Multielement analysis in the fish hepatic cytosol as a screening tool in the monitoring of natural waters

The possibility of direct measurement of trace elements in hepatic cytosol of European chub (Squalius cephalus) by high-resolution inductively coupled plasma mass spectrometry (HR ICP-MS) after cytosol dilution with Milli-Q water and subsequent acidification was investigated. Due to low detection limits of this procedure, determination of 13 elements (As, Cd, Co, Cu, Fe, Mn, Mo, Pb, Sb, Sn, Sr, V and Zn) was possible in the chub hepatic cytosol, exhibiting excellent measurement repeatability in duplicates. Some of these elements were also measured by HR ICP-MS in acid digested cytosols (Cd, Co, Cu, Fe, Mn, Mo, Sr, V and Zn). Good agreement of the results obtained after sample dilution and sample digestion indicated that complex organic matrix of hepatic cytosol did not affect measurement reliability. Cytosolic concentrations of 13 trace elements in the chub liver were quantified in the following order: Fe, Zn>Cu>Mn>Mo>Sr, V, Cd>Co>As, Pb>Sn>Sb. Unlike Cd, Cu, Fe, Mn and Zn for which the cytosolic concentrations were previously reported after measurement by AAS, cytosolic concentrations of eight additional trace elements characteristic for the liver of chubs inhabiting the low contaminated river water were reported here for the first time (in nanogrammes per gramme)—Mo, 136.8–183.6; Sr, 32.7–63.0; V, 17.5–69.0; Co, 24.3–30.7; As, 9.9–29.5; Pb, 5.8–35.6; Sn, 5.5–12.4; and Sb, 0.9–2.6. The simultaneous measurement of large number of trace elements in the cytosolic fractions of fish tissues, which comprise potentially metal-sensitive sub-cellular pools, could be beneficial as a screening tool in the monitoring of natural waters, because it would enable timely recognition of increased fish exposure to metals.     

Load of Heavy Metals in the Airborne Dust Particulates of an Urban City of Central India

The geographical and temporal distribution patterns of airborne dust particulates have been studied in different representative areas of Raipur City. Dust fall samples from different sites were collected and some selected toxic metals namely Cr, Mn, Fe, Ni, Cu, Zn, Sb and Pb in them were determined by AAS. Total annual flux of 11.7, 541.4, 2751.0, 14.2, 9.8, 90.9, 17.6, and 17.7 kg km(-2) y(-1) were measured for Cr, Mn, Fe, Ni, Cu, Zn, Sb, and Pb respectively. The occurrence of metal concentration were generally in the order industrial > heavy traffic > commercial > residential area in Raipur city. The results of analysis show the existence of toxic metal concentration in the order Fe > Mn > Zn > Pb approximately Sb > Ni > Cr > Cu in Raipur city. These large levels of metal pollutants have also been correlated with some meteorological parameters like temperature, relative humidity and wind velocity, and strong positive correlations have been observed.     

Spatial distribution and risk assessment of heavy metals in sediments from a hypertrophic plateau lake Dianchi, China

The sediment in Dianchi Lake, a hypereutrophic plateau lake in southwest China, was investigated and the concentration of heavy metals (Cu, Cr, Ni, Zn, Pb, Fe, Mn, and Cd) in the sediment and sediment properties were determined. Their spatial distribution and sources were analyzed using multivariate statistics. The result indicated that the studied metals exhibited three distinct spatial patterns; that is, Cu, Pb, Zn, and Ni had a similar distribution, with a concentration gradient from the north to the south part of the lake; Cd and Cr presented a similar distribution; Fe and Mn presented a quite different distribution than other metals, which indicated their different sources and geochemistry processes. Correlation and cluster analysis (CA) provided origin information on these metals and the CA result was observed corresponding to those three spatial patterns. Principal component analysis further displayed metal source and driving factors; that is, Cu, Pb, Zn, Ni, Cd, and Cr were mainly derived from anthropogenic sources, and Fe and Mn were mainly the result of natural processes. Sediment assessment was conducted using geoaccumulation index (Igeo), potential ecological risk indices, and USEPA guidelines. The result indicated that, generally, Cd was the most serious risk metal; Pb and Cu posed moderate potential ecological risk; Cr, Zn, and Ni had slight ecological risk; Fe and Mn had little risk. Comparison of the assessment tools showed that each of the methods had its limitation and could bias the result, and the combined use of the methodologies and local knowledge on lithology or metal background value of soil in the practice would give a more comprehensive understanding of the metal risk or pollution. Statistical analysis also indicated that nutrients had different impacts on Fe, Mn, and trace elements, which implied that in the assessment of metal risk, nutrients impact should be taken into consideration especially for eutrophic waters.     

