Spatial variability of soils and stream sediments and the remediation effects in a Portuguese uranium mine area

The old Senhora das Fontes uranium mine, located in central Portugal, was closed down in 1971. The treatment of ores from this mine and other mines by heap-leach ended in 1982. Seven dumps partially covered by vegetation were left in the area. Soil and stream sediment samples were collected in December 2009. The remediation was carried out from May 2010 to January 2011. Stream sediment samples were collected again in October 2013. Before the remediation, soils from inside the mine influence area have higher Al, As, Co, Cr, Cu, Fe, Ni, Sr, Th, U and Zn concentrations than soils from outside this area, due to radionuclides, metals and metalloid released from the mine dumps. The principal component analysis (PCA) shows a distinction between soils from inside and outside the mine influence area. The U(VI), As(V) and metals from soils can be adsorbed to Fe-oxyhydroxides and the humic acid can increase the U uptake. Soils must not be used for public or private green and residential areas, because they are contaminated in U, As, Co, Cd and Ni. Before the remediation, downstream sediments have higher Al, As, Cu, Mn, Ni, Pb, U and Zn than upstream sediments, due to erosion and percolation of water through the mine dumps. The PCA shows a distinction between downstream and upstream sediments. The U(VI), Th and As(V) can be adsorbed to Fe-oxyhydroxides. The stream sediments are contaminated in As, Mn, Th and U. Downstream sediments are the most contaminated in U and As. After the remediation, upstream and downstream sediments have generally higher Al, Fe, As, Cr, Ni, Th, U and Zn concentrations than before the remediation, attributed to the relocation of dumps. Radionuclides, metals and metalloids were transported by surface water. Consequently downstream sediments have higher Al, As, Cu, Mn, Ni, Th, U and Zn concentrations than upstream sediments. The U(VI), Th and As(V) can be adsorbed to Fe-oxyhydroxides. Stream sediments became more contaminated in U, Th and As than before the remediation, but more intensively downstream.     

Occurrence of hexavalent chromium in ground water in the western Mojave Desert,California

About 200 samples from selected public supply, domestic, and observation wells completed in alluvial aquifers underlying the western Mojave Desert were analyzed for total dissolved Cr and Cr(VI). Because Cr(VI) is difficult to preserve, samples were analyzed by 3 methods. Chromium(VI) was determined in the field using both a direct colorimetric method and EPA method 218.6, and samples were speciated in the field for later analysis in the laboratory using a cation-exchange method developed for the study described in this paper. Comparison of the direct colorimetric method and EPA method 218.6 with the new cation-exchange method yielded r² values of 0.9991 and 0.9992, respectively. Total dissolved Cr concentrations ranged from less than the 0.1 μg/l detection limit to 60 μg/l, and almost all the Cr present was Cr(VI). Near recharge areas along the mountain front pH values were near neutral, dissolved O₂ concentrations were near saturation, and Cr(VI) concentrations were less than the 0.1 μg/l detection limit. Chromium(VI) concentrations and pH values increased downgradient as long as dissolved O₂ was present. However, low Cr(VI) concentrations were associated with low dissolved O₂ concentrations near ground-water discharge areas along dry lakes. Chromium(VI) concentrations as high as 60 μg/l occurred in ground water from the Sheep Creek fan alluvial deposits weathered from mafic rock derived from the San Gabriel Mountains, and Cr(VI) concentrations as high as about 36 μg/l were present in ground water from alluvial deposits weathered from less mafic granitic, metamorphic, and volcanic rocks. Chromium(III) was the predominant form of Cr only in areas where dissolved O₂ concentrations were less than 1 mg/l and was detected at a median concentration of 0.1 μg/l, owing to its low solubility in water of near-neutral pH. Depending on local hydrogeologic conditions and the distribution of dissolved O₂, Cr(VI) concentrations may vary considerably with depth. Samples collected under pumping conditions from different depths within wells show that Cr(VI) concentrations can range from less than the 0.1 μg/l detection limit to 36 μg/l in a single well and that dissolved O₂ concentrations likely control the concentration and redox speciation of Cr in ground water.     

