Heavy metals in nearshore sediments of Kalpakkam,southeast coast of India

Kalpakkam, a tiny fishing hamlet dotting the east coast, halfway between Chennai and Pondicherry has become prominent due to the Madras Atomic Power Station. The present study aims at assessing the spatial and temporal distribution pattern of heavy metals (Cd, Pb, Zn, Cu, Ni, Cr, and Fe) from 12 stations along the inner shelf of Bay of Bengal, India, during pre-monsoon (PRM), monsoon, and post-monsoon (POM) seasons. The order of occurrence of the metals in sediments of Kalpakkam is Cr > Zn > Ni > Cu > Pb > Cd (excluding Fe since unit is in %) and exhibits a unique seasonal pattern with the highest values (average) during POM except for Cd which shows highest (average) concentration during PRM. In order to determine the sample association according to their geochemical composition and their granulometric characteristics, a correlation matrix was generated and sediment pollution indices viz., sediment enrichment factor and geoaccumulation index were computed. The results confirm anthropogenic input of Cd to nearshore sediments of Kalpakkam. Sources of Cd can be attributed to dredging activities at Edaiyur, direct dumping and sewage sludge from anthropogenic activities, which reach the study area through the Buckingham Canal opening at the backwaters—Sadras and Edaiyur, and extreme use of antifouling paints by fishing trawlers.     

Distribution and immobilization of heavy metals in Pliocene aquifer sediments in Wadi El Natrun depression, Western Desert

The Pliocene aquifer receives inflow of Miocene and Pleistocene aquifer waters in Wadi El Natrun depression. The aquifer also receives inflow from the agricultural activity and septic tanks. Nine sediment samples were collected from the Pliocene aquifer in Wadi E1 Natrun. Heavy metal (Cu, Sr, Zn, Mn, Fe, Al, Ba, Cr, Ni, V, Cd, Co, Mo, and Pb) concentrations of Pliocene aquifer sediments were investigated in bulk, sand, and mud fractions. The determination of extractable trace metals (Cu, Zn, Fe, Mn, and Pb) in Pliocene aquifer sediments using sequential extraction procedure (four steps) has been performed in order to study environmental pathways (e.g., mobility of metals, bounding states). These employ a series of successively stronger chemical leaching reagents which nominally target the different compositional fractions. By analyzing the liquid leachates and the residual solid components, it is possible to determine not only the type and concentration of metals retained in each phase but also their potential ecological significance. Cu, Sr, Zn, Mn, Fe, and Al concentrations are higher in finer sediments than in coarser sediments, while Ba, Cr, Ni, V, Cd, Co, Mo, and Pb are enriched in the coarser fraction. The differences in relative concentrations are attributed to intense anthropogenic inputs from different sources. Heavy metal concentrations are higher than global average concentrations in sandstone, USEPA guidelines, and other local and international aquifer sediments. The order of trace elements in the bulk Pliocene aquifer sediments, from high to low concentrations, is Fe?>?Al?>?Mn?>?Cr?>?Zn?>?Cu?>?Ni?>?V?>?Sr?>?Ba?>?Pb?>?Mo?>?Cd?>?Co. The Pliocene aquifer sediments are highly contaminated for most toxic metals, except Pb and Co which have moderate contamination. The active soluble (F0) and exchangeable (F1) phases are represented by high concentrations of Cu, Zn, Fe, and Mn and relatively higher concentrations of Pb and Cd. This may be due to the increase of silt and clay fractions (mud) in sediments, which act as an adsorbent, retaining metals through ion exchange and other processes. The order of mobility of heavy metals in this phase is found to be Pb?>?Cd?>?Zn?>?Cu?>?Fe?>?Mn. The values of the active phase of most heavy metals are relatively high, indicating that Pliocene sediments are potentially a major sink for heavy metals characterized by high mobility and bioavailability. Fe–Mn oxyhydroxide phase is the most important fraction among labile fractions and represents 22% for Cd, 20% for Fe, 11% for Zn, 8% for Cu, 5% for Pb, and 3% for Mn. The organic matter-bound fraction contains 80% of Mn, 72% of Cu, 68% of Zn, 60% of Fe, 35% of Pb, and 30% of Cd (as mean). Summarizing the sequential extraction, a very good immobilization of the heavy metals by the organic matter-bound fraction is followed by the carbonate-exchangeable-bound fraction. The mobility of the Cd metal in the active and Fe–Mn oxyhydroxide phases is the highest, while the Mn metal had the lowest mobility.     