Comparison of trace metal bioavailabilities in European coastal waters using mussels from Mytilus edulis complex as biomonitors

Mussels from Mytilus edulis complex were used as biomonitors of the trace metals Fe, Mn, Pb, Zn, and Cu at 17 sampling sites to assess the relative bioavailability of metals in coastal waters around the European continent. Because accumulated metal concentrations in a given area can differ temporally, data were corrected for the effect of season before large-scale spatial comparisons were made. The highest concentration of Fe was noted in the North Sea and of Mn in the Baltic. Increased tissue concentrations of Pb were recorded in the mussels from the Bay of Biscay and the Baltic Sea. Low concentrations of metals were determined in the mussels from the Mediterranean Sea and the Northern Baltic. Relatively low geographic variations of Cu and Zn indicate that mussels are able to partially regulate accumulated body concentrations, which means Cu and Zn are, to some extent, independent of environmental concentrations.     

Heavy metals concentration in edible fishes from coastal region of Kalpakkam, southeastern part of India

Concentrations of Cu, Mn, Zn, Fe, Cr, and Pb were estimated using ICP-MS in nine commercially important and locally consumed fish species (Sarda orientalis, Scomberomorus commerson, Rastrelliger kanagurta, Sardinella longiceps, Paraplagusia bilineata, Cynoglossus lida, Cynoglossus macrostomus, Lepturacanthus savala, and Siganus javus) collected from coastal waters of Kalpakkam, eastern part of India. Their concentration (μg g(-1)) in the examined fish species ranged as follows: Cu (0.8-6.5), Zn (14.3-27.9), Mn (0.5-8.8), Fe (17.6-117.0), Cr (0.24-1.78), and Pb (0.18-2.29). Concentrations of most of the metals in the fish species studied were found to be safe for human consumption barring Mn.     

Natural concentrations and reference values of heavy metals in sedimentary soils in the Brazilian Amazon

The soils of the Brazilian Amazon exhibit large geochemical diversity reflecting the different soil formation processes in an area covering 49% of the Brazilian territory. Soil contamination by heavy metals is one of the threats to the sustainability of this Biome but establishing quality reference values (QRVs) for the region is a challenging owing to the immense territorial area of the Amazon. This study aimed to determine the natural background of heavy metals in soils from the southwestern Brazilian Amazon in order to propose QRVs for Ba, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Sb, and Zn for alluvial sedimentary soils. One hundred and twenty-eight soil samples were collected at a depth of 0.0–0.2 m in sites with minimal anthropogenic interference. Soil sample digestion was based on the EPA 3051A method and metal concentrations were determined by ICP-OES. QRVs calculated for the southwestern Brazilian Amazon are among the lowest recorded in Brazil (mg kg^?1): Ba (16.5), Cd (0.1), Cr (6.9), Cu (2.8), Fe (15.4), Mn (13.4), Ni (1.7), Pb (4.4), Sb (0.9), and Zn (5.7). The low metal concentration is likely a result of the sedimentary origin of the soils. The results of this study can serve as a basis for defining public policies to investigate the environmental impacts resulting from changes in land use in areas of the Brazilian Amazon.     

