Biogeochemical redox cycling of arsenic in mine-impacted lake sediments and co-existing pore waters near Giant Mine,Yellowknife Bay,Canada

Lacustrine sediments, submerged tailings, and their pore waters have been collected at several sites in Yellowknife Bay, Great Slave Lake, Canada, in order to investigate the biogeochemical controls on the remobilization of As from mining-impacted materials under different depositional conditions. Radiometric dating confirms that a mid-core enrichment of Pb, Zn, Cu and Sb corresponds to the opening of a large Au mine 60 a ago. This was evident even in a relatively remote site. Arsenic was enriched at mid-core, coincident with mining activity, but clearly exhibited post-depositional mobility, migrating upwards towards the sediment water interface (SWI) as well as down-core. Deep-water (15 m) Yellowknife Bay sediments that contain buried mine waste are suboxic, relatively organic-rich and abundant in microbes with As in pore waters and sediments reaching 585 μg/L and 1310 mg/kg, respectively. Late summer pore waters show equal proportions of As(III) and As(V) (16–415 μg/L) whereas late winter pore waters are dominated by As(III) (284–947 μg/L). This can be explained by As(III) desorption mechanisms associated with the conversion of FeS to FeS₂ and the reduction of As(V) to As(III) through the oxidation of dissolved sulfide, both microbially-mediated processes. Processes affecting As cycling involve the attenuating efficiency of the oxic zone at the SWI, sediment redox heterogeneity and the reductive dissolution of Fe(hydr)oxides by labile organic matter, temporarily and spatially variable.     

Arsenic and antimony contamination of waters,stream sediments and soils in the vicinity of abandoned antimony mines in the Western Carpathians,Slovakia

Environmental contamination with As and Sb caused by past mining activities at Sb mines is a significant problem in Slovakia. This study is focused on the environmental effects of the 5 abandoned Sb mines on water, stream sediment and soil since the mines are situated in the close vicinity of residential areas. Samples of mine wastes, various types of waters, stream sediments, soils, and leachates of the mine wastes, stream sediments and selected soils were analyzed for As and Sb to evaluate their geochemical dispersion from the mines. Mine wastes collected at the mine sites contained up to 5166 mg/kg As and 9861 mg/kg Sb. Arsenic in mine wastes was associated mostly with Fe oxides, whereas Sb was present frequently in the form of individual Sb, Sb(Fe) and Fe(Sb) oxides. Waters of different types such as groundwater, surface waters and mine waters, all contained elevated concentrations of As and Sb, reaching up to 2150 μg/L As and 9300 μg/L Sb, and had circum-neutral pH values because of the buffering capacity of abundant Ca- and Mg-carbonates. The concentrations of Sb in several household wells are a cause for concern, exceeding the Sb drinking water limit of 5 μg/L by as much as 25 times. Some attenuation of the As and Sb concentrations in mine and impoundment waters was expected because of the deposition of metalloids onto hydrous ferric oxides built up below adit entrances and impoundment discharges. These HFOs contained >20 wt.% As and 1.5 wt.% Sb. Stream sediments and soils have also been contaminated by As and Sb with the peak concentrations generally found near open adits and mine wastes. In addition to the discharged waters from open adits, the significant source of As and Sb contamination are waste-rock dumps and tailings impoundments. Leachates from mine wastes contained as much as 8400 μg/L As and 4060 μg/L Sb, suggesting that the mine wastes would have a great potential to contaminate the downstream environment. Moreover, the results of water leaching tests showed that Sb was released from the solids more efficiently than As under oxidizing conditions. This might partly explain the predominance of Sb over As in most water samples.     

