Molecular mechanisms of nickel carcinogenesis: gene silencing by nickel delivery to the nucleus and gene activation/inactivation by nickel-induced cell signaling

We have summarized the molecular and cellular events involved in nickel (Ni) compound induced carcinogenesis. The major hypothesis for nickel carcinogenic action has involved the ability of the Ni compound to deliver high concentrations of Ni intracellularly, enter the nucleus and interact with chromatin. Ni has been found to selectively damage heterochromatin, and a major action of Ni is its ability to silence the expression of genes located near heterochromatin by inducing a loss of histone H4 and H3 acetylation and DNA hypermethylation. When Ni silences critical genes, such as tumor suppressor genes, the cell is altered to a greater state of neoplastic transformation. The carcinogenic hazard of Ni compounds has been directly related to the ability of that Ni compound to raise the intracellular Ni ions. The mechanisms of Ni-induced gene silencing will be discussed. However, recently it has been found that soluble Ni ions can interact with the cell surface receptors and activate cell signaling resulting in the induction of a variety of cellular genes. In particular, the Ca and hypoxia inducible factor pathway is activated in all cells exposed to soluble Ni ions. In the case of HIF-1 induction, a cell is now equipped with the expression of a variety of genes that will allow the cell to survive the lack of oxygen and thus should enable a previously initiated cancer cell to progress into a full malignant state and metastasize. These new findings support the view that soluble Ni ions exhibit carcinogenic potential by activating cell promotion and lend strength to the epidemiological data showing soluble Ni to be associated with cancer risk in Ni refinery workers.     

Response mechanisms of antioxidants in bryophyte (Hypnum plumaeforme) under the stress of single or combined Pb and/or Ni

The short-term responses and mechanisms of antioxidants in moss Hypnum plumaeforme subjected to single or combined Pb and/or Ni stress has been revealed in this study, in order to clarify (1) the relationship between the stress intensity and antioxidant fluctuation, (2) the difference between single and combined stress, and (3) the possibility of biomonitoring by the application of antioxidant fluctuation under stress. The results showed that the stress induced dose dependent formation of reactive oxygen species (ROS) and subsequent lipid peroxidation. Total chlorophyll (Chl) content and superoxide dismutase (SOD) activity were initiated under lower stress but were inhibited under higher stress. Both single and combined stress decreased catalase (CAT) activity but increased peroxidase (POD) activity, indicating POD in the moss played an important role in resisting the oxidative stress induced by Pb and Ni. The accumulation of (.)O2(-) and H2O2 in H. plumaeforme was respectively related to the low activity of SOD and the decreased activity of CAT. The study indicated that Pb and Ni had synergistic effect in inducing the oxidative stress in moss H. plumaeforme, especially under the combination of high concentration of Ni (0.1, 1.0 mM) and Pb. POD and CAT activity, as well as H2O2 and MDA content, which increased or decreased regularly with a dose dependent under Pb and Ni stress, could be used as an effective indicator in moss biomonitoring, especially in the case of light pollution caused by heavy metals without the changes in the appearance of mosses.     

Solid phase extraction of Cu(II), Ni(II), Pb(II), Cd(II) and Mn(II) ions with 1-(2-thiazolylazo)-2-naphthol loaded Amberlite XAD-1180