Monitoring of total and bioavailable heavy metals concentration in agricultural soils

The aim of this paper is to evaluate total and bioavailable concentration of heavy metals in agricultural soils in order to estimate their distribution, to identify the possible correlations among toxic elements and the pollution sources, to distinguish the samples in relation to sampling site or to sampling depth, and to evaluate the available fraction providing information about the risky for plants. In particular, we reinvestigated total concentrations of As, Be, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sb, V, and Zn and available concentrations of As, Be, Cd, Cr, Cu, Hg, Ni, Pb, Sb, and Zn in soil from Apulia (Southern Italy). Analytical results showed that total concentrations, for all soils, are in the range permitted by regulations in force in Italy, but some soils evidence slight enrichment of Cd, Cr, Cu, Pb, and Zn. All the heavy metals in the available fraction were below the detection limits of the analytical techniques used except Cu, Ni, Pb, and Zn.     

Characterization of land-based sources of pollution in Jobos Bay,Puerto Rico: status of heavy metal concentration in bed sediment

As part of an assessment of land-based sources of pollution in Jobos Bay, Puerto Rico, sediment samples were collected at 43 sites to characterize concentrations of a suite of pollutants, including metals. Fifteen major and trace metals (Ag, Al, As, Cd, Cr, Cu, Fe, Hg, Mn Ni, Pb, Sb, Se, Sn, and Zn) were measured along with total organic carbon and grain size in surficial sediments. For most metals, maximum concentrations were seen in the eastern bay; however, values were still within concentration ranges found in other estuarine systems. In contrast, silver was higher in the western region. In general, metal distribution in the bay was positively correlated with grain size. Additionally, correlations between Al and other metals suggest natural sources for metals. The data presented here suggest that, although the Jobos Bay watershed contains both urban centers along with industrial and agricultural developments, anthropogenic inputs of metals may be negligible.     

Statistical distributions of trace metal concentrations in the northwestern Mediterranean atmospheric aerosol

The concentrations of 11 crustal and anthropogenic trace metals (Li, Al, V, Mn, Fe, Co, Ni, Cu, Zn, Cd, Pb) were measured from 2006 to 2008 in the atmospheric aerosol at a northwestern Mediterranean coast (station of Cap Ferrat, situated on the southeastern coast of France). Statistical models (lognormal, Weibull, and gamma) that best represented the trace metal distribution for this environment are described. The lognormal model was selected for the distributions of (in decreasing strength of the fit) Al, Co, Li, Zn, Mn, Cu, Pb, and Cd, i.e., metals that are introduced into the atmospheric aerosol by pulses inducing temporal variability in their concentrations. The gamma model was associated with Fe, i.e., metals that exhibit less inter-annual variability than the former trace metals. The third mode (Weibull) represented the distribution of the concentrations of V and Ni. The statistical approach presented in this study contributed to better define and constrain the distribution of the 11 trace metals of the atmospheric aerosol from the northwestern Mediterranean coast. In a close future, knowledge of these statistical distributions will allow using convolution models to separate their natural and anthropogenic contributions, therefore increasing our ability to study anthropogenic emissions of trace metals and their impact on the environment.     

Assessment of background levels of trace metals in water and soil from a remote region of Himalaya

Selected trace metals were estimated by atomic absorption spectrometry in the water and soil samples collected from the remote region of Himalaya. The soil samples were analysed for soluble and acid extractable fraction of trace metals. In water samples, Ca, Na, Mg and K emerged as dominant contributors, whereas, Ca, Na, K, Mg, Fe and Pb were estimated at comparatively higher levels in the water extract of the soil. In case of acid extract of the soil samples, Ca, K, Fe, Mg, Mn and Na were found at elevated concentrations. Based on mean levels of the metals, following decreasing concentration order was observed in water samples: Ca > Na > Mg > K > Pb > Co > Cu > Zn > Mn > Cr > Fe > Cd > Li, however, in the acid extract of the soil, following order was noted: Ca > K > Fe > Mg > Mn > Na > Pb > Zn > Cr > Li > Cu > Co > Cd. The correlation study revealed appreciably diverse mutual relationships of trace metals in the water and soil samples. The multivariate cluster analyses exhibited divergent apportionment of trace metals in water and soil samples. Among the trace metals, Cd, Pb, Li, Zn, Cr, Cu, Mn and Co exhibited extreme to significant anthropogenic enrichment in the soil samples, while the rest of the metals were mostly contributed by the natural processes.     