Chromium oxidation by manganese (hydr)oxides in a California aquifer

There are increasing concerns with elevated levels of Cr(VI) in the environment because it is a strong oxidant, corrosive, and carcinogenic. The concerns extend to the presence of Cr(VI) in many aquifers in California and elsewhere, where relatively high levels have been attributed to both industrial pollution and natural processes. The authors have, therefore, determined if natural redox processes contribute to the presence of high Cr(VI) concentrations (6–36 μg L⁻¹) in an aquifer in central California relative to non-detectable concentrations (<0.1 μg L⁻¹) in an adjacent aquifer. Specifically, the distribution and the redox speciation of dissolved (<0.45 μm) Cr have been compared with those of particulate Mn and Fe oxy-hydroxides in sediments, using X-ray absorption spectroscopy at the Mn and Fe L-edges. The analyses show a correlation between the presence of dissolved Cr(VI) and Mn (hydr)oxide minerals, which are the only common, naturally occurring minerals known to oxidize Cr(III) in laboratory experiments. This covariance substantiates the results of those experiments and previous field studies that indicate natural oxidation mechanisms might account for the relatively high levels of Cr(VI) in the study site, as well as for elevated concentrations in other aquifers with similar biogeochemical conditions.     

Factors controlling the heterogeneous distribution of Cr(VI) in soil, plants and groundwater: Evidence from the Assopos basin, Greece

The effective influence of industry or ultramafic rocks by natural processes to soil, plants and groundwater contamination by chromium, which is often a subject of debate, was investigated for the case of the Assopos basin, Greece. The Neogene Assopos basin, is mainly composed by Tertiary and Quaternary sediments of more than 400 m thick and is characterized by brittle type deformation (fault zones, faults). Chromium in soil, ranging from 67 to 204 ppm, is mostly hosted in chromite, Fe-chromite, Cr-bearing goethite and silicates.Special attention was given to the plants, which are a major source of organic matter that serves as the driving force for Cr(VI) reduction. The increase of the Fe, Mn and Ni contents, with the increasing Cr content in the plant-roots, in particular at the external parts of roots and those of bulb-type plants, suggest reduction and immobilization of Cr(VI) and that redox reactions play a significant role to the translocation processes from root to shoot.Groundwater samples from the Assopos aquifer showed a wide spatial variability, ranging from <2 to 180 ppb Cr_total content [almost same to the Cr(VI)-values] despite their spatial association. The presence of Cr(VI)-contaminated groundwater at depths >200 m is attributed to a direct injection of Cr(VI)-rich industrial wastes at depth rather than that Cr(VI) is derived from the Assopos river or by the interaction between water and Cr-bearing rocks. The heterogeneous distribution of Cr in groundwater may be related with the intense neotectonic deformation, as is exemplified by several sharp tectonic contacts between sediment types, while the Cr content in soil is mostly depend on the transported chromite grains.     

Spatial distribution,environmental assessment and source identification of metals content in surface sediments of freshwater reservoir,Pakistan

Surface sediments were collected from different sites of a freshwater reservoir, Pakistan, and analyzed for eight metals (Cd, Co, Cr, Cu, Fe, Mn, Pb and Zn) using flame atomic absorption spectrometry. The estimated metals levels were found higher than other reported studies. The environmental indices including geoaccumulation index, enrichment factor and contamination factor identified Cd, Co, Pb and Zn as the priority pollutants of concern. Chromium, Cu and Mn were also found to be enriched in some areas. The pollution load index (≥1) indicated progressive deterioration of the sediments quality. Principal component and cluster analyses revealed that Cd, Co, Pb and Zn were mainly originated from agricultural activities, domestic wastes, road runoffs and recreational activities. Chromium, Cu, Fe and Mn were mainly derived from natural sources though Cr, Cu and Mn were partially contributed by human inputs. Based on spatial distribution, inlet and middle sites of the reservoir were found more contaminated. This study would drive urgent attention to develop preventive actions and remediation processes for aquatic system protection and future restoration of the reservoir.     