A new method for separation and preconcentration of trace amounts of Cu(II), Ni(II), Pb(II), Cd(II) and Mn(II) ions in various matrices was proposed. The method is based on the adsorption and chelation of the metal ions on a column containing Amberlite XAD-1180 resin impregnated with 1-(2-thiazolylazo)-2-naphthol (TAN) reagent prior to their determination by flame atomic absorption spectrometry (FAAS). The effect of pH, type, concentration and volume of eluent, sample volume, flow rates of sample and elution solutions, and interfering ions have been investigated. The optimum pH for simultaneous retention of all the metal ions was 9. Eluent for quantitative elution was 20 ml of 2 mol l(-1) HNO(3). The optimum sample and eluent flow rates were found as 4 ml min(-1), and also sample volume was 500 ml, except for Mn (87% recovery). The sorption capacity of the resin was found to be 0.77, 0.41, 0.57, and 0.30 mg g(-1) for Cu(II), Ni(II), Cd(II), and Mn(II), respectively. The preconcentration factor of the method was 200 for Cu(II), 150 for Pb(II), 100 for Cd(II) and Ni(II), and 50 for Mn(II). The recovery values for all of the metal ions were > or = 95% and relative standard deviations (RSDs) were < or = 5.1%. The detection limit values were in the range of 0.03 and 1.19 microg l(-1). The accuracy of the method was confirmed by analysing the certified reference materials (TMDA 54.4 fortified lake water and GBW 07605 tea samples) and the recovery studies. This procedure was applied to the determination of Cu(II), Ni(II), Pb(II), Cd(II) and Mn(II) in waste water and lake water samples.     

Near-real-time determination of hydrogen peroxide generated from cigarette smoke

The ability to monitor hydrogen peroxide (H2O2) in aqueous smoke extracts will advance our understanding of the relationship between cigarette smoke-induced oxidative stress, inflammation, and disease and help elucidate the pathways by which the various smoke constituents exert their pathogenic effects. We have demonstrated, for the first time, the measurement of H2O2 production from cigarette smoke without prior separation of the sample. Cigarettes were tested on a commercial smoking machine, such that the whole smoke or gas vapor phase was bubbled through phosphate buffered saline solution at pH 7.4. Aliquots of these solutions were analyzed using an Amplex Red/horseradish peroxidase fluorimetric assay that required only a 2 minute incubation time, facilitating the rapid, facile collection of data. Catalase was used to demonstrate the selectivity and specificity of the assay for H2O2 in the complex smoke matrix. We measured approximately 7-8 microM H2O2 from two reference cigarettes (i.e., 1R4F and 2R4F). We also observed 9x more H2O2 from whole smoke bubbled samples compared to the gas vapor phase, indicating that the major constituent(s) responsible for H2O2 formation reside in the particulate phase of cigarette smoke. Aqueous solutions of hydroquinone and catechol, both of which are particulate phase constituents of cigarette smoke, generated no H2O2 even though they are free radical precursors involved in the production of reactive oxygen species in the smoke matrix.     

The heterogeneous composition of working place aerosols in a nickel refinery: a transmission and scanning electron microscope study

Size, morphology and chemical composition of individual aerosol particles collected in a nickel refinery were analyzed by scanning electron microscopy and energy-dispersive X-ray microanalysis (EDX). The phase composition was determined by selected area electron diffraction and EDX in a transmission electron microscope. Most particles are heterogeneous on a nanometer scale and consist of various phases. Nickel phases observed in the roasting and anode casting departments include metallic nickel, bunsenite (NiO), trevorite (Ni,Cu)Fe2O4, heazlewoodite Ni3S2, godlevskite (Ni,Cu)9S8, orthorhombic NiSO4 and an amorphous Ni,Cu.Al,Pb sulfate of variable composition. Additional phases encountered include corundum (Al2O3), murdochite (PbCu6O8), hexagonal Na2SO4, anhydrite (CaSO4), graphite (C) and amorphous carbon. The implications of the occurrence of the different Ni phases and their nanometer size for the study of adverse health effects are explored.     

