cu and Mo concentrations; and the gills contained the highest Al, Cr, Fe and Pb concentrations. Concentrations of Pb, As and Sr were significantly different (p?≤?0.05) between size groups amongst locations.     

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.     

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...     

An ozone flux-response relationship for wheat

The concentrations of heavy metals in the fine fraction (<63 microm) of 19 surficial sediment samples from the border region of Baja California (Mexico) and California (USA) were determined. The concentration ranges (in microg g(-1)) of the metals were: Cu, 4.9-23; Zn, 39-188; Ni, 16-44; Cr, 56-802; Pb, 6-21; Cd, 0.08-0.64; Ag, 0.01-0.28; and Mn, 392-1506; the intervals (percentage) for Fe and Al were 1.36-4.6 and 3.61-8.55, respectively. The heavy metals in these sediments indicate a relative enrichment of Cr (>3000%), Zn (>350%), Ni (>300%) and Cu (>150%) off the wastewater outfall at Punta Bandera in Tijuana, Baja California, with respect to non-polluted sediments of the region. Pb, Cd and Ag have low concentrations off the same outfall and enrichment factors are generally lower than 300% (Pb) and lower than 150% (Cd and Ag). This suggests that these metals have a different origin, or that they are controlled by a different geochemical mechanism than the former. The concentrations of Mn, Fe and Al occurred within ranges typical for coastal areas and probably reflect the mineralogical composition of the sediments of the region.     

Analysis of essential and non-essential trace elements in the organs of a mother–fetus pair of spotted seals (Phoca largha) from the Sea of Japan

Environmental Science and Pollution Research - Concentrations of 22 essential and non-essential trace elements (Be, Al, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Mo, Ag, Cd, Sb, Ba, Tl, Pb, Th, U, and...     

Comprehensive assessment of toxic metals in urban and suburban street deposited sediments (SDSs) in the biggest metropolitan area of China

A set of toxic metals, i.e. As, Hg, Pb, Cd, Cu, Zn, Ni and Cr, in urban and suburban SDSs were investigated comparatively in the biggest metropolitan area of China, Shanghai. Results showed that all of the metals except As were accumulated greatly, much higher than background values. Geo-accumulation index indicated that metal contamination in urban SDSs was generally heavier than that in suburban SDSs. Potential ecological risk index demonstrated that overall risks caused by metals were considerable. Cd contributed 52% to the overall risk. Multivariate statistical analysis revealed that in urban SDSs, Zn, Ni, Cd, Pb, Cu and Cr were related to traffic and industry; coal combustion led to elevated levels of Hg; soil parent materials controlled As contents. In suburban SDSs, Pb, Cu, As and Cd largely originated from traffic pollution; Zn, Ni and Cr were associated with industrial contaminants; Hg was mainly from domestic solid waste.     

Levels and composition of atmospheric particulates (PM10) in a mining-industrial site in the city of Lavrion,Greece

The present work focuses on the characterization of air quality and the identification of pollutant origin at a former mining site in the city of Lavrion, Greece. A historical metallurgy complex is reused for establishing the Lavrion Technology and Cultural Park (LTCP). A serious problem with this is the severe soil contamination that resulted from intensive mining and metallurgical activities that has taken place in the greater area for the past 3,000 years. Among other consequences, surface-polluted depositions, rich in heavy and toxic metals, are loose and easily wind-eroded, resulting in transportation of particulate matter (PM) in the surrounding atmosphere. On the other hand, there are a number of industries relatively close to the site that are potential sources of PM air pollution. The current study deals with the collection and analysis of PM10 samples with respect to their concentration in heavy metals, such as Pb, Cd, Cu, Fe, Zn, Mn, Cr, and Ni. Though not a heavy metal, As also is included. Furthermore, the source of these elements is verified using statistical correlation and by calculating enrichment factors (EFs), considering that some substances are certainly of contaminated soil origin. Results show that PM10 and element concentrations are relatively low during winter but significantly increase during summer. Fe, Pb, Zn, Mn, and Cu may be considered of contaminated soil origin, while As, Ni, Cd, and Cr are very much enriched with respect to contaminated soil, indicating another possible source attributed to the adjacent industrial plants.     

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.