Temporal and spatial variability of trace metals in suspended matter of the Mandovi estuary,central west coast of India

Studies on the suspended particulate matter (SPM) in the Mandovi estuary, western India indicate that during the monsoon and pre-monsoon, the SPM increases, and the major and trace metals decrease from stations in the upstream to downstream of the estuary. SPM is consistently low at all stations during the post-monsoon. Trace metals (Cu, Ni, Zn, Cr, and Pb) show strong inter-relationships. They correlate well with Fe and Mn only during the monsoon. The concentrations of Cr, Cu, and Pb are high during the post-monsoon. Enrichment factors and I _geo values of metals indicate that Mn shows significant to strong pollution in all seasons, while Cr, Ni, and Zn during monsoon, and Cr during the post-monsoon show moderate pollution. SPM is controlled by the turbidity maximum, while major and trace metals are governed seasonally by a combination of river discharge, resuspension, spillage of Fe–Mn particulates, and anthropogenic contamination. Incursion of saline waters deep into the river channel during the dry season facilitates aggregation and settling of particulate-borne pollutants close to the discharge area, thereby keeping the estuarine waters free from major contamination.     

Major ion chemistry and metal distribution in coal mine pit lake contaminated with industrial effluents: constraints of weathering and anthropogenic inputs

Ion chemistry of mine pit lake water reveals dominance of alkaline earths (Ca²⁺ and Mg²⁺) over total cation strength, while SO₄ ^2? and Cl^? constitute the majority of total anion load. Higher value of Ca²⁺?+?Mg²⁺/Na⁺?+?K⁺ (pre-monsoon 5.986, monsoon 8.866, post-monsoon 7.09) and Ca²⁺?+?Mg²⁺/HCO₃ ^??+?SO ₄ ² (pre-monsoon 7.14, monsoon 9.57, post-monsoon 8.29) is explained by weathering of Ca?CMg silicates and dissolution of Ca²⁺-bearing minerals present in parent rocks and overburden materials. Silicate weathering supposed to be the major geological contributor, in contrast to bicarbonate weathering does a little. Distribution coefficient for dissolved metals and sorbed to surface sediments is in the order of Cd?>?Pb?>?Fe?>?Zn?>?Cu?>?Cr?>?Mn. Speciation study of monitored metals in surface sediments shows that Fe and Mn are dominantly fractionated in exchangeable-acid reducible form, whereas rest of the metals (Cr, Pb, Cd, Zn, and Cu) mostly in residual form. Cd, Pb, and Zn show relatively higher recalcitrant factor that indicates their higher retention in lake sediments. Factor loading of monitored physico-chemical parameters resembles contribution/influences from geological weathering, anthropogenic inputs as well as natural temporal factors. Ionic load/strength of lake water accounted for geochemical process and natural factors, while pollutant load (viz BOD, COD and metals, etc.) is associated with anthropogenic inputs through industrial discharge.     

Assessment of heavy metal pollution in surface water

A total of 96 surface water samples collected from river Ganga in West Bengal during 2004–05 was analyzed for pH, EC, Fe, Mn, Zn, Cu, Cd, Cr, Pb and Ni. The pH was found in the alkaline range (7.21–8.32), while conductance was obtained in the range of 0.225–0.615 mmhos/cm. Fe, Mn, Zn, Ni, Cr and Pb were detected in more than 92% of the samples in the range of 0.025–5.49, 0.025–2.72, 0.012–0.370, 0.012–0.375, 0.001–0.044 and 0.001–0.250 mg/L, respectively, whereas Cd and Cu were detected only in 20 and 36 samples (0.001–0.003 and 0.003–0.032 mg/L). Overall seasonal variation was significant for Fe, Mn, Cd and Cr. The maximum mean concentration of Fe (1.520 mg/L) was observed in summer, Mn (0.423 mg/L) in monsoon but Cd (0.003 mg/L) and Cr (0.020 mg/L) exhibited their maximum during the winter season. Fe, Mn and Cd concentration also varied with the change of sampling locations. The highest mean concentrations (mg/L) of Fe (1.485), Zn (0.085) and Cu (0.006) were observed at Palta, those for Mn (0.420) and Ni (0.054) at Berhampore, whereas the maximum of Pb (0.024 mg/L) and Cr (0.018 mg/L) was obtained at the downstream station, Uluberia. All in all, the dominance of various heavy metals in the surface water of the river Ganga followed the sequence: Fe > Mn > Ni > Cr > Pb > Zn > Cu > Cd. A significant positive correlation was exhibited for conductivity with Cd and Cr of water but Mn exhibited a negative correlation with conductivity.     

