Environmental aspects of selected trace metals in soils and waters surrounding Singaran Nala, Raniganj Coalfield

The Raniganj Coalfield is the oldest coalfield in India that has been continuously and extensively mined since the late eighteenth century. The present study reports a geochemical investigation and environmental quality assessment using soil and water in the area surrounding a stream, locally known as Singaran Nala （Nala means storm water drains in Bengali）, in the Raniganj Coalfield. Soil （top soil, mud, silty clay and laterite） and rock samples （sandstone and shale） were collected from the study area and were analyzed for trace metals （Cr, Cu, Fe, Mn, Ni and Zn）. Surface waters from the stream and the Damodar River as well as ground waters from hand pumps and underground mine pits were collected. Water samples were analyzed for major ions （Na^＋, Ca^2＋, Mg^2＋, Cl^-, HNO3^- and SO4^2-） and trace metals （Cu, Fe, Mn, Ni, and Zn）. Trace metal concentrations in soil samples are found higher than the average world soil composition. Nevertheless, trace metal （Cr, Cu, Ni and Zn） concentrations in soils exceed or reach the maximum allowable concentrations （MAC） proposed by the European Commission for agricultural soils. In particular, Ni concentrations exceed the typical value for cultivated soils. Chromium, Cu and Ni concentrations in laterite and Cr concentration in topsoil exceed the ecotoxicological limit.     

GGR Critical Review of Analytical Developments in 2004–2005

In 2005 Geostandards and Geoanalytical Research embarked upon a new initiative for its readers. Key researchers in various fields of geoanalytical technique development and their application were identified and invited to provide reviews pertinent to their expertise. As noted in the first of these publications "…instead of revisiting the historical context or decades of development in each analytical technique, the goal here has been to capture a snapshot of "hot topics" across a range of fields as represented in the… literature" (Hergt et al . 2005). Rather than prepare an annual review, a decision was taken earlier this year to provide a biennial summary of progress and accomplishments, in this case for the years 2004–2005. The principal techniques employed in Earth and environmental sciences are covered here, and include laser ablation and multicollector ICP-MS, ICP-AES, thermal ionisation and secondary ion mass spectrometry, as well as neutron activation analysis, X-ray fluorescence and atomic absorption spectrometry. A comprehensive review of the development of reference materials, often essential to these techniques, is also provided. The contributions assembled serve both to keep readers informed of advances they may be unfamiliar with, but also as a means of showcasing examples of the breadth and depth of work being conducted in these fields.     

High resolution profiles of trace metals in pore waters of marine and riverine sediments assessed by DET and DGT

In polluted aquatic systems, toxic metals are often accumulated in bottom sediments. They are, however, not necessarily stored definitively because diagenetic processs can modify redox, pH and even the amount of complexing ligands, releasing the trace metals back into the pore waters and the water column. Especially the labile metal fraction in the pore waters is important since this is the bioavailable fraction determining the bio-toxicity of the sediments. The goal of our study was therefore to assess, with novel sampling techniques, this bioavailable metal fraction in the pore waters as well as the flux towards the overlying water column. High-resolution profiles of trace metals in pore waters of marine and riverine sediments were assessed by DET （diffusive equilibrium in thin films） and DGT （diffusive gradients in thin films） gel techniques. The DET technique uses a diffusive gel layer that equilibrates with the aquatic system and with this technique the concentrations of total dissolved trace metals are obtained directly. The DGT technique uses an acrylamide diffusive gel backed by a resin gel （Chelex） which binds trace metals. With the DGT technique only labile species of selected metals can be captured. According to the redox potential measurements, the marine sediments were suboxic （200 mV to -220 mV versus Ag/AgCl electrode）, while the riverine sediments were completely anoxic （-160 mV to -220 mV versus Ag/AgCl electrode）. This redox potential was apparently controlling the trace metals species in the pore waters： for example a strong correlation between Mn and Co was found in the riverine sediments （for DET and DGT sampling）, while in the marine sediments trace metals presented various behaviors.     