Simultaneous oxidation of arsenic and antimony at low and circumneutral pH,with and without microbial catalysis

Arsenic and Sb are common mine-water pollutants and their toxicity and fate are strongly influenced by redox processes. In this study, simultaneous Fe(II), As(III) and Sb(III) oxidation experiments were conducted to obtain rates under laboratory conditions similar to those found in the field for mine waters of both low and circumneutral pH. Additional experiments were performed under abiotic sterile conditions to determine the biotic and abiotic contributions to the oxidation processes. The results showed that under abiotic conditions in aerated Fe(III)–H₂SO₄ solutions, Sb(III) oxidizes slightly faster than As(III). The oxidation rates of both elements were accelerated by increasing As(III), Sb(III), Fe(III), and Cl⁻ concentrations in the presence of light. For unfiltered circumneutral water from the Giant Mine (Yellowknife, NWT, Canada), As(III) oxidized at 15–78 μmol/L/h whereas Sb(III) oxidized at 0.03–0.05 μmol/L/h during microbial exponential growth. In contrast, As(III) and Sb(III) oxidation rates of 0.01–0.03 and 0.01–0.02 μmol/L/h, respectively, were obtained in experiments performed with acid unfiltered mine waters from the Iberian Pyritic Belt (SW Spain). These results suggest that the Fe(III) formed from microbial oxidation abiotically oxidized As(III) and Sb(III). After sterile filtration of both mine water samples, neither As(III), Sb(III), nor Fe(II) oxidation was observed. Hence, under the experimental conditions, bacteria were catalyzing As and Sb oxidation in the Giant Mine waters and Fe oxidation in the acid waters of the Iberian Pyrite Belt.     

The behavior of arsenic and antimony at Pezinok mining site,southwestern part of the Slovak Republic

Arsenic and antimony contamination is found at the Pezinok mining site in the southwest of the Slovak Republic. Investigation of this site included sampling and analysis of water, mineralogical analyses, sequential extraction, in addition to flow and geochemical modeling. The highest dissolved arsenic concentrations correspond to mine tailings (up to 90,000 μg/L) and the arsenic is present predominately as As(V). The primary source of the arsenic is the dissolution of arsenopyrite. Concentration of antimony reaches 7,500 μg/L and its primary source is the dissolution of stibnite. Pore water in mine tailings is well-buffered by the dissolution of carbonates (pH values between 6.6 and 7.0) and arsenopyrite grains are surrounded by reaction rims composed of ferric iron minerals. Based on sequential extraction results, most solid phase arsenic is in the reducible fraction (i.e. ferric oxyhydroxides), sulfidic fraction, and residual fraction. Distribution of antimony in the solid phase is similar, but contents are lower. The principal attenuation mechanism for As(V) is adsorption to ferric oxide and hydroxides, but the adsorption seems to be limited by the competition with Sb(V) produced by the oxidation of stibnite for adsorption sites. Water in mine tailings is at equilibrium with gypsum and calcite, but far from equilibrium with any arsenic and antimony minerals. The concentrations of arsenic and antimony in the surrounding aquifer are much lower, with maximum values of 215 and 426 μg/L, respectively. Arsenic and antimony are transported by ground water flow towards the Blatina Creek, but their loading from ground water to the creek is much lower compared with the input from the mine adits. In the Blatina Creek, arsenic and antimony are attenuated by dilution and by adsorption on ferric iron minerals in stream sediments with resulting respective concentrations of 93 and 45 μg/L at the site boundary south of mine tailing ponds.     

Environmental impact and geochemistry of old tailing pile from the Sanggok mine creek, Republic of Korea

This study evaluates the pollution load on a creek based on the physicochemical and mineralogical properties of old tailings. The Sanggok mine is one of the largest lead–zinc producers in the Hwanggangri mining district, Republic of Korea. The vertical profile of the old tailings in the mine area can be divided into three units based on color change, and mineralogical and textural variations, as well as physical and chemical properties. Unit I (surface accumulation and oxidized heterogeneous tailing soil) has lower pH and higher Eh than unit II (originally unoxidized dumped tailing soil) and unit III (pebble-bearing bottom soil). The conductivity data indicates that unit I and II have very high values compared to unit III and basement. The mine area consists mainly of carbonate rocks; however, mineral constituents of tailing soil and sediments near the mine were mainly composed of quartz, mica, feldspar, amphibole, calcite, dolomite, magnesite, and clay minerals. Units I and II are characterized by high abundances of siderite, locally pyrite, and dolomite. Precipitates in the mining drainage mainly included: smectite, illite, berthierine, quartz, siderite, hexahydrite, and Ca-ferrate. Among the separated metallic minerals, tailing soils and sediments of highly concentrated toxic metals are found: some pyrite, arsenopyrite, chalcopyrite, sphalerite, galena, malachite, goethite, various hydroxide, and uncertain secondary minerals. Units I and II are characterized by relatively high concentrations of Ca, Fe, Mn and low contents of Al, Mg, K, Na, Ti, rare earth elements (REEs) that correlated with the proportion of secondary minerals. Potentially toxic elements such as Ag, As, Cd, Cu, Pb, Sb, and Zn are highly enriched in the upper two units. This metal concentration can be influenced by changes in the depth because of oxic and suboxic zonal distribution. The removal zone (unit I) has probably migrated below the elevation of the maximum enrichment layer due to deepening of the oxic/suboxic boundary. In most of the materials, the enrichment index is higher than 3.62. The highest value of 42.55 is found in the oxidation surface soils of the tailing pile. An average enrichment index of the profiles and precipitates are 27.62 and 22.62, respectively. Rocky basement soils have an average enrichment index of 6.63, which is influenced by overlying the tailing pile. The water quality and habitat of the Sanggok creek are severely polluted. Polluted surface water may also negatively impact the agricultural soil and groundwater.     

