http://www.sciencedirect.com/science/article/pii/S1674987111001149

An integrated approach was performed on the soil,plant-crops and groundwater system at the Thiva basin,to evaluate the extent and intensity of the heavy metal contamination,the percentage of metals tra...     

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.     

A regional-scale study of chromium and nickel in soils of northern California, USA

A soil geochemical survey was conducted in a 27,000-km² study area of northern California that includes the Sierra Nevada Mountains, the Sacramento Valley, and the northern Coast Range. The results show that soil geochemistry in the Sacramento Valley is controlled primarily by the transport and weathering of parent material from the Coast Range to the west and the Sierra Nevada to the east. Chemically and mineralogically distinctive ultramafic (UM) rocks (e.g. serpentinite) outcrop extensively in the Coast Range and Sierra Nevada. These rocks and the soils derived from them have elevated concentrations of Cr and Ni. Surface soil samples derived from UM rocks of the Sierra Nevada and Coast Range contain 1700–10,000 mg/kg Cr and 1300–3900 mg/kg Ni. Valley soils west of the Sacramento River contain 80–1420 mg/kg Cr and 65–224 mg/kg Ni, reflecting significant contributions from UM sources in the Coast Range. Valley soils on the east side contain 30–370 mg/kg Cr and 16–110 mg/kg Ni. Lower Cr and Ni concentrations on the east side of the valley are the result of greater dilution by granitic sources of the Sierra Nevada.Chromium occurs naturally in the Cr(III) and Cr(VI) oxidation states. Trivalent Cr is a non-toxic micronutrient, but Cr(VI) is a highly soluble toxin and carcinogen. X-ray diffraction and scanning electron microscopy of soils with an UM parent show Cr primarily occurs within chromite and other mixed-composition spinels (Al, Mg, Fe, Cr). Chromite contains Cr(III) and is highly refractory with respect to weathering. Comparison of a 4-acid digestion (HNO₃, HCl, HF, HClO₄), which only partially dissolves chromite, and total digestion by lithium metaborate (LiBO₃) fusion, indicates a lower proportion of chromite-bound Cr in valley soils relative to UM source soils. Groundwater on the west side of the Sacramento Valley has particularly high concentrations of dissolved Cr ranging up to 50 μg L⁻¹ and averaging 16.4 μg L⁻¹. This suggests redistribution of Cr during weathering and oxidation of Cr(III)-bearing minerals. It is concluded that regional-scale transport and weathering of ultramafic-derived constituents have resulted in enrichment of Cr and Ni in the Sacramento Valley and a partial change in the residence of Cr.     

Chromium contamination from chromite mine

Among the dominant species of chromium, the trivalent form widely occurs in nature in chromite ores or in silicate minerals and is extremely immobile. The higher oxidation state Cr(VI), is, however, rarely found in nature, is more mobile, and several times more toxic than Cr(III). Cr(VI) occurs in chromates and dichromates manufactured from chromite ores. The hexavalent state is stable in an oxidizing alkaline environment, whereas the trivalent state is stable in a reducing acidic environment. Serpentinization and Mg release during deuteric alteration of ultramafic rocks create alkaline pore water and lateritization is an intensive oxidation process. Chromite ore bodies in oxidized serpentinite therefore may generate hexavalent chromium from the inert chromites and cause hazardous chromium pollution of the water. With this end in view, a combined field and laboratory study has been made on chromite-bearing oxidized serpentinite rocks of Sukinda in Orissa, India. Laboratory leaching studies on mine overburden samples, chemical analyses of streamwater, and hydrolysate incrustation on detrital grains taken from stream beds have indicated the possibility of chromium mobilization from the chromite ores into the waterbodies.     