Heavy metals in freshly deposited sediments of the river Subernarekha, India: an example of lithogenic and anthropogenic effects

Heavy metal distribution patterns in river sediments aid in understanding the exogenic cycling of elements as well as in assessing the effect of anthropogenic influences. In India, the Subernarekha river flows over the Precambrian terrain of the Singhbhum craton in eastern India. The rocks are of an iron ore series and the primary rock types are schist and quartzite. One main tributary, the Kharkhai, flows through granite rocks and subsequently flows through the schist and quartzite layers. The Subernarekha flows through the East Singhbhum district, which is one of India’s industrialised areas known for ore mining, steel production, power generation, cement production and other related activities. Freshly deposited river sediments were collected upstream and downstream the industrial zone. Samples were collected from four locations and analysed in <63-μm sediment fraction for heavy metals including Zn, Pb, Cd and Cu by anodic stripping voltammetry. Enrichment of these elements over and above the local natural concentration level has been calculated and reported. Sediments of the present study are classified by Muller’s geo-accumulation index (I _geo) and vary from element to element and with climatic seasons. During pre-monsoon period the maximum I _geo value for Zn is moderately to highly polluted and for Cu and Pb is moderately polluted, respectively, based on the Muller’s standard. Anthropogenic, lithogenic or cumulative effects of both components are the main reasons for such variations in I _geo values. The basic igneous rock layer through which the river flows or a seasonal rivulet that joins with the main river may be the primary source for lithogenic components.     

Will the river Irtysh survive the year 2030? Impact of long-term unsuitable land use and water management of the upper stretch of the river catchment (North Kazakhstan)

The Irtysh river basin all the way from river spring in China across Kazakhstan as far as the Russian part of Siberia is among the most ecologically endangered and affected regions on our planet. The study provides a summary of the historical reasons for anthropological interventions in this area, which began with the construction of plants of the military—industrial complexes in the forties of the last century during World War II. These plants have a major share in extreme high concentrations of heavy metals in surface as well in groundwaters locally. The Semipalatinsk nuclear polygon plays a specific role as a source of contamination of local waters. The release of top secret data enabled us to gain knowledge about serious problems related to high radioactivity of groundwaters, which should spread uncontrollably through a system of secondary fissures activated by nuclear blasts. Another serious problem in this region is the quantitative aspect of contamination. Model simulations of water balance indicate that large industrial development in the spring area in China and continuously increasing water consumption in Kazakhstan may lead to desiccation of the lower stretch of this large river in Siberia during the summer months of 2030.     

Sediment-Based Study of the Effects of Decreasing Mine Water Pollutionon a Heavily Modified, Nutrient Enriched Lake

Ni and Cu mining and ore processing in Hitura, Western Finland, have resulted in emissions of metal-rich wastewaters into the nearby Kalajoki River since 1970. The wastewaters are discharged into the river 3 km upstream from the eutrophic Lake Pidisjärvi, which is a widening of the river by the town of Nivala. The water level of the lake was elevated by 1.5 m and the extensive macrophyte stands were cut in 1979, profoundly changing the environmental conditions. The effects of the decreasing metal emissions and nutrient concentrations since 1979 on the now open 3.9 km² lake were studied with paleolimnological techniques. A 2-m sediment core was taken from the lake in February 2004 and analysed for sediment chemistry and diatom assemblages. At the coring site, 13 cm of sediment had been deposited since 1979, on top of a bed of undecomposed macrophyte remains. When the sediment chemistry was compared with records of decreasing metal loading since 1979, no correlation was found because post-depositional mobility and changes in sediment characteristics affect the sediment metal profiles. Thus, the reduced emissions from the mine and the lower lake water phosphorus levels have not caused a corresponding decrease in sediment metal and P concentrations. However, both of these environmental variables accounted for a statistically significant percentage of variation in the sedimentary diatom assemblages in a redundancy analysis constrained to a single variable. This relationship persisted for Ni loading even in a partial analysis, while the importance of nutrients was confirmed by the good correlation between diatom-inferred and measured P concentrations. The results suggest that reductions in metal and nutrient loading have had an effect on the algal assemblages even though the sediment concentrations of Ni, Cu or P have not decreased.     

Lead, zinc, and antimony contamination of the Rio Chilco-Rio Tupiza drainage system, Southern Bolivia

An intense, but localized rainfall event in February 2003, led to the severe erosion and failure of a tailings disposal impoundment at the Abarόa Antimony Mine in southern Bolivia. The failure released approximately 5,500 m³ of contaminated tailings into the Rio Chilco-Rio Tupiza drainage system. The impacts of the event on sediment quality are examined and compared to contamination resulting from historic mining operations in the headwaters of the basin. Of primary concern are contaminated floodplain soils located along downstream reaches of the Rio Tupiza which were found to contain lead (Pb), zinc (Zn), and antimony (Sb) concentrations that locally exceed Canadian, German, and Dutch guidelines for agricultural use. Spatial patterns in sediment-borne trace metal concentrations, combined with Pb isotopic data, indicate that Pb, Zn, and Sb are derived from three tributary basins draining the Abarόa, Chilcobija, and Tatasi-Portugalete mining districts. Downstream of each tributary, geographical patterns in trace metal concentrations reflect local geomorphic changes throughout the drainage system. Trace metal concentrations within the Rio Chilco decrease rapidly downstream as a result of dilution by uncontaminated sediments and storage of metal enriched particles (e.g., sulfide minerals) in the channel bed as a result of ongoing aggradation. Storage in the floodplains is limited. These processes significantly reduced the dispersal and, thus, the relative environmental affects of tailings eroded from the Abarόa Mine during the 2003 flood. In contrast, storage of Pb, Zn, and Sb in floodplains along the Rio Tupiza is significant, the majority of which is derived from historic mining operations, particularly mining within the Tatasi-Portugalete district.     