Spatial distribution of trace metals (Cd, Pb, Hg, Cu, Zn, Fe and Mn) and oligo-elements (Mg, Ca, Na and K) in surface sediments of the Gulf of Tunis (Northern Tunisia)

The purpose of this paper is to evaluate the levels and spatial distribution of trace metals (Cd, Pb, Cu, Hg, Zn, Fe, and Mn), oligo-elements (Mg, Ca, Na and K), total organic carbon (TOC), and total nitrogen (TN) in the fine fraction of surface sediments collected from 38 stations in Gulf of Tunis (Mediterranean Sea, Northern Tunisia) between 2004 and 2005. The results showed that metals, oligo-elements, TOC, and TN concentrations in the sediments of the Gulf of Tunis are generally low compared to those found in other similar coastal marine areas. The spatial distribution of metals showed areas of major accumulation of Pb, Cd, Cu, Fe, and Zn in the central area of the Gulf and near the Mejerda River. The marine currents are influencing factors on metal accumulation in sediments. The principal component analysis applied to our elemental analytical results showed that there is a positive correlation between Fe, Zn, Cu, and Pb. These metals have a stronger affinity with site connection in the sediments than Ca and Mn.     

Characterization of heavy metals in water and sediments in Taihu Lake, China

To explore a comprehensive status of heavy metals in the Taihu Lake, which is one of the most important waters in China, water and sediment samples were taken throughout the lake during April to May of 2010, and metal elements (Cu, Cd, Cr, Ni, Pb, Sn, Sb, Zn, Mn) were analyzed in the water column, interstitial water and sediment. Relevant standards were used to assess the sediment and water quality. Results show that, in the lake water column, the average concentration of all metals ranged from 0.047 μg/l (Cd) to 8.778 μg/l (Zn). The concentration in the river water was usually higher than in the lake water for many metals. In the interstitial water Mn was significantly higher than that in water column, and other metals had no significant difference between the two media. In the surface sediment, average metal content ranged from 1.325 mg/kg (Cd) to 798.2 mg/kg (Mn). Spatially, contents of many metals were higher in Zhushan Bay than in other lake areas, and there existed a clear content gradient from the river to the lake for both water and sediment. On the sediment profiles, many metals presented an increasing trend from the depth of 15-20 cm to the top, which is indicative of the impact of increasingly intensive human activities from that period. Quality assessment indicates that metals in water phase are generally safe compared with USEPA "National Recommended Water Quality Criteria," with the exception of Mn in the interstitial water and Sb in the river water. Whereas the sediment is widely contaminated with metals to some extent compared with the "Consensus-Based Sediment Quality Guidelines," and Cu, Cr, and Ni are more likely to raise ecological risks. This work could be a basis for the ongoing China's criteria strategy.     

Seasonal Variability of Heavy Metals in Surface Sediment of Lake Sapanca, Turkey

Lake Sapanca is exposed to heavy urbanization and industrialization because of its natural beauty and its proximity to the metropolitan İstanbul, Turkey. In this study, it was aimed to investigate seasonal changes of some heavy metals (Pb, Cr, Cu, Mn, Ni, Zn and Cd) concentration of surface sediment. Nine different stations were chosen as sampling points. Samples were taken every three months and the seasonal and annual average concentration of the elements were determined. Seasonal highest values of heavy metals were observed as follows; Cr, Cu, Mn, Ni and Zn in Summer, Cd in Autumn. There was no seasonal difference for Pb, Cr and Cd. It seems that Lake Sapanca has not been polluted yet. However, it was found that Cu and Ni concentrations in surface sediment exceed lowest effect level.     

Trace metal bioaccumulation in eight common coastal Australian polychaeta

Whole tissue trace metal concentrations of ten metals in eight common coastal Australian polychaete species collected from uncontaminated locations were measured. The mean concentration range for each trace metal was: Mn: 2.6-13 microg g(-1); Co: 0.8-4.6 microg g(-1); Cu: 3.4-26 microg g(-1); Zn: 47-225 microg g(-1); As: 18-101 microg g(-1); Se: 2.2-20.4 microg g(-1); Ag: 0.03-2.5 microg g(-1); Cd: 0.07-17 microg g(-1); Hg: 0.08-0.88 microg g(-1) and Pb: 0.09-3.2 microg g(-1)dry mass. Principal components analysis of trace metal signatures revealed that the habitat, i.e. exposed coast sand or rock, estuarine sand or estuarine mud substrate in which a polychaete species was found, had a significant influence on the bioaccumulation of six trace metals (Mn, Cu, Zn, Ag, Cd and Pb). However, there is no clear relationship between trace metal concentrations in substrates and polychaetes. The results of the current study contribute to a reference dataset of polychaete species-specific natural background trace metal concentrations for use in determining the extent of trace metal contamination by urban and industrial sources.     