Biogenic nano-magnetite and nano-zero valent iron treatment of alkaline Cr(VI) leachate and chromite ore processing residue

Highly reactive nano-scale biogenic magnetite (BnM), synthesized by the Fe(III)-reducing bacterium Geobacter sulfurreducens, was tested for the potential to remediate alkaline Cr(VI) contaminated waters associated with chromite ore processing residue (COPR). The performance of this biomaterial, targeting aqueous Cr(VI) removal, was compared to a synthetic alternative, nano-scale zero valent iron (nZVI). Samples of highly contaminated alkaline groundwater and COPR solid waste were obtained from a contaminated site in Glasgow, UK. During batch reactivity tests, Cr(VI) removal from groundwater was inhibited by ∼25% (BnM) and ∼50% (nZVI) when compared to the treatment of less chemically complex model pH 12 Cr(VI) solutions. In both the model Cr(VI) solutions and contaminated groundwater experiments the surface of the nanoparticles became passivated, preventing complete coupling of their available electrons to Cr(VI) reduction. To investigate this process, the surfaces of the reacted samples were analyzed by TEM-EDX, XAS and XPS, confirming Cr(VI) reduction to the less soluble Cr(III) on the nanoparticle surface. In groundwater reacted samples the presence of Ca, Si and S was also noted on the surface of the nanoparticles, and is likely responsible for earlier onset of passivation. Treatment of the solid COPR material in contact with water, by addition of increasing weight % of the nanoparticles, resulted in a decrease in aqueous Cr(VI) concentrations to below detection limits, via the addition of ⩾5% w/w BnM or ⩾1% w/w nZVI. XANES analysis of the Cr K edge, showed that the % Cr(VI) in the COPR dropped from 26% to a minimum of 4–7% by the addition of 5% w/w BnM or 2% w/w nZVI, with higher additions unable to reduce the remaining Cr(VI). The treated materials exhibited minimal re-mobilization of soluble Cr(VI) by re-equilibration with atmospheric oxygen, with the bulk of the Cr remaining in the solid fraction. Both nanoparticles exhibited a considerable capacity for the remediation of COPR related Cr(VI) contamination, with the synthetic nZVI demonstrating greater reactivity than the BnM. However, the biosynthesized BnM was also capable of significant Cr(VI) reduction and demonstrated a greater efficiency for the coupling of its electrons towards Cr(VI) reduction than the nZVI.     

A chromate-contaminated site in southern Switzerland – Part 1: Site characterization and the use of Cr isotopes to delineate fate and transport

The risk of groundwater contamination by chromate at a former chromite ore processing industrial site in Rivera (Switzerland) was assessed by determining subsoil Cr(VI) concentrations and tracking naturally occurring Cr(VI) reduction with Cr isotopes. Using a hot alkaline extraction procedure, a total Cr(VI) contamination of several 1000 kg was estimated. Jarosite, KFe₃((SO₄)_x(CrO₄)_1−x)₂(OH)₆, and chromatite (CaCrO₄) were identified as Cr(VI) bearing mineral phases using XRD, both limiting groundwater Cr(VI) concentrations. To track assumed Cr(VI) reduction at field scale δ⁵³Cr values of contaminated subsoil samples in addition to groundwater δ⁵³Cr data are used for the first time. The measurements showed a fractionation of groundwater δ⁵³Cr values towards positive values and subsoil δ⁵³Cr towards negative values confirming reduction of soluble Cr(VI) to insoluble Cr(III). Using a Rayleigh fractionation model, a current Cr(VI) reduction efficiency of approximately 31% along a 120 m long flow path was estimated at an average linear groundwater velocity of 3.3 m/d. Groundwater and subsoil δ⁵³Cr values were compared with a site specific Rayleigh fractionation model proposing that subsoil δ⁵³Cr values can possibly be used to track previous higher Cr(VI) reduction efficiency during the period of industrial activity. The findings strongly favor monitored natural attenuation to be part of the required site remediation measures.     

Geochemistry of Neogene sedimentary rocks from Borneo Basin,East Malaysia: Paleo-weathering,provenance and tectonic setting

Multi-element geochemistry and mineralogy are used to characterize the chemical composition, degree of paleo-weathering, provenance and tectonic settings of the Neogene sedimentary rocks of Borneo Basin of east Malaysia. Sedimentary rocks are classified as extremely weathered sandstones (i.e. wacke, arkose, litharenite, Fe-sandstone and quartz arenite). Wacke, arkose, litharenite and Fe-sandstone are characterized by post-depositional K-metasomatism and zircon enrichment through sediment recycling. Geochemical characteristics suggest a mixed-nature provenance for the sandstones and the variable tectonic settings possibly mirror the complexity of the basin. Enriched Cr in quartz arenite and Fe-sandstone are related to the contribution from ophiolite or fractionation of Cr-bearing minerals.     