Arsenic remobilization from sediments contaminated with mine tailings near the Adak mine in Västerbotten district (northern Sweden)

Weathering of mine tailings have resulted in high As concentrations in water (up to 2900 μg l^− 1) and sediment (up to 900 mg kg^− 1) samples around the Adak mine. Notably, As occurs as As(III) species (15–85%) in the oxic surface and ground water samples, which is not common. Time-series based sediment incubations were set up in the laboratory with contaminated sediments to study the microbial processes involved in transformation and remobilization of As across the sediment–water interface. The microcosm experiments indicate that microorganisms are capable of surviving in As-rich sediments and reduce As(V) to As(III). A decrease in total As concentration in sediments is coupled to an increase in As(III) concentration in the aqueous media. In contrast, the controls (treated with HgCl₂ and formaldehyde) did not show growth, and As(V) concentrations increased steadily in the sediments and aqueous medium. The results imply that active metabolism is necessary for As(V) reduction. These microorganisms possess reduction mechanisms that are not necessarily coupled to respiration, but most likely impart resistance to As toxicity.     

大冶铁山地区河流水体及水系沉积物中重金属元素分布特征

矿产资源的长期勘探、开采和冶炼活动给大冶铁山地区的自然生态环境造成了严重破坏.对该区西港河、东港河河水和水系沉积物中重金属元素分布特征的研究结果表明,该区矿山开采和冶炼活动形成的重金属污染元素主要为Cd、As、Zn;其主要污染源为冶炼厂排放的废水,其次是采矿废弃物堆积渗漏水;重金属元素在河水与水系沉积物中的空间分布特征较相似,但水系沉积物中元素质量分数比河水中的普遍增高,元素变化的剧烈程度加剧.     

Arsenic mobility in weathered gold mine tailings under a low-organic soil cover

Historical gold mining operations in Nova Scotia, Canada, resulted in numerous deposits of publicly accessible, arsenic (As)-rich mine waste that has weathered in situ for 75–150 years, resulting in a wide range of As-bearing secondary minerals. The geochemical heterogeneity of this mine waste creates a challenge for identifying a single remediation approach that will limit As mobility. A 30-cm-thick, low-organic content soil cover was evaluated in a laboratory leaching experiment where, to simulate natural conditions, the equivalent of 2 years of synthetic rainwater was leached through each column and two dry seasons were incorporated into the leaching protocol. Each column was a stratigraphic representation of the four major tailings types found at the historical Montague and Goldenville gold mine districts: hardpan tailings, oxic tailings, wetland tailings, and high Ca tailings. Hardpan tailings released acidic, As-rich waters (max 12 mg/L) under the soil cover but this acidity was buffered by surrounding oxic tailings. Leachate from the oxic tailings was circumneutral, with average As concentrations between 4.4 and 9.7 mg/L throughout the experiment. The presence of carbonates in the high Ca tailings resulted in near-neutral to weakly alkaline leachate pH values and average As concentrations between 2.1 and 6.1 mg/L. Oxidation of sulfides in the wetland tailings led to acidic leachate over time and a decrease in As concentrations to values that were generally less than 1 mg/L. This study shows that the use of a low-organic content soil cover does not create reducing conditions that would destabilize oxidized, As-bearing secondary phases in these tailings. However, oxygen penetration through the cover during dry seasons would continue to release As to tailings pore waters via sulfide oxidation reactions.     