Distribution and bioavailability of Cr in central Euboea, Greece

Plants and soils from central Euboea, were analyzed for Cr_(totai), Cr(VI), Ni, Mn, Fe and Zn. The range of metal concentrations in soils is typical to those developed on Fe-Ni laterites and ultramafic rocks. Their bioavailability was expressed in terms of concentrations extractable with EDTA and 1 M HNO₃, with EDTA having a limited effect on metal recovery. Cr(VI) concentrations in soils evaluated by alkaline digestion solution were lower than phytotoxic levels. Chromium and Ni — and occasionally Zn — in the majority of plants were near or above toxicity levels. Cr(VI) concentrations in plants were extremely low compared to total chromium concentrations. Cr_(total) in ground waters ranged from <1 μg.L^?1 to 130 μg.L^?1, with almost all chromium present as Cr(VI). With the exception of Cr_(total) and in some cases Zn, all elements were below regulatory limits for drinking water. On the basis of Ca, Mg, Cr_(total) and Si ground waters were classified into three groups: Group(I) with Cr concentrations less than 1 μg.L^?1 from a karstic aquifer; Group(II) with average concentrations of 24 μg.L^?1 of Cr and relatively high Si associated with ophiolites; and Group(III) with Cr concentrations of up to 130 μg.L^?1, likely due to anthropogenic activity. Group(III) is comparable to ground waters from Assopos basin, characterized by high Cr(VI) concentrations, probably due to industrial actrivities.     

Oxidation of aqueous Cr(III) at birnessite surfaces: constraints on reaction mechanism

X-ray Photoelectron Spectroscopy (XPS) was used to investigate oxidation of aqueous Cr(III) at the surface of 7 Å-birnessite [MnO_1.75(OH)_0.25]. Special emphasis was placed on detection of intermediate oxidation states of chromium due to their critical environmental significance. No previous studies have been able to identify these intermediate oxidation states of chromium (namely, Cr[IV] and Cr[V]) on mineral surfaces or in natural solutions. Mn(2p_3/2), Cr(2p_3/2) and O(1s) spectra of the reacted surfaces reveal that Mn(IV) of synthetic birnessite undergoes reductive dissolution in two steps. The first step involves Mn(IV) reduction to Mn(III),that forms at the oxide surface probably as an oxyhydroxide (MnOOH), and in the second step Mn(III) is reduced to Mn(II) that is subsequently taken into solution. Each reductive reaction step involves transfer of only one electron to the Mn ion. After Cr(III)_aq is adsorbed onto the MnO₂ surface, it undergoes oxidation in three separate steps, each involving the loss of one electron to Mn ions, so that Cr(IV), Cr(V) and Cr(VI) are produced. The intermediate reaction products, namely Mn(III), and Cr(V) were positively identified by XPS spectral analyses. Similarity in XPS binding energy values of Cr(III) and Cr(IV) as well as that of Cr(V) and Cr(VI), however, preclude separate identification of Cr(III) from Cr(IV) and Cr(VI) from Cr(V) multiplets on the near-surface of the solid. A parallel reaction scheme (exclusive of sorption reactions) best describes the birnessite-Cr(III)_aq redox reactions. The two parallel reactions proceed by separate mechanisms with a monodentate complex formed in one mechanism and a bidentate complex in another. The bulk of Cr(IV) probably is formed via the monodentate complex and Cr(V) via the bidentate complex. The rate expressions associated with these reactions display near-perfect correlation with changing surface abundances of Cr(IV) and Cr(V) as a function of reaction time. Copyright © 1999 Elsevier Science Ltd.     

Effects of indigenous bacteria on Cr(VI) reduction in Cr-contaminated sediment with industrial wastes

Black, clay-like sediments have been obtained from the area of the pigment manufacturing factories in Dongducheon city, Korea. These sediments were contaminated by heavy metals, especially chromium (700 mg/kg). Indigenous bacteria in the sediments were isolated to investigate their ability to reduce Cr(VI) to Cr(III). The enriched bacterial consortium reduced over 99% of dissolved Cr(VI) in 96 h from the onset of the experiments under anaerobic condition, while there was no change in Cr(VI) concentration until 300 h in abiotic controls. Total amount of dissolved Cr decreased simultaneously when Cr(VI) was reduced, which was likely due to precipitation of Cr(OH)₃ after microbial reduction of Cr(VI) to Cr(III). Under aerobic condition, only 30% of dissolved Cr(VI) was reduced by indigenous bacteria until 900 h. The reduction of Cr(VI) did not accompany bacterial growth since the amount of protein did not show a significant change with time both in the presence and absence of O₂. These indigenous bacteria may play a role in the treatment of Cr(VI)-contaminated sediments.     