Influence of environmental parameters on the accuracy of nitrogen dioxide passive diffusion tubes for ambient measurement

Two studies at three sites in the UK provided confirmation that systematic positive bias in NO2 diffusion tube measurement occurred because of changes to "within-tube" chemistry, rather than eddy diffusion at the mouth of the tube. In the first study in Cambridge, UK, sampler overestimation for 1 and 2 week exposures was compared to corresponding time-averaged monitor measurements (NO-NO2-NOx, O3) and weather variables. Noninearity between sampler and monitor NO2 measurements was interpreted in terms of spatial and temporal variations in relative and absolute availability of NO, NO2 and O3 at the site. A maximum overestimation occurred for an exposure mean NO2/NOx approximately 0.5. The separate contributions of reduced NO2 photolysis and eddy diffusion were compared in Study II using samplers of two materials, acrylic and quartz, and of different lengths (40, 55, 71 and 120 mm) at three sites: Norwich background, Cambridge intermediate, London kerbside. For compared sites, NO2 measured by acrylic samplers was significantly higher than for equivalent quartz samplers. For quartz samplers [NO2]mean was only just above the monitor at Norwich and London; sampler/monitor NO2 = 1.04 (P = 0.59) and 1.01(P = 0.76), respectively. For acrylic samplers the order of [NO2]mean was 40 mm > 120 mm > 71 mm > or = 55 mm. Excepting 40 mm samplers, this accords with a chemical bias where co-diffusing NO and 03 molecules in longer tubes have more time to react to form excess NO2. Bias in 40 mm samplers is discussed. Eddy diffusion is negligible for standard samplers because [NO2]mean was equivalent for 55 mm and 71 mm acrylic samplers and close to monitor NO2 for 71 mm quartz tubes. Both studies showed that sampler accuracy was dependent on location. Significantly, overestimation was greatest (approximately 3-4 ppb) where the NO2 annual mean was approximately 20 ppb, close to the UK and EU air quality standard of 21 ppb.     

Nickel(II) biosorption from aqueous solutions by shrimp head biomass

The present study evaluates the capacity of shrimp (Farfantepenaeus aztecus) head to remove toxic Ni(II) ions from aqueous solutions. Relevant parameters that could affect the biosorption process, such as shrimp head pretreatment, solution pH level, contact time and initial Ni(II) concentration, were studied in batch systems. An increase in Ni(II) biosorption capacity and a reduction in the time required to reach Ni(II) biosorption equilibrium was manifested by shrimp head biomass pretreated by boiling in 0.5 N NaOH for 15 min; this biomass was thereafter denominated APSH. The optimum biosorption level of Ni(II) ions onto APSH was observed at pH 7.0. Biosorption increased significantly with rising initial Ni(II) concentration. In terms of biosorption dynamics, the pseudo-second-order kinetic model described Ni(II) biosorption onto APSH best. The equilibrium data adequately fitted the Langmuir isotherm model within the studied Ni(II) ion concentration range. According to this isotherm model, the maximum Ni(II) biosorption capacity of APSH was 104.22 mg/g. Results indicate that APSH could be used as a low-cost, environmentally friendly, and promising biosorbent with high biosorption capacity to remove Ni(II) from aqueous solutions.     

Inhibitor resistance and in situ capability of nanoparticle based gene quantification

We have demonstrated the preliminary results of the in situ monitoring capability of an inhibitor resistant gene quantification assay using magnetic bead (MB) and quantum dot (QD) nanoparticles (hereafter "MB-QD assay") for the detection of E. coli O157:H7 in environmental samples. The selectivity of the MB-QD assay was demonstrated via the discrimination of the target bacteria in the presence of nonspecific microbial populations. The effect of temperature on the assay was examined to evaluate the necessity of elevated temperature incubation. The reagents (i.e., particle complex and particle-DNA conjugate) were also shown to have a stability of at least 10 days without refrigeration, therefore enabling prior preparation and the subsequent storage of these reagents. In addition, it was found that the MB-QD assay was resistant to the presence of naturally occurring inhibitors (i.e., humic acids, Ca(2+)) and residual reagents from DNA extraction (i.e., surfactant, ethanol). Overall the results indicated that the MB-QD assay is potentially suitable for further development as an in situ bacteria monitoring method for working with inhibitor laden samples without requiring additional purification steps and elevated temperature processes.     