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.     

Chromium and nickel distribution in soils, active river, overbank sediments and dust around the Burrel chromium smelter (Albania)

Chromium ore was treated to produce ferrochromium from 1979 until 2000 in a smelter in Burrel, 35 km NE of Tirana (Albania). As a consequence, large amounts of solid waste, i.e. slags (about 9.10⁶ m³) have been disposed next to the smelter, disfiguring the landscape. In an attempt to define contaminated sites, heavy metal content of the different sampling media have been compared with respective background samples.In the study area, the determination of background values in soil samples is complicated due to the different geological substrates. Cr and Ni background concentrations in serpentinite-derived soils, west of the smelting plant, are markedly higher than in the Pliocene gravel/sandy soils, where the smelter is situated (Cr 2147 and 193 mg/kg, respectively; Ni 2356 and 264 mg/kg). These values are clearly lower than those encountered around the smelter. Average total Cr and Ni concentrations in soils around the smelter are 3117 and 1243 mg/kg, respectively. The highest concentrations of Cr (up to 2.3 wt.%), were recorded in samples taken near the smelting compartment within the industrial plant and next to the slags clearly indicating that the smelter forms a point source of Cr contamination. The Cr / Fe ratio is the best indicator to differentiate non-polluted (Cr / Fe Serpentinite soil: 130–390; Pliocene soils: < 130) from polluted areas (> 390 smelting nearby of the slags).Cr and Ni values for local backgrounds in stream and overbank sediments were taken in the Mat river 6 km upstream and to the east of the smelter (268 and 430 mg/kg for Cr, and 306 and 604 mg/kg for Ni, respectively). Equivalent sediments taken from the Zalli i Germanit river, which drains the smelter area are respectively 816 and 1126 mg/kg for Cr and 1115 and 1185 mg/kg for Ni.Dust samples, taken from the lofts of houses up to 2 km from the smelter, display high concentrations of Cr, Ni and Zn (average contents of 2899, 436 and 902 mg/kg, respectively). The later concentrations in the dust samples have been confirmed by mineralogical analysis where Cr-bearing mineral phases such as ferrochromium and chromium oxides, clearly relate to the activity of the smelter. Consequently, atmospheric deposition of dust particles forms a serious problem and can also be responsible for the elevated contents encountered in soil samples around the smelter.All these data show that the degree of contamination caused by industrial activity of the Burrel Cr-smelter is severe, although no Cr(VI) was detected in soil water extractions nor in the surface or groundwater where concentrations were < 0.01 mg/kg.     

A study on soil physico-chemical, microbial and metal content in Sukinda chromite mine of Odisha, India

Soil samples from chromite mining site and its adjacent overburden dumps and fallow land of Sukinda, Odisha, were analysed for their physico-chemical, microbial and metal contents. Chromite mine soils were heterogenous mixture of clay, mud, minerals and rocks. The pH of the soils ranges between 5.87 and 7.36. The nutrient contents of the mine soils (N, P, K and organic C) were found to be extremely low. Analysis of chromite mine soils revealed accumulation of a number of metals in high concentrations (Fe > Cr > Mn > Ni > Zn > Pb > Sr) which exceeded ecotoxicological limits in soil. Correlation and cluster analysis of metals revealed a strong relation between Cr, Ni, Fe, Mn among the different attributes studied. Assessment of different microbial groups such as fungi, actinomycetes and bacteria (heterotrophic, spore forming, free-living nitrogen fixing, phosphate solubilising and cellulose degrading) from mine soils were found to be either extremely low or absent in some soil samples. Further chromium tolerant bacteria (CTB) were isolated using 100 mg/L Cr(VI) enriched nutrient agar medium and were screened for their tolerance towards increasing concentrations of hexavalent chromium and other toxic metals. Out of 23 CTB isolates, three bacteria tolerated up to 900 mg/L, 6 up to 500 mg/L, 20 up to 200 mg/L of Cr(VI). These bacteria were also found to be sensitive towards Cu > Co > Cd and very few CTB strains could show multiple metal tolerance. These strains have great scope for their application in bioremediation of toxic chromium ions in presence of other metals ions, which needs to be explored for their biotechnological applications.     