Removal of arsenic from aqueous solution by natural siderite and hematite

Batch and column experiments were conducted to examine the capability of naturally formed hematite and siderite to remove As from drinking water. Results show that both minerals were able to remove As from aqueous solutions, but with different efficiencies. In general, each material removed arsenate much more efficiently than As–DMA (dimethylarsinic acid), with the lowest adsorption efficiency for arsenite. The best removal efficiency for As species was obtained using a hematite, with a grain size range between 0.25 and 0.50 mm. The adsorption capacity for inorganic As(V) reached 202 μg/g. The pH generally had a great impact on the arsenate removal by the Fe minerals studied, while arsenite removal was slightly dependent on the initial pH of between 3 and 10. The presence of phosphate always had a negative effect on arsenate adsorption, due to competitive adsorption between them. A column packed with hematite in the upper half and siderite in the lower half with a grain size range of 0.25–0.5 mm proved to be an efficient reactive filter for the removal of all As species, causing a decrease in As concentration from 500 μg/L (including 200 μg/L As(V) as arsenate, 200 μg/L As(III) as arsenite and 100 μg/L As(V) as DMA) to less than 10 μg/L after 1055 pore volumes of water were filtered at a flow rate of 0.51 mL/min. After 2340 pore volumes passed through the column filter, the total inorganic As in the effluent was less than 5 μg/L. The total As load in the column filter was estimated to be 0.164 mg/g. Results of μ-synchrotron X-ray fluorescence analysis (μ-XRFA) suggest that coatings of fresh Fe(III) oxides, formed on the surface of the siderite grains after two weeks of operation, greatly increased the adsorption capacity of the filling material towards As.     

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

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

Trace element fractionation and transport in boreal rivers and soil porewaters of permafrost-dominated basaltic terrain in Central Siberia

The chemical status of ∼40 major and trace elements (TE) and organic carbon (OC) in pristine boreal rivers draining the basaltic plateau of Central Siberia (Putorana) and interstitial solutions of permafrost soils was investigated. Water samples were filtered in the field through progressively decreasing pore size (5 μm → 0.22 μm → 0.025 μm → 10 kDa → 1 kDa) using cascade frontal filtration technique. Most rivers and soil porewaters exhibit 2-5 times higher than the world average concentration of dissolved (i.e., <0.22 μm) iron (0.03-0.4 mg/L), aluminum (0.03-0.4 mg/L), OC (10-20 mg/L) and various trace elements that are usually considered as immobile in weathering processes (Ti, Zr, Ga, Y, REEs). Ultrafiltration revealed strong relationships between concentration of TE and that of colloidal Fe and Al. According to their partition during filtration and association with colloids, two groups of elements can be distinguished: (i) those weakly dependent on ultrafiltration and that are likely to be present as truly dissolved inorganic species (Li, Na, K, Si, Mn, Mo, Rb, Cs, As, Sb) or, partially (20-30%) associated with small size Fe- and Al-colloids (Ca, Mg, Sr, Ba) and to small (<1-10 kDa) organic complexes (Co, Ni, Cu, Zn), and (ii) elements strongly associated with colloidal iron and aluminum in all ultrafiltrates largely present in 1-100 kDa fraction (Ga, Y, REEs, Pb, V, Cr, Ti, Ge, Zr, Th, U). TE concentrations and partition coefficients did not show any detectable variations between different colloidal fractions for soil porewaters, suprapermafrost flow and surface streams. TE concentration measurements in river suspended particles demonstrated significant contribution (i.e., ?30%) of conventionally dissolved (<0.22 μm) forms for usually “immobile” elements such as divalent transition metals, Cd, Pb, V, Sn, Y, REEs, Zr, Hf, Th. The Al-normalized accumulation coefficients of TE in vegetation litter compared to basalts achieve 10-100 for B, Mn, Zn, As, Sr, Sn, Sb, and the larch litter degradation is able to provide the major contribution to the annual dissolved flux of most trace elements. It is hypothesized that the decomposition of plant litter in the topsoil horizon leads to Fe(III)-, Al-organic colloids formation and serves as an important source of elements in downward percolating fluids.     