Catalytic hydrogenation of polyaromatic hydrocarbon (PAH) compounds in supercritical carbon dioxide over supported palladium

A series of supported palladium catalysts were evaluated for their ability to mediate the complete hydrogenation of polycyclic aromatic hydrocarbon (PAH) compounds. Benzo[a]pyrene (B[a]P) or phenanthrene (Phe) in hexane was merged with a hydrogen-carbon dioxide [5% (w/w) H(2)/CO(2)] stream and transferred to a flow through mini-reactor (capacity ca. 1 g) that was maintained at 90 degrees C under a back-pressure of 20.68 MPa. Effluent from the reactor trapped in hexane was monitored/quantified by gas chromatography-mass spectrometry. Catalyst formulations supported on iron powder, high density polyethylene (HDPE) or gamma-alumina were prepared and compared in terms of hydrogenation activity as measured by the quantity of substrate per unit time that could be perhydrogenated to toxicologically innocuous products. Both of the Pd preparations supported on gamma-alumina were more efficient than a commercial Pd(0) (5% w/w) on gamma-Al(2)O(3) formulation or preparations supported on HDPE or the iron powder. Bimetallic mixtures with Pd increased the hydrogenation activity when co-deposited with Cu or Ni but not with Ag or Co. However, increases in hydrogenation activity by increasing the loading of Pd (or bimetallic mixture) on this surface were limited. Despite using supercritical carbon dioxide (scCO(2)) to swell the surfaces of the polymer, the deposition of nanoparticles within the polyethylene formulation was appreciably less active than either the oxidic or the Fe(0) formulations.     

Utility of cefixime as a complexing reagent for the determination of Ni(II) in synthetic mixture and water samples

A simple, sensitive, and accurate UV spectrophotometric method has been developed for the determination of nickel in synthetic mixture and water samples. The method is based on the complexation reaction of nickel ion with cefixime, thus leading to the formation of Ni–cefixime complex in ethanol-distilled water medium at room temperature. The complex showed the maximum absorption wavelength at 332 nm. Beer’s law is obeyed in the working concentration range of 0.447–4.019 μg?mL^?1 with apparent molar absorptivity of 7.314?×?10³?L?mol^?1?cm^?1 and Sandell’s sensitivity of 0.008 μg/cm²/0.001 absorbance unit. The limits of detection and quantitation for the proposed method are 0.016 and 0.054 μg?mL^?1, respectively. The factors such as cefixime concentration and solvent affecting the complexation reaction were carefully studied and optimized. The method is validated as per the International Conference on Harmonisation guideline. The method is successfully applied to the determination of Ni(II) in synthetic mixture and wadi water samples collected from Al Rustaq. The same water samples are also analyzed by atomic absorption spectrophotometry. Both methods determined the amount of Ni(II) in water sample and found to be approximately the same.     

水和废水中总氮的现场快速分析方法研究

在现行水中总氮分析方法的基础上,利用便携式分光光度计和密封消解管,实验了过硫酸钾氧化、硫酸联氨还原、重氮－偶联反应的最佳条件,讨论了碱性过硫酸钾溶液用量及硫酸联氨溶液用量对分析结果的影响,从而建立了水体总氮的碱性过硫酸盐消解－分光光度分析方法,该方法可在现场简便快速地测定水和废水中的总氮。     

应用小鼠淋巴细胞彗星试验检测地下水遗传毒性

应用小鼠淋巴细胞彗星试验对长治市5个点位地下水水质作遗传毒性研究。结果表明,各水样有机浓集物均可对小鼠淋巴细胞DNA产生不同程度的遗传损伤,随着剂量的增加,Olive尾矩与阴性对照组(0.72±0.09)相比均有显著性差异(P0.05,P0.01)。在试验浓度范围内,以彗星尾部DNA含量、彗星尾长、尾矩和Olive尾矩所指示的DNA损伤程度随剂量增大而逐渐增加,存在显著的剂量-效应关系,其相关系数0.815。     

Comparison of leaching tests for the study of trace metals remobilisation in soils and sediments