ANC,BNC and mobilization of Cr from polluted sediments in function of pH changes

During the manufacturing of chromate salts (1972–1992) large quantities of Chromite Ore Processing Residue (COPR) were released into a decantation pond east of the former chemical plant of Porto-Romano (Durres, Albania), giving rise to yellow colored pond sediments. These Cr(VI) bearing sediments were deposited upon Quaternary silty-clay lagoonal sediments rich in iron oxides and organic matter. The pH values in these lagoonal sediments vary around 6.6, while in the pond sediments, it is mainly acidic (due to the presence of the sulfur stock piles in the area and the release of the H₂SO₄ from the activity of the former chemical plant), varying between 1.4 and 3.8. Continuous leaching of the COPR waste resulted in yellow-colored surface water runoff. The prediction of pH changes in the different types of sediments based upon acid/base neutralizing capacity (ANC/BNC) jointly with the quantitative data on release of heavy metals and especially Cr is considered an important advantage of the pH_stat leaching test if compared to conventional leaching procedures. Thus, factors controlling the leaching of Cr(VI), Cr(III), Ca, Al, Fe, Mg from the COPR were investigated by means of pH_stat batch leaching tests and mineralogical analysis. Moreover, mathematical and geochemical modeling complemented the study. The COPR in the area contain very high concentrations of chromium 24,409 mg/kg, which mainly occurs as Cr(III) (75–90%) as well as Cr(VI) (25–10%). The leaching of Cr(VI) occurs in all the range (2–10) of the tested pH values, however, it decreases under acidic conditions. Beside some reduction of Cr(VI) to Cr(III), the Cr(VI) content of the leachtes remains relatively high in the acidic environment, while the limning of Cr(VI) pond sediments will increase the release of the latter specie. The leaching of the Cr(III) occurs strictly under acidic conditions, whereby limning of these sediments will give rise to the lower solubility of Cr(III). The key mineral phases responsible for the fast release of the Cr(VI) are: the chromate salts (i.e. sodium chromate and sodium dichromate), while sparingly soluble chromatite (CaCrO₄) and hashemite (BaCrO₄) release Cr(VI) very slowly. Thus, pH and mineral solubility have been identified as key factors in the retention and the release of the hexavalent CrO₄ ²⁻ and Cr₂O₇ ⁻ from the COPR-rich pond sediments.     

Geochemistry and Cr stable isotopes of Cr-contaminated groundwater in León valley,Guanajuato, México

León valley, located in the Mexican state of Guanajuato, has a long history (35+ a) of Cr contamination of groundwater and surface water. Here data are presented for Cr, major ion and trace element concentrations and Cr stable isotope measurements of groundwater in a heavily contaminated aquifer in Buenavista, where Cr ore processing residue piles (COPRPs) located in a chromate production factory are the main source of Cr. The aquifer directly beneath the factory still retains very high Cr(VI) concentrations (∼121 mg/L). Ongoing pump and treat remediation is keeping the high concentration plume confined to the factory area and immediate vicinity, though Cr is also detected at some distance away. Chromium isotope data of the aquifer directly under the factory show only a small increase in δ⁵³Cr (+0.33‰ to +0.81‰) and indicates minimal reduction of Cr(VI) to Cr(III). Very high Cr(VI) concentrations have possibly overwhelmed natural reductants and furthermore fresh Cr(VI) was being leached into the groundwater from the COPRP. From just one year of Cr isotope data it is clear that more aggressive remediation techniques will be necessary to reduce or eliminate the contamination. The fringes of the Cr plume have substantially lower concentrations and can be partially explained by transport of the main plume or mixing between waters from the nearby landfill and highly contaminated waters from QC. While the source of Cr at the fringes of the plume could be attributed to a source from the nearby landfill instead of the main plume from the factory, the Cr stable isotope data show enrichment in the heavier isotopes and point to varying amounts of reduction. Isotopic enrichment seen between 2007 and 2008 along the fringe may indicate either reduction or less unreacted Cr(VI) is being transported to the fringes. In either case some potential for natural attenuation of Cr(VI) exists at the western margin of the plume with the landfill playing a role.     