Role of monsoon rain on concentrations and dispersion patterns of metal pollutants in sediments and soils of the Ganga Plain, India

 Monsoon rain causes large scale sediment-water movement and reworking of sediments of the Ganga Plain which is one of the largest fluvial systems on Earth. Geomorphology and drainage type combined with sedimentation processes play a substantial role on dispersion and transport patterns of metals bound to sediments and soils. The study area of Kanpur-Unnao industrial region in the Ganga Plain has been divided into five independent geochemical domains on the basis of sediment-geomorphic, hydrological and geochemical characters. The monsoon hydrography and physico-chemical parameters (pH, conductivity) of the river and urban drain waters play a prominent role in regulating the concentrations and behaviour of the metals in the aquatic system of the Ganga Plain. Values of pH and specific electrical conductivity of the river water of the study area decrease whereas those of the urban drain water increase in post-monsoon period. The monsoon rain reduces the contents of Co, C-org, Cr, Fe and Ni and enhances the contents of Cd, Sn and Zn in sediments of post-monsoon period. In soils, it reduces the contents of Al, Co, Fe, Mn and Ni and enhances the contents of Cd, Sn and Zn in the post-monsoon period. These changes in concentrations vary from metal to metal and from one geochemical domain to the other. An increase in the concentrations of few metals in the soils from pre- to post-monsoon periods indicates that these metals were mobilized from the overflooding of metal rich waste-water onto the fields during high water stage and also by reworking of the soils through sheet floods during the monsoon time. Despite the changes in concentrations, metal dispersion patterns in each domain remain similar both in pre- and post-monsoon periods which indicate that the geochemical and sediment-geomorphic processes operating for the metal dispersion and mobilization in sediments are persistent even after large scale sediment-water movement and reworking of the sediments during the monsoon period. Received: 4 May 1998 · Accepted: 20 October 1998     

Assessment of heavy metal accumulation in macrophyte, agricultural soil, and crop plants adjacent to discharge zone of sponge iron factory

The present study deals with the characterization of effluent released from sponge iron industries and distribution of heavy metals in soil and macrophytes near to effluent discharge channel. Apart from this, accumulation of heavy metals in nearby soil and vegetation system irrigated with effluent-contaminated water is also the subject of this study. Physico-chemical analysis of effluent reveals that the concentration of total suspended solids (TSS), total hardness (TH), iron (Fe²⁺), and oil and grease are greater than the IS (1981) norms for discharge of water into inland water body. The soil along the sides of the effluent channel also shows higher concentration of heavy metals than the background soil. The enrichment of the heavy metals are in the order of Chromium (Cr) > Iron (Fe) > Manganese (Mn) > Zinc (Zn) > Copper (Cu) > Cadmium (Cd). Macrophytes growing along the sides of the effluent channel also show significant accumulation of heavy metals almost in the same order as accumulated in soil. Higher uptake of heavy metals by these varieties reveals that these species can be used for future phytoremediation. The effluent as well as contaminated water is extensively used for irrigation for growing vegetables like tomato (Lycopersicon esculatum) in the surrounding areas. Heavy metal accumulation in this agricultural soil are in the sequence of Cr > Fe > Mn > Zn > Cu > Cd. More or less similar type of accumulation pattern are also found in tomato plants except Fe and Zn exceeding Cr and Mn. Transfer Factor of heavy metals from soil to tomato plants (TF_S) shows average value of <1, suggesting less uptake of heavy metals from soil. Among the plant parts studied, fruit shows least accumulation. Although tomato plants show some phenotypic changes, the survival of tomato plants as well as least accumulation of metals in fruit reveals their tolerance to heavy metals. Therefore it may be suggested that this plant can be grown successfully in the heavy metal contaminated soil. Further research work on in situ toxicity test will be necessary in order to identify the most resistive variety on this particular type of contaminated site.     