On the genesis of demantoid from Xinjiang,China

Demantoid is a rare gem mineral. The Xinjiang Cr-bearing demantoid reported in this paper has been discovered for the first time in China. It contains more than 90% end-member molecule of andradite, close to the pure end-member composition, as revealed by chemical analysis, X-ray powder diffraction, Mössbauer spectrometry and both infrared and optical absorption spectrometry. The Fe²⁺ content lies beyond the detection limit of Mössbauer spectrometry. It was found that the green color of demantoid is directly related geological occurrence and mineral association the genesis of demantoid is inferred as follows. In ultramafic to Fe³⁺ in the octahedral site and that the presence of Cr³⁺ greatly enhances its inferred as follows. In ultramafic rocks olivine and pyroxene were replaced by serpentine under the reaction of residual volatiles, creating an Fe-rich and Al-poor environment. In such an environment late-stage hydrothermal metasomatism was developed along the fissures of serpentine, resulting in the crystallization and precipitation of demantoid in asbestos veins. On the other hand, local tectonic compression and dislocation gave rise to the formation of demantoid aggregates cemented by serpentine asbestos. Evidence has shown that the trace Cr was derived from chromite and Cr-spinel in the ultramafic rock bodies.     

Chromium speciation in oxide-type compounds: application to minerals,gems, aqueous solutions and silicate glasses

Cr K-edge XANES spectra were obtained for a variety of Cr-bearing model compounds containing Cr(II), Cr(III), Cr(IV), Cr(V) and Cr(VI), in which the Cr-site symmetry is D4h, Oh and Td. The centroid position of the pre-edge feature is a better indicator of the Cr valence than the edge position. In Cr-rich oxides, higher-energy transitions must be excluded in order to refine a robust valence for Cr. The pre-edge for chromates is not unique and varies as a function of the CrO₄ ^2? moiety distortion, which is often related to Cr-polymerization (monochromate vs. dichromate). Both the analogy with the Mn K-pre-edge information and ab initio FEFF calculations of the pre-edge feature for Cr(III) and Cr(VI) confirm the experimental trends. This methodology is applied to the Cr K-edge pre-edge feature collected in gems (emerald, spinel and ruby), the layered minerals fuchsite and kämmererite, two Cr-bearing aqueous solutions and a set of sodo-calcic silicate glasses used for bottling sparkling white wine. In emerald and fuchsite, the Cr-site is differently distorted than its ruby or spinel counterpart. In a Cr(III)-bearing aqueous solution and sodo-calcic glass, no evidence for Cr(III) with Td and C3v symmetry is detected. However, minor amounts of chromate moieties (most likely monomeric) are detected in a glass synthesized in air. Preliminary spectra for the wine bottle glass suggest that only trace amounts of chromates might possibly be present in these glasses.     

青岛八仙墩海相碎屑岩的岩石地球化学特征及其油气研究意义

青岛八仙墩剖面出露了一套海相陆源碎屑沉积层序。这套碎屑岩受崂山花岗岩侵入已经发生变质,岩性以硬砂岩为主,夹有页岩、含锰细砂岩、长石砂岩,富含白云质。这套地层保留了各种原生的沉积构造,发育有浊积岩的底模构造,同沉积变形,水平层理、微粒序层理。岩石地球化学分析结果表明:碎屑岩的SiO_2含量在59.6%～71.6%之间,含量的多少与岩性无相关性;而黑色页岩的Al_2O_3含量变化于12.31%～16.39%之间,多在15%以上,高于灰白色砂岩的含量(普遍小于14.5%)。镜下特征和Al203含量都表明砂岩的成熟度低。除一个样品外,碎屑岩的∑REE含量高,在146.75×10~(-6)～245.78×10~(-6)之间,La在30.35×10~(-6)～61.39×10~(-6)之间,对球粒陨石标准化的(La/Yb)_N在8.68×10~(-6)～21.89×10~(-6)之间。对PASS标准化碎屑岩的(La/Ce)_N值为1.07～1.18,显示了陆源碎屑物质的主要贡献。该地层弱的Ce/Ce*负异常和富含白云质岩层指示了海相沉积环境。主量元素判别图解和微量元素判别图解表明这套碎屑岩具有活动大陆边缘背景和大陆岛弧的共同特征,但高的∑REE含量、La和Ce丰度支持了活动大陆边缘的沉积环境,但有待于采用更准确的重矿物分析来确定其物源区的大地构造性质。这套碎屑岩的出露指示了南黄海盆地深部应有奥陶统盆地相浊积沉积体系的存在,可能具有良好的浊积砂岩油气储层。     