Investigations on different positions of electrodes and their effects on the distribution of Cr at the water sediment interface

In most mining areas, significant concentrations of metals such as Pb, Cu, Cr, Zn, Cd, Fe, Mn, Co, Ni, Hg, Ar, halogenated organic compounds and radionuclides are found. Of those, Cr is one of the well-known heavy metals that forms toxic species. It is necessary to study the mobilization and accumulation of Cr at the sediment water interface in an electric field at varying different positions and conditions of the electrode arrangement. The tests were carried out with a natural sediment containing heavy metals from the river Weisse Elster (Germany). The electrokinetic experiments have been performed in columns filled with sediment using electrodes made of conductive polymers (polyethylene with carbon black) at a maximum current density of 0.5 mA/cm². The experimental results suggest that the mobilization and accumulation of Cr highly depends on chemical factors for e.g., pH value, redox potential, respectively redox status and the content of Fe, A1 and organic matter in the soil or sediment. The sorption of Cr (III, VI) is very high in the pH range > 4.5. As expected, a high mobilization of Cr (III, VI) was seen in the case of the experiments with the anode at the sediment, because the pH value was lower than mentioned above. On the opposite, the best conditions for the Cr (III, VI) immobilization is high pH values (cathode at the sediment).     

Heavy metal distribution in recent sediments of the Tietê-Pinheiros river system in São Paulo state,Brazil

The concentrations and possible chemical associations of Al, Fe, Mn, Ca, Cu, Pb, Cd, Zn, Ni and Cr in sediments of the Tietê-Pinheiros river system in São Paulo state, Brazil, were studied using a 3-step sequential extraction protocol recommended by the Standards, Measurements and Testing Programme (SM&T, formerly BCR). A single extraction with 0.1 mol l⁻¹ HCl was applied in parallel to anoxic and air-dried samples. The river system crosses the metropolitan area of São Paulo (MASP), which houses a population of nearly 17 million people, and receives a large load of industrial and domestic wastes. Samples were collected from reservoirs in the surroundings of MASP, named Billings, Pirapora and Rasgão, and from the Barra Bonita reservoir, that is located in the Tietê river, 270 km downstream from São Paulo city. The distribution of metals indicates the recent pollution characteristics for samples from the Billings, Pirapora and Rasgão reservoirs. In these sediments the metals are associated to a large degree with reactive forms such as sulphides and carbonates, or adsorbed to amorphous oxyhydroxides of Fe and Mn. In samples from Barra Bonita, heavy metals are mainly associated with the residual fraction, suggesting that their concentrations are controlled significantly by transport processes with fine particles as carriers from diffuse pollution sources.     

Heavy metals in freshly deposited sediments of the Gomati River (a tributary of the Ganga River): effects of human activities

 The concentrations of various metals (Cr, Cu, Co, Fe, Mn, Ni, Pb, Zn, and Cd) were determined in recently deposited surface sediments of the Gomati River in the Lucknow urban area. Markedly elevated concentrations (milligrams per kilogram) of some of the metals, Cd (0.26–3.62), Cu (33–147), Ni (45–86), Pb (25–77), and Zn (90–389) were observed. Profiles of these metals across the Lucknow urban stretch show a progressive downstream increase due to additions from 4 major drainage networks discharging the urban effluents into the river. The degree of metal contamination is compared with the local background and global standards. The geoaccumulation index order for the river sediments is Cd>Zn>Cu>Cr>Pb. Significant correlations were observed between Cr and Zn, Cr and Cu, Cu and Zn and total sediment carbon with Cr and Zn. This study reveals that the urbanization process is associated with higher concentrations of heavy metals such as Cd, Cu, Cr, Pb, and Zn in the Gomati River sediments. To keep the river clean for the future, it is strongly recommended that urban effluents should not be overlooked before their discharge into the river. Received: 16 February 1996 · Accepted: 29 February 1996     