Vertical distribution and water solubility of phosphorus and heavy metals in sediments of the St. Lucie Estuary, South Florida, USA

Accumulation and distribution of heavy metals and phosphorus in sediments impact water quality. There has been an increasing concern regarding fish health in the St. Lucie Estuary, which is related to increased inputs of nutrients and metals in recent decades. To investigate vertical changes of contaminants (P, Cd, Cr, Co, Cu, Ni, Pb, Zn, and Mn) in sediments of the St. Lucie Estuary in South Florida, 117 layer samples from six of the 210 to 420 cm depth cores were analyzed for their total and water-soluble P and heavy metals, clay, total Fe, Al, K, Ca, Mg, Na, and pH. Principal component analysis (PCA) was used in two sets of analytical data (total and water-soluble contaminant concentrations) to document changes of contaminants in each core of sediments. The PCA of total contaminants and minerals resulted in two factors (principal components). The first and second factors accounted for 61.7 and 17.2 % of the total variation in all variables, and contrast indicators associated with contaminants of P, Cd, Co, Cr, Ni, Pb, Zn, and Mn and accumulation of Fe and Al oxides, respectively. The first factor could be used for overall assessment of P and heavy metal contamination, and was higher in the upper 45–90 cm than the lower depths of each core. The concentrations of P and heavy metals in the surface layers of sediments significantly increased, as compared with those in the sediments deeper than 45–90 cm. The PCA of water-soluble contaminants developed two factors. The second factor (Cu–P) was higher in the upper than the lower depths of the sediment, whereas the highest score of the first factor (Cd–Co–Cr–Ni–Pb–Zn–Mn) occurred below 100 cm. The water-soluble Cu and P concentrations were mainly dependent on their total concentrations in the sediments, whereas the water-soluble Cd, Co, Cr, Ni, Pb, Zn, and Mn concentrations were mainly controlled by pH.     

Dissolved Trace Metal–Organic Complexes in the Lot–Garonne River System Determined Using the C18 Sep-Pak System

An 11-month observation of dissolved and particulate organic matter, chlorophyll a(Chl a), C18 Sep-Pak extractable hydrophobic dissolved organic matter (hDOM) fraction and associated dissolved trace metals (Cd, Cu, V, Co, Ni, Mo, U) was performed in the Lot–Garonne River system. This system includes the Riou Mort, the Lot River and the downstream reaches of the Garonne River and represents the fluvial transport path of trace metals between the major point source of polymetallic pollution, located in the Riou Mort watershed and the Gironde estuary. Spatial and temporal variations of dissolved and particulate organic carbon and Chl areflect the presence of different types of organic matter and their relation with the hDOM fraction. Maximum Chl a/POC ratios (up to 0.03), indicate intense phytoplankton production from March to May. In the Lot River (Temple), DOC and POC concentrations were clearly higher and mean Chl a concentration (2.8 mg g⁻¹) was about three times higher than those of the other sites. High Chl a/POC ratios suggest high phytoplankton activity with maxima in spring and late summer. In the Riou Mort River, very high POC concentrations of up to 40 (mean: 20) occurred, whereas Chl a concentrations were relatively low indicating low phytoplankton activity. High, strongly variable DOC and POC concentrations suggest important natural (Carboniferous soils, forests) or anthropogenic (e.g., former coal mines, waste areas, agriculture, sewage) carbon sources within the small Riou Mort watershed. Despite high DOC concentrations in the Riou Mort River, hDOM metal fractions were generally lower than those at the other sites. The general order of decreasing binding strength between metals and the organic hydrophobic phase (Cu, U > Co, Ni > V, Mo > Cd) at all four sites was in good agreement with the Irving–William series of transition element affinity towards organic ligands. Accordingly, the role of the hydrophobic phase in dissolved Cd transport appeared to be negligible, whereas the hDOM–Cu fraction strongly contributed to dissolved Cu transport.