Movement of seasonal eddies and its relation with cyclonic heat potential and cyclogenesis points in the Bay of Bengal

Movement of seasonal eddies in the Bay of Bengal (BOB) and its relation with cyclonic heat potential (CHP) and cyclogenesis points have been investigated in this study using 6 years (2002–2007) of global ocean monthly analysis datasets based on the Simple Ocean Data Assimilation (SODA) package (SODA v2.0.4) of Carton et al. (2005) and Indian Meteorological Department cyclogenesis points. The region dominated by anticyclonic eddies with CHP greater than 70 × 10⁷ J/m² as well as good correlations (>0.9) with sea surface height (SSH) and 26°C isothermal depth (D ₂₆) can be a potential region of cyclogenesis. The region dominated by cyclonic eddies with CHP greater than 50 × 10⁷ J/m² and good correlation (>0.9) with both SSH and D ₂₆ can serve as a potential region of high-level depression. Potential cyclogenesis regions are the southern BOB (5°N–12°N) for the post-monsoon season and the head of BOB (north of 15°N) during southwest monsoon. Seven potential regions are identified for the eddy formation for different seasons, which are consistent with the cyclogenesis points. The CHP distributions alone are able to explain the cyclone tracks for the pre-monsoon and post-monsoon seasons but not for the monsoon season.     

Sources and flux of trace elements in river water collected from the Lake Qinghai catchment,NE Tibetan Plateau

River waters play a significant role in supplying naturally- and anthropogenically-derived materials to Lake Qinghai, northeastern Tibetan Plateau. To define the sources and controlling processes for river water chemistry within the Lake Qinghai catchment, high precision ICP-MS trace element concentrations were measured in water samples collected from the Buha River weekly in 2007, and from other major rivers in the post-monsoon (late October 2006) and monsoon (late July 2007) seasons. The distributions of trace elements vary in time and space with distinct seasonal patterns. The primary flux in the Buha River is higher TDS and dissolved Al, B, Cr, Li, Mo, Rb, Sr and U during springtime than those during other seasons and is attributed to the inputs derived from both rock weathering and atmospheric processes. Among these elements, the fluxes of dissolved Cr, B and Rb are strongly influenced by eolian dust input. The fluxes of dissolved Li, Mo, Sr and U are also influenced by weathering processes, reflecting the sensitivity of chemical weathering to monsoon conditions. The anthropogenic sources appear to be the dominant contribution to potentially harmful metals (Ni, Cu, Co, Zn and Pb), with high fluxes at onset of the main discharge pulses due, at least partially, to a runoff washout effect. For other major rivers, except for Ba, concentrations of trace elements are higher in the monsoon than in the post-monsoon season. A total of 38.5 ± 3.1 tons of potentially harmful elements are transported into the lake annually, despite human activities within the catchment being limited. Nearly all river water samples contain dissolved trace elements below the World Health Organization guidelines for drinking water, with the exception of As and B in the Daotang River water samples collected in late July probably mobilized from underlying lacustrine sediments.     

Contamination,bioaccessibility and human health risk of heavy metals in exposed-lawn soils from 28 urban parks in southern China's largest city,Guangzhou

The total concentrations and oral bioaccessibility of heavy metals in surface-exposed lawn soils from 28 urban parks in Guangzhou were investigated, and the health risks posed to humans were evaluated. The descending order of total heavy metal concentrations was Fe > Mn > Pb > Zn > Cu > Cr > Ni > Cd, but Cd showed the highest percentage bioaccessibility (75.96%). Principal component analysis showed that Grouped Cd, Pb, Cr, Ni, Cu and Zn, and grouped Cr and Mn could be controlled two different types of human sources. Whereas, Ni and Fe were controlled by both anthropogenic and natural sources. The carcinogenic risk probabilities for Pb and Cr to children and adults were under the acceptable level (<1 × 10⁻⁴). Hazard Quotient value for each metal and Hazard Index values for all metals studied indicated no significant risk of non-carcinogenic effects to children and adults in Guangzhou urban park soils.     

Spatio-temporal dynamics of heavy metals in sediments of the river estuarine system: Mahanadi basin (India)