Chromium,chromium isotopes and selected trace elements,western Mojave Desert,USA

Chromium(VI) concentrations in excess of the California Maximum Contaminant Level (MCL) of 50 μg/L occur naturally in alkaline, oxic ground-water in alluvial aquifers in the western Mojave Desert, southern California. The highest concentrations were measured in aquifers eroded from mafic rock, but Cr(VI) as high as 27 μg/L was measured in aquifers eroded from granitic rock. Chromium(VI) concentrations did not exceed 5 μg/L at pH < 7.5 regardless of geology. δ⁵³Cr values in native ground-water ranged from 0.7 to 5.1‰ and values were fractionated relative to the average δ⁵³Cr composition of 0‰ in the earth’s crust. Positive δ⁵³Cr values of 1.2 and 2.3‰ were measured in ground-water recharge areas having low Cr concentrations, consistent with the addition of Cr(VI) that was fractionated on mineral surfaces prior to entering solution. δ⁵³Cr values, although variable, did not consistently increase or decrease with increasing Cr concentrations as ground-water flowed down gradient through more oxic portions of the aquifer. However, increasing δ⁵³Cr values were observed as dissolved O₂ concentrations decreased, and Cr(VI) was reduced to Cr(III), and subsequently removed from solution. As a result, the highest δ⁵³Cr values were measured in water from deep wells, and wells in discharge areas near dry lakes at the downgradient end of long flow paths through alluvial aquifers. δ⁵³Cr values at an industrial site overlying mafic alluvium having high natural background Cr(VI) concentrations ranged from −0.1 to 3.2‰. Near zero δ⁵³Cr values at the site were the result of anthropogenic Cr. However, mixing with native ground-water and fractionation of Cr within the plume increased δ⁵³Cr values at the site. Although δ⁵³Cr was not necessarily diagnostic of anthropogenic Cr, it was possible to identify the extent of anthropogenic Cr at the site on the basis of the δ⁵³Cr values in conjunction with major-ion data, and the δ¹⁸O and δD composition of water from wells.     

Chromium Transformations in Natural Environments: The Role of Biological and Abiological Processes in Chromium(VI) Reduction

Chromium is a redox-dynamic element that has many industrial uses. As a consequence, it is often introduced at elevated levels into the surface environment through human activity. Additionally, ultramafic rocks such as serpentinite are commonly enriched in chromium, and thus can also lead to appreciable levels of this element within soils and waters. In the trivalent state, it poses little hazard to biological activity, but, unfortunately, in the hexavalent state it is very toxic to living matter. One must therefore assess the oxidation state of Cr in a given system and determine the potential for transformation between valence states. The objective of this paper to is review and provide new insight on reduction reactions of Cr(VI) within natural environments. A number of aerobic and anaerobic bacteria demonstrate the enzymatic ability to reduce Cr(VI) to Cr(III); two species can even grow using Cr(VI) as the terminal electron acceptor in respiration. The ability to reduce chromium in itself is not evidence that the process will take place at appreciable levels in natural environments, however. Reduced materials such as ferrous iron or hydrogen sulfide may compete with biological pathways in the reduction of Cr(VI). On the basis of measured reaction rates and derived rate expressions, we demonstrate that biological pathways are not likely to contribute to the reduction of chromate in anaerobic systems. Ferrous iron will dominate the reduction of chromate at pH values greater than ～ 5.5, whereas hydrogen sulfide will dominate at pH values below this value. In contrast, bacteria may be the principal means by which Cr(VI) is converted to Cr(III) in aerobic environments. Thus, the process by which Cr(VI) is reduced will depend primarily on the aeration status of the system, and secondarily on pH and the concentrations of specific reduced phases.     

Managanese and iron in the White Sea: Sedimentation and diagenesis

Iron and manganese in bottom sediments studied along the sublatitudinal transect from Kandalaksha to Arkhangelsk are characterized by various contents and forms depending on sedimentation environments, grain size of sediments, and diagenetic processes. The latter include redistribution of reactive forms leading to enrichment in Fe and Mn of the surface sediments, formation of films, incrustations, and ferromanganese nodules. Variations in the total Fe content (2–8%) are accompanied by changes in the concentration of its reactive forms (acid extraction) and the concentration of dissolved Fe in the interstitial water (1–14 μM). Variations in the Mn content in sediments (0.03–3.7%) and the interstitial water (up to 500 μM) correspond to a high diagenetic mobility of this element. Changes in the valence of chemical elements results in the redox stratification of sediment strata with maximum concentrations of Fe, Mn, and sulfides. Organic matter of sediments with a considerable terrestrial constituent is oxidized by bottom water oxygen mainly at the sediment surface or in anaerobic conditions within the sediment strata. The role of inorganic components in organic matter oxidation changes from surface sediments, where manganese oxyhydroxide dominates among oxidants, to deeper layers, where sulfate of interstitial water serves as the main oxidant. Differences in river runoff and hydrodynamics are responsible for geochemical asymmetry of the transect. The deep Kandalaksha Bay serves as a sediment trap for manganese (Mn content in sediments varies within 0.5–0.7%), whereas the sedimentary environment in the Dvina Bay promotes its removal from sediments (Mn 0.05%).     