Several leaching tests were applied and compared to study metal remobilisation on various unpolluted and contaminated soils and on several contaminated sediments. The trace elements considered were Cd, Cr, Cu, Ni, Pb and Zn, and leaching tests consisted of the application of reagents with contrasting characteristics and strengths in order to assess the information provided. An extraction with aqua regia permitted the estimation of the pseudo-total metal content in the sample. Mild extractants such as H2O, CaCl2 and NaNO3 showed low and similar leaching capacities. Acid (CH3COOH) and complexing (EDTA) agents were more effective in remobilising trace metals from soils and sediments. Cd and Zn showed similar extraction characteristics under both extractant solutions, whereas Cu and Pb were more sensitive to complexation, and Ni and Cr to acidification processes. Sequential chemical extractions provided additional information on the association of the trace elements with the different soil and sediment phases. Cd and Zn showed the highest mobility, Pb was associated to reducible solid phases, Cu and Ni to oxidisable phases, and Cr remained mostly in the residual fraction. The results obtained in this paper provided valuable information for choosing a leaching test, which is an instrument of environmental analysis for the estimation of trace metal mobility.     

Goose barnacle Pollicipes pollicipes as biomonitor of metal contamination in the northwest coast of Portugal

The main objective of this work was to assess the potential use of goose barnacle Pollicipes pollicipes as biomonitor of metal contamination in northwest (NW) coast of Portugal. The concentrations of Cd, Cr, Cu, Fe, Mn, Ni and Zn were determined in coastal seawaters and tissues of P. pollicipes, which allowed establishing correlations between metals in coastal seawaters and P. pollicipes and calculating metal bioaccumulation factors (BAFs). The results of this study showed that P. pollicipes soft tissues can be used for monitoring metal contamination in these coastal seawaters: (1) there were significant correlations (p??0.05); (2) soft tissues were sensitive to spatial variations of metal bioavailabilities and their concentrations ranged 0.70-2.22?mg?Cd?kg(-1), 0.49-1.40?mg?Cr?kg(-1), 1.37-2.07?mg?Ni?kg(-1), 2.4-3.3?mg?Cu?kg(-1), 5-59?mg?Mn?kg(-1), 134-578?mg?Fe?kg(-1)and 728-1,854?mg?Zn?kg(-1); (3) mean logarithmic bioaccumulation factors (log BAF) of Fe, Cd and Zn were higher, 5.57, 5.47 and 4.41, respectively, than mean log BAFs of Cr, Mn, Cu and Ni, 4.18, 4.14, 3.98 and 3.51, respectively. In contrary, P. pollicipes shell plates were not considered ideal material to monitor metal bioavailabilities in these coastal seawaters. Regarding the very high concentrations of Zn obtained in the coastal seawaters and P. pollicipes soft tissues, the NW coast of Portugal should be classified as "Class III/IV - Remarkably/Highly Polluted".     

微波消解-原子吸收光度法测定土壤中铜锌铅镉镍铬

用微波消解－原子吸收光度法测定土壤中铜，锌，铅，镉，镍和铬。通过硝酸－氢氟酸－过氧化氢体系消解液对土壤样品消解，选择出微波最佳消解条件。对硝酸－盐酸－过氧化氢体系消解液和硝酸－氢氟酸－过氧化氢体系消解液进行消解对比试验，发现前者不能将土壤样品完全消解，后者能将样品消解完全，但需将消解液中剩余的酸赶尽，否则测定结果将明显偏低。微波消解土壤与传统电热消解相比，操作简便快速，可提高工作效率。     

The effect of the presence of trace metals on the oxidation of Sb(III) by hydrogen peroxide in aqueous solution