Dynamics of heavy metals in the surface sediments of Mahanadi river estuarine system were studied for three different seasons. This study demonstrates that the relative abundance of these metals follows in the order of Fe > Mn > Zn > Pb > Cr > Ni ≥ Co > Cu > Cd. The spatial pattern of heavy metals supported by enrichment ratio data, suggests their anthropogenic sources possibly from various industrial wastes and municipal wastes as well as agricultural runoff. The metal concentrations in estuarine sediments are relatively higher than in the river due to adsorption/accumulation of metals on sediments during saline mixing, while there is a decreasing trend of heavy metal concentrations towards the marine side. The temporal variations for metals, such as Fe, Mn, Zn, Ni and Pb exhibit higher values during monsoon season, which are related to agricultural runoff. Higher elemental concentrations are observed during pre-monsoon season for these above metals (except Ni) at the polluted stations and for metals, such as Cr, Co and Cd at all sites, which demonstrate the intensity of anthropogenic contribution. R-mode factor analysis reveals that “Fe–Mn oxy hydroxide”, “organic matter”, “CaCO₃”, and “textural variables” factors are the major controlling geochemical factors for the enrichment of heavy metals in river estuarine sediment and their seasonal variations, though their intensities were different for different seasons. The relationships among the stations are highlighted by cluster analysis, represented in dendrograms to categorize different contributing sites for the enrichment of heavy metals in the river estuarine system.     

Studies on the variations of heavy metals in the marine sediments off Kalpakkam,East Coast of India

During the last two decades, the coastal environment of southeast India has experienced intense developments in industry, urbanization and aquaculture. Moreover, the 2004 mega tsunami has devastated this coast, thus affecting the coastal sediment characteristics. These two phenomena prompted a study to characterize the sediment, to understand the mechanisms influencing the distribution of heavy metals and to create baseline data for future impact assessment. Results showed that the coastal sediment was carpeted with a mosaic of sand and silty sand with a minor amount of clay. Heavy metal values showed maximum variation for Fe and minimum for Cd. Their average values showed the following decreasing trend: Fe > Cu > Zn > Pb > Cr > Ni > Cd. This study shows that the major source of metals at Kalpakkam coast are land-based anthropogenic ones, such as, discharge from industrial waste, agricultural waste, urban, municipal and slum sewage into the Buckingham canal, which in turn discharges into the sea through backwaters, particularly during northeast monsoon period. A clear signature of the role of backwater discharge increasing the concentration of a few metals in the coastal sediments during monsoon period was observed. Assessments of the degree of pollution, concentration factor (CF), geoaccumulation index (I _geo) and pollution load index (PLI) have been calculated. CF values and I _geo indicated that the coastal sediment is moderately polluted by Cu and Cd. Increase in Cu, Pb and Zn concentration during the monsoon period (October–January) compared to the rest of the year was noticed. Factor analysis and correlation among the heavy metals concluded that Cr, Ni, Cd and Fe are of crustal origin, whereas, Cu, Pb and Zn are from anthropogenic sources. Organic carbon content in the sediment increased during monsoon period, pointing to the role of land runoff and backwater discharge in enhancing its content. The study also elucidates the impact of the recent tsunami in depleting metal content in the coastal sediment as compared to the pre-tsunami period.     

Characterisation of hydrous ferric oxides derived from iron-rich groundwaters and their contribution to the suspended sediment of streams

When Fe(II) bearing groundwaters surface in streams, particulate authigenic Fe-rich material is produced by oxidation. Such freshly precipitated Fe minerals may be transported as suspended sediment and have a profound impact on the fate of trace metals and nutrients in rivers. The objective of this study was to monitor changes in mineralogy and composition of authigenic material from its source to streams of increasing order. Groundwaters, surface waters, and suspended sediment in streams of different order were sampled in the Kleine Nete catchment (Belgium), a lowland with Fe-rich groundwaters (3.5–53.8 mg Fe/L; pH 6.3–6.9). Fresh authigenic material (>0.45 μm) was produced by oxidising filtered (<0.45 μm) groundwater and surface water. This material contained, on average, 44% Fe, and smaller concentrations of C, P, and Ca. Iron EXAFS (Extended X-ray Absorption Fine Structure) spectroscopy showed that the Fe was present as poorly crystalline hydrous ferric oxides with a structure similar to that of ferrihydrite. The Fe concentration in the suspended sediment samples decreased to 36–40% (stream order 2), and further to 18–26% (stream order 4 and 5). Conversely, the concentrations of organic C, Ca, Si, and trace metals increased with increasing stream order, suggesting mixing of authigenic material with suspended sediment from a different source. The Fe speciation in the suspended sediment was similar to that in fresh authigenic material, but more Fe–Fe interactions were observed, i.e. it was increasingly hydrolysed, suggesting ageing reactions. The suspended sediment in the streams of order 4 and 5 is estimated to contain between 31% and 59% of authigenic material, but more data are needed to refine this estimate. The authigenic material is an important sink for P in these streams which may alleviate the eutrophication risk in this catchment.     