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.     

Origin of the Zedang and Luobusa Ophiolites,Tibet

The Zedang and Luobusa ophiolites are located in the eastern section of the Yalung Zangbo ophiolite belt,and they share similar geological tectonic setting and age.Thus,an understanding of their origins is very important for discussion of the evolution of the Eastern Tethys Ocean.There is no complete ophiolite assemblage in the Zedang ophiolite.The Zedang ophiolite is mainly composed of mantle peridotite and a suite of volcanic rocks as well as siliceous rocks,with some blocks of olivinepyroxenite.The mantle peridotite mainly consists of Cpx-harzburgite,harzburgite,some lherzolite,and some dunite.A suite of volcanic rocks is mainly composed of caic-aikaline pyroclastic rocks and secondly of tholeiitic pillow lavas,basaltic andesites,and some boninitic rocks with a lower TiO2 content （TiO2 ＜ 0.6％）.The pyroclastic rocks have a LREE-enriched REE pattern and a LILE-enriched （compared to HFSE） spider diagram,demonstrating an island-arc origin.The tholeiitic volcanic rock has a LREE-depleted REE pattern and a LILE-depleted （compared to HFSE） spider diagram,indicative of an origin from MORB.The boninitic rock was generated from fore-arc extension.The Luobusa ophiolite consists of mantle peridotite and mafic-ultramaflc cumulate units,without dike swarms and volcanic rocks.The mantle peridotite mainly consists of dunite,harzburgite with low-Opx （Opx ＜ 25％）,and harzburgite （Opx ＞ 25％）,which can be divided into two facies belts.The upper is a dunite-harzburgite （Opx ＜ 25％） belt,containing many dunite lenses and a large-scale chromite deposit with high Cr203; the lower is a harzburgite （Opx ＞25％） belt with small amounts of dunite and lherzolite.The Luobusa mantle peridotite exhibits a distinctive vertical zonation of partial melting with high melting in the upper unit and low melting in the lower.Many mantle peridotites are highly depleted,with a characteristic U-shaped REE pattern peculiar to fore-arc peridotite.The Luobusa cumulates are composed of wehrlite and olivine-pyroxenite,of the P-P-G ophiolite series.This study indicates that the Luobusa ophiolite was formed in a fore-arc basin environment on the basis of the occurrence of highly depleted mantle peridotite,a high-Cr2O3 chromite deposit,and cumulates of the P-P-G ophiolite series.We conclude that the evolution of the Eastern Tethys Ocean involved three stages：the initial ocean stage （formation of MORB volcanic rock and dikes）,the forearc extension stage （formation of high-Cr203 chromite deposits and P-P-G cumulates）,and the islandarc stage （formation of caic-alkaline pyroclastic rocks）.     

Mantle(?) xenoliths in the carbonatites of northern Transbaikalia

The composition and nature of high-Cr minerals in lithic clasts from the carbonatites of the Veseloe occurrence, northern Transbaikalia, were considered. In order to determine their source, the Cr-bearing phases were compared with chromite, magnetite, and rutile from ultrabasic rocks, mantle xenoliths, and eclogites. It was suggested that the xenoclasts studied were formed at great depths, whereas the carbonatites were directly derived from the mantle rather than formed by the crustal differentiation of a silicate-carbonate melt.     