Concentrations of toxic heavy metals and trace elements in raw milk of Simmental and Holstein-Friesian cows from organic farm

Concentrations of toxic heavy metals (cadmium (Cd), lead (Pb)) and major nutritional and trace elements (Ca, Mg, P, Cu, Fe, Mn, Se, Zn) were analyzed in the milk of Simmental (n?=?20) and Holstein-Friesian (n?=?20) cows from an organic farm. Elements were determined using inductively coupled plasma emission atomic spectrometry. The conducted research showed that the milk of Simmental cows was characterized by the more advantageous mineral composition and lower concentration of noxious heavy metals compared to the milk of Holstein-Friesian cows. In the milk of Simmental cows, significantly lower concentrations of Pb and Cd (P?<?0.001) and Cu (P?<?0.05) and significantly higher concentrations of Fe and Mg (P?<?0.05) as well as nonsignificantly higher concentrations of Ca, Mn, and Se were found. In the milk of both breeds, very low Cu concentrations were recorded. The higher-than-recommended concentration of Pb in milk was also found. In the milk of both breeds, the significant positive correlations between concentrations of the following elements were observed: Pb–Cd, Pb–Se, Cd–Se, Cd–Mn, Zn–Cu, Zn–P, Ca–P, Ca–Mg, and Mg–P. The correlations between other elements within each of the analyzed breeds separately were also found.     

Characterization and source identification of airborne trace metals in Singapore

Airborne particulate trace metals have important health implications. As a consequence, their concentrations are increasingly monitored in many urban locations worldwide. In this study, fine atmospheric particles (PM(2.5)) were collected in Singapore over a period of 83 consecutive days during 2000, and analysed to determine the concentration of trace elements using ICP-MS. Altogether, eighteen airborne trace metals were quantified: Al, Ag, Ba, Cd, Cr, Co, Cu, Fe, Ga, Li, Mn, Ni, Pb, Sr, Zn, V, Si, and Ti. While Li was the least abundant trace metal with a mean concentration of 0.2 ng m(-3), Zn showed the maximum mean concentration of 279.1 ng m(-3). Calculation of enrichment factors indicated that the elements Pb, Zn, Cd, V, Ni, Cr, and Cu were enriched by factors of 30 to 5000 relative to their natural abundance in crustal soil. The extent of metal pollution in the study area was assessed by comparing the measured concentrations to those reported in the literature for a selected number of urban sites in other parts of the world. Factor analysis was used to identify the major sources affecting particulate air pollution in Singapore. The sources that contribute to the loading of trace metal-bearing aerosols in the Singapore urban atmosphere include fuel oil-fired power plants, metal processing industry, land reclamation and construction activities, municipal solid waste incinerators, and traffic emissions.     

Trend in metals variation in Tasik Chini, Pahang, Peninsular Malaysia

Water from 15 sampling stations in Tasik Chini (Chini Lake), Peninsular Malaysia were sampled for 12 months from September 2004 until August 2005 and analyzed for 11 metals including iron (Fe), aluminum (Al), manganese (Mn), barium (Ba), zinc (Zn), lead (Pb), copper (Cu), cadmium (Cd), nickel (Ni), chromium (Cr) and cobalt (Co). Results showed that the mean (min-max) metal concentrations (in micrograms per liter) in Tasik Chini waters for the 12 months sampling based on 15 sampling stations (in descending order) for Fe, Al, Mn, Ba, Zn, Pb, Cu and Cd were 794.84 (309.33-1609.07), 194.53 (62.37-665.93), 29.16 (16.68-79.85), 22.07 (15.64-29.71), 5.12 (2.224-6.553), 2.36 (1.165-4.240), 0.832 (0.362-1.443) and 0.421 (0.254-0.696) respectively. Concentration for three metals i.e. Ni, Cr and Co were too low and not detected by the graphite furnace Atomic Absorption Spectrophotometry (AAS). Comparison with various water quality standards showed that the mean metals concentration in surface water of Tasik Chini were low and within the range of natural background except for Fe and Al. In general, metal concentrations in Tasik Chini water varied temporally and spatially. The main factors influencing these metal concentrations in the water were the raining season and mining activities. Stations located at Tanjung Jerangking and Melai areas were the most effected due to those factors.     