Diel variation of arsenic,molybdenum and antimony in a stream draining natural As geochemical anomaly

The Mokrsko Stream in the central Czech Republic is an oxic and slightly alkaline stream that drains a natural As geochemical anomaly. Although long-term monitoring has characterized the general seasonal trends in trace element concentrations (i.e., As, Mo, Cu, Zn) in this stream, little is known about solubility controls and sorption processes that influence diel cycles in trace element concentrations. Trace elements (including As species, Cu, Mn, Mo, Pb and Sb) and other parameters were monitored over two 24-h periods in unfiltered and filtered (0.1 μm) samples collected in August 2010 and June 2011. Copper and Pb were predominantly (>92% of the mass) associated with the particulate fraction (>0.1 μm). Arsenic, Mo and Sb were predominantly (>88% of the mass) in the “dissolved” (<0.1 μm) form. Particulate-associated elements displayed up to a factor of 13 differences between minimum and maximum concentrations, most likely due to increased streamflow related to rainfall events. Dissolved concentrations of the trace metal cations (Cu, Fe, Mn and Pb) were consistently low and displayed no diel trends. Dissolved As(V), Mo and Sb varied on a diel cycle, with increased concentrations (up to 36%) during the late afternoon and decreased concentrations during the nighttime. Diel trends in trace anionic elements are explained by temperature-dependent sorption, as the diel changes in pH during base flow were very small (0.07 std. units). Very low concentrations of As(III), which have been shown to vary in a diel cycle, were attributed to enhanced hydraulic exchange with As(III)-rich hyporheic water during rainfall events.     

Occurrence and mobility of major and trace elements in groundwater from pristine volcanic aquifers in Jeju Island,Korea

Major and trace elements in groundwater from basaltic aquifers in pristine conditions were investigated in a volcanic island to evaluate sources, sinks, and mobility of elements over a wide range of mineralization conditions with total dissolved solids from 50 mg/L to 3400 mg/L. Groundwater was highly undersaturated with respect to primary silicate minerals, indicating that dissolution of basaltic rocks may continue under conditions with precipitation of calcite and secondary silicates. Evolution of B/Cl ratio in groundwater from marine aerosols to basaltic rocks showed that the ratio could be used as a conservative tracer for interactions between water and basaltic rocks. Relative mobility (RM) of elements calculated using the concentrations of elements in the local basaltic rocks and those in groundwater showed that mobility decreased in the order of B > Rb > Na > K > Mg > Ca > Mo > V > Si > Sr > Sc > P > U > Zn > Pb > Cr > Cu > Ba > Ni > Ti > (Mn, Al, Fe, Co, Th) indicating that oxyanion-forming elements and alkali metals had the highest mobility. Compared to average RM, V had decreased mobility, and Fe and Mn had increased mobility in anoxic groundwater while V, Mo, and U had higher mobility in oxic-alkaline water. The sources of V, Cr, Cu, and Zn in rocks were estimated using the partition coefficients between minerals and basaltic melt, and the disparity between sources and mobility indicated that sinks are more important for controlling the concentrations of these elements in groundwater than the contents in the rocks. Principal component analysis (PCA) of hydrogeochemical parameters in groundwater produced three principal components (PC) which represent dissolution of basaltic rocks without significant attenuation of released solutes, higher degree of water–rock interactions resulting in oxic-alkaline conditions, and attenuation of Zn and Cu in higher pH, respectively. Spatial distribution of PCs revealed that groundwater with elevated concentrations of mobile elements was concentrated in the southwestern area and that concentrations of V and Cr were more scattered, which is likely to be controlled by pH and redox states of groundwater as well as degree of water–rock interactions.     

Geochemistry of trace metals and Pb isotopes of sediments from the lowermost Xiangjiang River, Hunan Province (P. R. China): implications on sources of trace metals