Origin and mobility of hexavalent chromium in North-Eastern Attica,Greece

An integrated framework that is comprised of field surveys of groundwater, surface water and soils, laboratory process experiments and hydrologic and geochemical modeling is used to identify the origin (anthropogenic versus geogenic sources), fate and transport of hexavalent Cr in Tertiary and Quaternary deposits of Oropos plain in Greece. Groundwater and soils were analyzed in May 2008 and exhibited considerable Cr concentrations. Mineralogical analysis and micro-XRF analysis of the heavy soil fractions (metallic components) showed Cr bearing phases like chromites, Cr-silicate phases with positive correlation between Si, Al, Fe and Cr soil concentrations. Column experiments showed the Cr(VI) desorption ability of soils, e.g. concentration of 20 μg L⁻¹ was detected after the application of 50 mm of rain. The groundwater model simulated the variability of Cr concentrations emanating from both anthropogenic and geogenic sources, successfully using rate constants obtained from the laboratory experiments, e.g. 4.24 nM h⁻¹ for serpentine soil and 0.77 nM h⁻¹ for soil in alluvial deposits. The mineralogical and geochemical results support a geogenic origin for Cr in soils and groundwater of Oropos plain while modeling results suggest that contaminants transported by Asopos River have affected only the upper layers of the subsurface in the vicinity of the river. The framework can be used to establish background concentrations or clean up levels of Cr-contaminated soils and groundwater.     

Characterization and evaluation of a tropical peat for the removal of Cr(VI) from solution

Tropical peat soils present higher ash content than those generated at temperate climate areas. Therefore, this study evaluated the characteristics of a Brazilian organic soil (OS), commercialized as peat, as well as its capacity in removing Cr(VI) from contaminated waters. The OS is composed of 35.5 wt% of organic matter and 56 wt% of inorganic fraction (ash), which is formed by minerals and phytoliths rich in silica (29.2 wt%) and alumina (23.6 wt%). The Cr(VI) removal tests were carried out in batch and column systems using OS and solutions of Cr(VI) prepared with distilled water and groundwater. Batch tests revealed that the organic substances in the OS caused the reduction of Cr(VI) to Cr(III), with an efficiency depending on solution pH. At pH 5.0 the Cr(VI) removal was 0.45 mg g^?1 in 24 h; whereas at pH 2.0, this removal increased to 1.10 mg g^?1. Since this redox reaction is very slow, the removal of Cr(VI) at pH 5.0 increased to around 2 mg g^?1 after 5 days. The removal of Cr(VI) was more effective in the column tests than in the batch test due to the greater solid/solution ratio, and their half-lives were 4.4 and 26.2 h, respectively. Chemical analysis indicated that Cr(VI) was reduced by the humic substances of OS, followed by the precipitation and/or adsorption of Cr(III) into the organic and inorganic components, as anatase. The presence of Cr(III) increased the stability of anatase structure, avoiding its transformation into rutile, even after being heated at 800 °C/2 h.     

Anomalous content of chromium in a Cretaceous sandstone aquifer of the Bauru Basin,state of São Paulo,Brazil

Anomalous and natural concentrations of Cr⁶⁺, occasionally exceeding the permitted limit for human consumption (0.05 mg/L), have been detected in groundwater in the northwestern region of the state of São Paulo. As part of a water-rock interaction investigation, this article describes the chemical and mineralogical characterization of rock samples taken from boreholes in the municipality of Urânia, with the objective of identifying Cr-bearing minerals and determining how chromium is associated with these minerals. Rock sample analysis were performed using X-ray Fluorescence, X-ray Diffraction, Scanning Electron Microscopy, electron microprobe and sequential extraction techniques. Chemical analyses indicated that the quartzose sandstones show a geochemical anomaly of chromium, with an average content of 221 ppm, which is higher than the reported chromium content of generic sandstones (35 ppm). Diopside was identified as the primary Cr-bearing mineral potentially subject to weathering processes, with a chromium content of up to 1.2% as Cr₂O₃. Many of the diopside grains showed dissolution features, confirming the occurrence of weathering. Sequential extraction experiments indicated that 99.3% of the chromium in samples is tightly bonded to minerals, whereas 0.24% is weakly bonded via adsorption. Assuming hypothetically that all adsorbed chromium is released via desorption, the theoretical Cr concentration in water would be one order of magnitude higher than the concentrations of Cr⁶⁺ detected in groundwater.