Chemometric study on the trace metal accumulation in the sediments of the Cochin Estuary―Southwest coast of India

The distribution and accumulation of trace metals in the sediments of the Cochin estuary during the pre-monsoon, monsoon and post-monsoon periods were investigated. Sediment samples from 14 locations were collected and analysed for the metal contents (Mg, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd and Pb), organic carbon, total nitrogen, total sulphur and grain size. The data were processed using statistical tools like correlation, factor and cluster analysis. The study revealed an enrichment of Cd and Zn in the study area particularly at station 2, which is confirmed by enrichment factor, contamination factor and geoaccumulation index. The factor analysis revealed that the source of Cd and Zn may be same. The study indicated that the spatial variation for the metals like Mg, Cr, Fe, Co, Ni, Cu, Zn, Cd and Pb were predominant unlike Mn which shows a temporal variation. The strong association of trace metals with Fe and Mn hydroxides and oxides are prominent along the Cochin estuary. The anthropogenic inputs of industrial effluents mainly control the trace metals enrichment in the Cochin estuary.     

Chemical speciation of inorganic pollutants in river–estuary–sea water systems

Monitoring studies and thermodynamic modeling were used to reveal the changes of inorganic chemical species of some water pollutants (nutrients and trace metals such as Fe, Mn, Zn, Cu, Cd and Pb) inthe river-estuary-sea water system. The case studies were two rivers, Kamchiya and Ropotamo, representing part of the Bulgarian Black Sea water catchment area, and having different flow characteristics. There were no major differences in inorganic chemical species of the two river systems. NO3(-) and NO2(-) chemical species showed no changes along the river-estuary-sea water system. Concerning phosphates six different species were calculated and differences between the three parts of the systems were established. The HPO4(2-) and H2PO4(-) species were found to be dominant in river waters. The H2PO4(-) species quickly decreased at the expense of HPO4(2-) and Ca, Mg and Na phosphate complexes in estuary and seawater. Trace metals showed a great variety of chemical species. Fe(OH)2(+) species prevailed in river waters, and Fe(OH)3(0) species--in sea waters. Me2+ and MeCO3(0) (Me = Cu, Pb) and PbHCO3(+) were dominant in river waters, while Cu(CO3)2(2-) and PbCl(-) species appear also in sea waters. Cd2+ species prevailed in river and estuary waters, and CdCln(2-n) (n = 1-3) species, in seawater. Free Zn2+ species predominated in all systems but downstream their percentage decreased at the expense of Zn phosphates, carbonates,sulfates and chlorides complexes. Only free Mn2+ species were dominant along the systems.     

An Effective Means of Biofiltration of Heavy Metal Contaminated Water Bodies Using Aquatic Weed Eichhornia crassipes

Various aquatic plant species are known to accumulate heavy metals through the process of bioaccumulation. World’s most troublesome aquatic weed water hyacinth (Eichhornia crassipes) has been studied for its tendency to bio-accumulate and bio-magnify the heavy metal contaminants present in water bodies. The chemical investigation of plant parts has shown that it accumulates heavy metals like lead (Pb), chromium (Cr), zinc (Zn), manganese (Mn) and copper (Cu) to a large extent. Of all the heavy metals studied Pb, Zn and Mn tend to show greater affinity towards bioaccumulation. The higher concentration of metal in the aquatic weed signifies the biomagnification that lead to filtration of metallic ions from polluted water. The concept that E. crassipes can be used as a natural aquatic treatment system in the uptake of heavy metals is explored.