This paper reports a geochemical study of trace metals and Pb isotopes of sediments from the lowermost Xiangjiang River, Hunan province (P. R. China). Trace metals Ba, Bi, Sc, V, Cr, Mn, Co, Ni, Cu, Zn, Mo, Cd, Sn, Sb, Pb, Tl, Th, U, Zr, Hf, Nb and Ta were analyzed using ICP-MS, and Pb isotopes of the bulk sediments were measured by MC-ICP-MS. The results show that trace metals Cd, Bi, Sn, Sc, Cr, Mn, Co, Ni, Cu, Zn, Sb, Pb and Tl are enriched in the sediments. Among these metals, Cd, Bi and Sn are extremely highly enriched (EF values >40), metals Zn, Sn, Sb and Pb significantly highly (5 < EF < 20), and metals Sc, Cr, Mn, Co, Ni, Cu and Tl moderately highly (2 < EF < 5) enriched in the river sediments. All these metals, however, are moderately enriched in the lake sediments. Geochemical results of trace metals Th, Sc, Co, Cr, Zr, Hf and La, and Pb isotopes suggest that metals in the river sediments are of multi-sources, including both natural and anthropogenic sources. Metals of the natural sources might be contributed mostly from weathering of the Indosinian granites (GR) and Palaeozoic sandstones (PL), and metals of anthropogenic sources were contributed from Pb–Zn ore deposits distributed in upper river areas. Metals in the lake sediments consist of the anthropogenic proportions, which were contributed from automobile exhausts and coal dusts. Thus, heavy-metal contamination for the river sediments is attributed to the exploitation and utilization (e.g., mining, smelting, and refining) of Pb–Zn ore mineral resources in the upper river areas, and this for the lake sediments was caused by automobile exhausts and coal combustion. Metals Bi, Cd, Pb, Sn and Sb have anthropogenic proportion of higher than 90%, with natural contribution less than 10%. Metals Mn and Zn consist of anthropogenic proportion of 60–85%, with natural proportion higher than 15%. Metals Sc, Cr, Co, Cu, Tl, Th, U and Ta have anthropogenic proportion of 30–70%, with natural contribution higher than 30%. Metals Ba, V and Mo might be contributed mostly from natural process.     

Assessment of heavy metal concentrations and associated resistant bacterial communities in bulk and rhizosphere soil of <Emphasis Type="Italic">Avicennia marina</Emphasis> of Pichavaram mangrove,India

Heavy metals are known to pose a potential threat to terrestrial and aquatic flora and fauna. Due to increasing human influence, heavy metal concentrations are rising in many mangrove ecosystems. Therefore, an assessment of heavy metal (Cd, Cr, Cu, Ni, Pb, Fe, Mn, and Zn) concentrations was conducted within the bulk soil and rhizosphere soil of Avicennia marina at the Pichavaram Mangrove Forest in India. The rhizosphere soil showed higher concentrations of metals than the bulk soil. Compared to the bulk soil, the metals Cd, Fe, Mn, and Zn were 6.0–16.7% higher, whereas Cr, Cu, Ni, and Pb were 1.7–2.8% higher concentration. Among the three selected sampling sites (dense mangrove forest, estuarine region, and sea region), the sea region had the highest concentration of all heavy metals except Zn. The trend of the mean metal concentration was Fe > Mn > Cr > Ni > Cu > Pb > Zn > Cd. Heavy metals concentrations elevated by the 2004 tsunami were persistent even after 4 years, due to sedimentary soil processes, the rhizosphere effect of mangroves, and anthropogenic deposition. Analysis of the heavy metal-resistant bacteria showed highest bacterial count for Cr-resistant bacteria and rhizosphere soil. The maximum level of heavy metal-resistant bacteria was observed at the site with the highest heavy metal contamination. The heavy metal-resistant bacteria can be used as indicator of heavy metal pollution and furthermore in bioremediation.     

Distribution of some elements in surface soil over the Kavadarci region,Republic of Macedonia

The results of a first systematic study of spatial distribution of different elements in surface soil over of the Kavadarci region, Republic of Macedonia, known for its nickel industrial activity are reported. The investigated region (360 km²) is covered by a sampling grid of 2 × 2 km²; whereas the sampling grid of 1 × 1 km² was applied in the urban zone and around the ferronickel smelter plant (117 km²). In total 344 soil samples from 172 locations were collected. At each sampling point soil samples were collected at two depths, topsoil (0–5 cm) and bottom soil (20–30 cm). Inductively coupled plasma-mass spectrometry (ICP-MS) was applied for the determination of 36 elements (Ag, Al, As, Au, B, Ba, Bi, Ca, Cd, Co, Cr, Cu, Fe, Ga, Hg, K, La, Mn, Na, Mg, Mo, Ni, P, Pb, S, Sb, Sc, Se, Sr, Th, Tl, Ti, U, V, W and Zn). Data analysis and construction of maps were performed using the Paradox (ver. 9), Statistica (ver. 6.1), AutoDesk Map (ver. 2008) and Surfer (ver. 8.09) software. Four geogenic and three anthropogenic geochemical associations were established. Within the research, natural and anthropogenic enrichment with heavy metals was determined. Principally, the natural enrichment is related especially to Ni. Pollution by As, Cd, Co, Cr, Cu, Hg, Mo, Pb and Zn is basically insignificant.     