Despite its importance for understanding the behaviour of antimony in the environment, the oxidation kinetics of Sb(III) with natural oxidants is still not well understood. We have studied the oxidation of Sb(III) by hydrogen peroxide on a time scale of hours in the presence of some trace metals, Cu(II), Mn(II), Zn(II) and Pb(II), under pH and concentration conditions close to natural ones. The effects that these trace metals have on Sb(iii) oxidation by hydrogen peroxide vary. Zn(II) had no catalytic effect at all, but Cu(II), Mn(II) and Pb(II) did, though their effects were not uniform. Cu(II) significantly accelerated the reaction, which remained first-order with respect to Sb(III) at any Cu(II) concentration tested. Pb(II) and Mn(II) also enhanced the reaction rates, but the apparent order of the reaction with respect to Sb(III) changed to two. The trace metal effect observed was concentration dependent for Pb(II). The addition of the hydroxyl radical scavenger 2-propanol suggests that the trace metal catalytic effect observed involves the action of hydroxyl radicals, but that they are not responsible for the oxidation of Sb(III) by H2O2 in the absence of trace metals. The fact that Sb(III) can be oxidized by hydroxyl radicals present in water, even if it is not capable of producing them, has important environmental implications because hydroxyl radicals are known to be abundant in many natural waters such as seawater, humic-rich surface waters or rainwater.     

Preconcentration of metal ions through chelation on a synthesized resin containing O, O donor atoms for quantitative analysis of environmental and biological samples

Nascent Amberlite XAD-4 has been used as the polymeric support for the synthesis of a stable extractor of metal ions, by incorporating phthalic acid through azo bridging. Elemental analyses and infra-red spectral and thermal studies were carried out for its characterization. The water regain value and hydrogen ion capacity were found to be 12.50 and 5.75 mmol g^?1, respectively. The optimum pH range for the maximum sorption of Ni(II), Mn(II), Cu(II), Zn(II), Cd(II), Cr(III), and Co(II) was observed at pH 5.5–8.0 with the corresponding half-loading time (t _1/2) of 9, 5, 9, 9, 3, 9, and 5 min, respectively. The preconcentration factor for Ni(II), Mn(II), Cu(II), Zn(II), Cd(II), Cr(III), and Co(II) are 190, 190, 190, 180, 180, 160, and 160, with the corresponding limit of preconcentration in the range of 5.25–6.25 μg L^?1. The detection limits, for flame atomic absorption spectrophotometry, were found to be 0.62, 0.60, 0.65, 0.75, 0.72, 0.84, and 0.85 μg L^?1, respectively. Method has been successfully applied to the analysis of water samples, multivitamin formulations, infant food substitutes, hydrogenated oil, and fishes.     

Development of a simple extraction cell with bi-directional continuous flow coupled on-line to ICP-MS for assessment of elemental associations in solid samples

A continuous-flow system comprising a novel, custom-built extraction module and hyphenated with inductively coupled plasma-mass spectrometric (ICP-MS) detection is proposed for assessing metal mobilities and geochemical associations in soil compartments as based on using the three step BCR (now the Measurements and Testing Programme of the European Commission) sequential extraction scheme. Employing a peristaltic pump as liquid driver, alternate directional flows of the extractants are used to overcome compression of the solid particles within the extraction unit to ensure a steady partitioning flow rate and thus to maintain constant operationally defined extraction conditions. The proposed flow set-up is proven to allow for trouble-free handling of soil samples up to 1 g and flow rates < or =10 mL min(-1). The miniaturized extraction system was coupled to ICP-MS through a flow injection interface in order to discretely introduce appropriate extract volumes to the detector at a given time and with a given dilution factor. The proposed hyphenated method demonstrates excellent performance for on-line monitoring of major and trace elements (Ca, Mn, Fe, Ni, Pb, Zn and Cd) released when applying the various extracting reagents as addressed in the BCR scheme, that is, 0.11 M CH(3)COOH, 0.1 NH(2)OH.HCl and 30% H(2)O(2), even when a well recognized matrix-sensitive detector, such as ICP-MS, is used. As a result of the enhanced temporal resolution of the ongoing extraction, insights into the breaking down of phases and into the kinetics of the metal release are obtained. With the simultaneous multielement detection capability of ICP-MS, the dynamic fractionation system presents itself as an efficient front-end for evaluation of actual elemental association by interelement comparison of metals leached concurrently during the extraction time. Thus, the intimate elemental association between Cd and Zn in contaminated soils could be assessed.     