Geochemical fractionation of manganese in the Riogrande II reservoir, Antioquia, Colombia

The Riogrande II reservoir in Colombia has a total storage capacity of 240 million m³ and lies 2,270 m above sea level. The reservoir is used for power generation, water supply and environmental improvement. Dissolved manganese (Mn) is removed from reservoir water dedicated to domestic use by purification processes. Removal of Mn, however, poses a major challenge to purification processes and warrants the study of ways to naturally reduce dissolved Mn levels in the reservoir. The source of Mn within the reservoir is not well understood, however, presumably arises from sediment mobilization initiated by variation in pH, redox potential (ORP or Eh), dissolved oxygen (O₂) and ionic strength conditions. This study investigated conditions within the reservoir to further understand Mn transfer from the sediment into the water column. O₂, pH, oxidation–reduction potential (ORP or Eh), organic matter content and electric conductivity were measured in water samples and sediment from the reservoir. Sequential extraction (SE) procedures were used to test the specific effects exerted by each of these conditions on Mn mobilization from the sediments. The European Community Bureau of Reference (BCR) sequential extraction procedure was used to quantify metals in sediment (referred to as the BCR extraction below). Statistical analysis of geochemical data from water samples (both water column and sediment pore water) and sediments demonstrated the conditions under which Mn can be released from sediments into the water column. The results indicated a primarily oxic water column and anoxic reducing conditions in the sediment (ORP or Eh ≤ ?80 mV). The pH of water in contact with bottom sediments varied from 7.6 to 6.8. The pH of sedimentary pore water varied from 6.8 to 4.7. The sediments contained significant amounts of organic matter (20 %). Chemical extractions showed that the exchangeable fraction contained over 50 % of the total Mn within sediments. Microscopic analysis using scanning electron microscopy–energy dispersive spectroscopy (SEM–EDS) indicated that Mn does not occur within well-crystallized mineral phases in the Riogrande II sediments. A large proportion of Mn exists instead as material adsorbed onto the surfaces of recently deposited sediment particles. Bacterial oxidation of organic matter may cause the observed anoxic conditions at the bottom of the reservoir. Mineralization of organic matter therefore contributes to reducing conditions within the sediments. Mobilization of Mn from the sediment into the water column may result from reductive dissolution of this fraction. Manganese release by this mechanism diminishes the water quality of the Riogrande II reservoir and warrants further study.     

Geochemistry of natural chromium occurrence in a sandstone aquifer in Bauru Basin, São Paulo State, Brazil

Anomalous concentrations of Cr(VI) occur in groundwaters of the Adamantina Aquifer, in a large region in the western state of São Paulo, sometimes exceeding the potability limit (0.05 mg L⁻¹). To identify the possible geochemical reactions responsible for the occurrence of Cr in groundwater in Urânia, borehole rock samples were collected in order to carry out mineralogical and chemical analyses. In addition, multilevel monitoring wells were installed and groundwater samples were analyzed. Analyses of the borehole rock samples show the occurrence of a geochemical anomaly of Cr in the quartzose sandstones (average concentrations of 221 ppm). Chrome-diopside is one of the main minerals contributing to this anomaly, having an average Cr content of 1505 ppm. Sequential extraction experiments indicated weakly adsorbed Cr in the order of 0.54 ppm, and this quantity is enough to provide the Cr concentrations observed in groundwater. Groundwaters from the monitoring wells proved to be stratified, with the highest concentrations of Cr(VI) (0.13 mg L⁻¹) being associated with high redox and pH values (over 10) and high concentrations of Na. Geochemical reactions that may explain the release of Cr from the solid phase to groundwater involve the release of Cr(III) from minerals (like chrome-diopside and Cr-Fe hydroxide), followed by oxidation of Cr(III) to Cr(VI), probably related to the reduction of Mn oxides present in the aquifer. Then cation exchange occurs and dissolution of carbonates which increases the pH of groundwater, resulting in the desorption and mobilization of Cr(VI) into groundwater.     

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.