Source,transport, and fate of rhenium,selenium, molybdenum,arsenic, and copper in groundwater associated with porphyry–Cu deposits,Atacama Desert,Chile

We collected groundwaters in and around a large (313 Mt at 1.08% Cu and 0.3% cutoff) undisturbed porphyry copper deposit (Spence) in the hyperarid Atacama Desert of northern Chile, which is buried beneath 30–180 m of Miocene piedmont gravels. Groundwaters within and down-flow of the Spence deposit have elevated Se (up to 800 μg/l), Re (up to 31 μg/l), Mo (up to 475 μg/l) and As (up to 278 μg/l) concentrations compared to up-flow waters (interpreted to represent regional groundwater flow). In contrast, Cu is only elevated (up to 2036 μg/l) in groundwaters recovered from within the deposit; Cu concentrations are low down gradient of the deposit. The differential behavior of the metals/metalloids occurs because the former group dissolves as anions, enhancing their mobility, whereas the base metals dissolve as cations and are lost from solution most likely through adsorption to clay surface exchange sites and through formation of secondary copper chlorides, carbonates, and oxides. Most groundwaters within and down-flow of the deposit have Eh–pH values around the Fe^II/Fe^III phase boundary, limiting the impact of Fe-oxyhydroxides on oxyanions mobility. Se, Re, Mo, and As are all mobile (with filtered/unfiltered samples ～ 1) to the limit of sampling 2 km down gradient from the deposit. The increase in ore-related metals, metalloids, and sulfate and decrease in sulfate–S isotope ratios (from values similar to regional salars, + 4 to + 8‰ δ³⁴S_CDT to lower values closer to hypogene sulfides, + 1 to + 4‰ δ³⁴S_CDT) is consistent with active water–rock reactions between saline groundwaters and the Spence deposit. It is likely that hypogene and/or supergene sulfides are being oxidized under the present groundwater conditions and mineral saturation calculations suggest that secondary copper minerals (antlerite, atacamite, malachite) may also be actively forming, suggesting that supergene and exotic copper mineralization is possible even under the present hyperarid climate of the Atacama Desert.     

Distribution and speciation of heavy metals and their sources in Kumho River sediment,Korea

The interaction between heavy metals and river sediment is very important because river sediment is the sink for heavy metals introduced into a river and it can be a potential source of pollutants when environmental conditions change. The Kumho River, the main tributaries of the Nakdong River in Korea, can be one of the interesting research targets in this respect, because it runs through different geologic terrains with different land use characteristics in spite of its short length. Various approaches were used, including mineralogical, geochemical, and statistical analyses to investigate the distribution and behavior of heavy metals in the sediments and their sources. The effect of geological factor on the distribution of these metals was also studied. No noticeable changes in the species or relative amounts of minerals were observed by quantitative X-ray diffraction in the sediments at different stations along the river. Only illite showed a significant correlation with concentrations of heavy metals in the sediments. Based on an average heavy metal concentration (the average concentrations of Cd, Co, Cr, Cu, Ni, Pb, and Zn were 1.67, 20.9, 99.7, 125, 97.6, 149, 298 ppm, respectively), the sediments of the Kumho River were classified as heavily polluted according to EPA guidelines. The concentrations of heavy metals in the sediments were as follows: Zn > Pb > Cu > Ni > Cr > Co > Cd. In contrast, contamination levels based on the average I _geo (index of geoaccumulation) values were as follows: Pb > Cd > Zn > Cu > Co = Cr > Ni. The concentrations of heavy metals increased downstream (with the exception of Cd and Pb) and were highest near the industrial area, indicating that industrial activity is the main factor in increasing the concentrations of most heavy metals at downstream stations. Sequential extraction results, which showed increased heavy metal fractions bound to Fe/Mn oxides at the downstream stations, confirmed anthropogenic pollution. The toxicity of heavy metals such as Ni, Cu, and Zn, represented by the exchangeable fraction and the fraction bound to carbonate, also increased at the downstream stations near the industrial complexes. Statistical analysis showed that Pb and Cd, the concentrations of which were relatively high at upstream stations, were not correlated with other heavy metals, indicating other possible sources such as mining activity.