Trace metal concentrations in tidal flat coastal sediments, Yamaguchi Prefecture, southwest Japan

Geochemical investigations of tidal flat coastal sediments at Ogori, Ozuki, and Kasado in Yamaguchi Bay of southwest Japan were conducted to determine their metal concentrations and to assess contamination levels, compared with sediment quality guidelines (SQG) and several pollutant indicators. Selected major oxides, trace elements, and total sulfur (TS) were determined by X-ray fluorescence. pH values of most samples were alkaline, indicating anoxic conditions. Average abundances of As, Pb, Zn, Cu, Ni, and Cr in Ozuki sediments were 11, 27, 109, 21, 19, and 52 mg/kg, respectively, compared to 9, 29, 80, 16, 18, and 42 mg/kg at Ogori and 12, 27, 151, 34, 30 and 80 mg/kg at Kasado, respectively. Average concentrations of As, Zn, and Cu in all samples and TiO(2), Fe(2)O(3), and P(2)O(5) at Kasado were greater than those of the upper continental crust. Contamination levels were assessed based on SQG, contamination factors (CF), pollution load index (PLI), enrichment factor (EF), and index of geoaccumulation (Igeo). According to the SQG of the US EPA, the sediments were heavily polluted with respect to As, whereas Zn, Cu, Ni, and Cr were classed as moderately polluted. The elevated CF values of As, Pb, and Zn identify moderate to considerable contamination, indicating that these metals are potentially toxic in the study area. Based on PLI and EF, the study sites are moderate to moderately severe polluted with As and Pb, moderately polluted with Zn, and weakly contaminated to noncontaminated with Cu, Ni, and Cr. The highest Igeo values for As, Pb, and Zn in the surface and core sediments reflected the tendency of metal contamination that seems to be related to their fine-grained nature, organic matter-rich sediments, and anthropogenic point sources. Trace metal contents were strongly correlated with Fe(2)O(3) and TiO(2), suggesting that Fe oxyhydroxides and detrital clastic load play a role in controlling abundances in the study area.     

Geochemistry and pH control of seepage from Ni-Cu rich mine tailings at Selebi Phikwe,Botswana

Acid mine drainage from mine tailings at Selebi Phikwe, eastern Botswana, has been investigated using a combination of total decomposition, sequential extraction, X-ray diffraction, Mössbauer spectroscopy, and SEM analyses of solid phase samples, water analyses, isotopic analyses, and geochemical modeling. The principal ferric phases in the seepage stream sediments are jarosite and goethite, which incorporate Ni and Cu. The Mössbauer spectroscopy (MS) indicated exclusively 3+ oxidation state of iron with typical features of ferric hydroxides/sulfates. A fraction of dissolved sulfate is also sequestered in gypsum which precipitates further downstream. Significant portions of Fe, Ni, and Cu are transported in suspension. Values of pH decreased downstream due to H⁺ generated by the precipitation of jarosite. Values of δ²H and δ¹⁸O indicate evaporation of pore water in the mine tailings before seepage. Values of δ³⁴S(SO₄) are consistent with the oxidation of sulfides, but sample from the seepage face is affected by dissolution of gypsum. No minerals of Ni and Cu were detected and the principal attenuation processes seem to be adsorption and co-precipitation with jarosite. Higher contents of Cu are sequestered in solid phases compared to Ni, in spite of much higher dissolved Ni concentrations. Based on the speciation calculations, seepage water is undersaturated with respect to all Ni and Cu phases and adsorption and co-precipitation with jarosite seems to be the principal attenuation processes. Direct geochemical modeling was able to reproduce downstream pH trends, thus confirming the precipitation of jarosite as the principal pH-controlling process.