Effect of arsenic concentration on microbial iron reduction and arsenic speciation in an iron-rich freshwater sediment

Depth profiles in the sediment porewaters of the Chattahoochee River (Georgia, USA) show that iron oxides scavenge arsenate in the water column and settle to the sediment-water interface (SWI) where they are reduced by iron-reducing bacteria. During their reduction, these particles seem to release arsenic to the porewaters in the form of arsenate only. Sediment slurry incubations were conducted to determine the effect of low concentrations of arsenic (?10 μM) on biogeochemical processes in these sediments. Experiments confirm that any arsenate (As(V)) added to these sediments is immediately adsorbed in oxic conditions and released in anoxic conditions during the microbial reduction of authigenic iron oxides. Incubations in the presence of ?1 μM As(V) reveal that arsenate is released but not concomitantly reduced during this process. Simultaneously, microbial iron reduction is enhanced significantly, spurring the simultaneous release of arsenate into porewaters and secondary formation of crystalline iron oxides. Above 1 μM As(V), however, the microbial reductive dissolution of iron oxides appears inhibited by arsenate, and arsenite is produced in excess in the porewaters. These incubations show that even low inputs of arsenic to riverine sediments may affect microbial processes, the stability of iron oxides and, indirectly, the cycling of arsenic. Possible mechanisms for such effects on iron reduction are proposed.     

Formation and composition of cemented layers in low-sulphide mine tailings, Laver, northern Sweden

Cemented layers (hardpans) are common in carbonate or sulphide-rich mine tailings and where pyrrhotite is the predominating Fe-sulphide. Laver, northern Sweden, is an abandoned Cu-mine where the tailings have low pyrrhotite content, almost no pyrite and no carbonates. Two cemented layers at different locations in the Laver tailings impoundment were investigated, with the aim to determine their effects on metal mobility. The cementing agents were mainly jarosite and Fe-oxyhydroxides in the layer formed where the tailings have a barren surface, whereas only Fe-oxyhydroxides were identified below grass-covered tailings surface. Arsenic was enriched in both layers which also exhibit high concentrations of Mo, V, Hg and Pb compared to unoxidised tailings. Sequential extraction indicates that these metals and As were mainly retained with crystalline Fe-oxides, and therefore potentially will be remobilised if the oxic conditions become more reducing, for instance as a result of remediation of the tailings impoundment.An erratum to this article can be found at     

Distribution of trace elements in filtered and non filtered aqueous fractions: Insights from rivers and streams of Sardinia (Italy)

The distribution of several trace elements in different aqueous fractions has been studied in running waters from Sardinia (Italy). Trace elements and major components were determined in water samples collected at high- and low-discharge from rivers (90 samples) and streams (70 samples). At selected sites, total (non filtered samples) and dissolved (0.4 μm and 0.015 μm pore-size filtered samples) amounts of trace elements were determined, and the composition of the solid matter retained on the filters was investigated for estimating the eventual interrelationship. The elements B, Li, Rb, Sr, Ba, As, Sb, Mo, Tl and U in the studied waters showed small differences between total and dissolved amounts; dissolved concentrations were higher under low flow conditions, when the contribution of rainwater to the rivers was minimum; their concentrations were often correlated with total dissolved solids (TDS), and appeared to be related to the intensity of water-rock interaction processes. The elements Al, Fe, Mn, Pb, Zn, Cd, Cu, Co, Ni, Cs, Y, REE and Th were not related to TDS and/or major ions; they showed higher concentrations under high flow conditions; marked differences occurred between total and dissolved amounts; much lower concentrations were generally observed in the water filtered through 0.015 μm than in the water filtered through 0.4 μm, especially when sampling was carried out after heavy rain events that enhanced the load of solid matter in the water. These observations indicate an aqueous transport via sorption processes on very fine particles, such as Fe-oxide/hydroxide and clay mineral particles, which have been inferred by SEM-EDX analyses of the matter retained on the filters.     

湘西金矿尾矿—水相互作用：1．环境地球化学效应

湘西金矿在生产过程中产生了大量的尾矿。该区尾矿－水相互作用强烈，并引起了尾矿中重金属元素的释放、迁移和对水体－土壤、蔬菜等表生环境的重金属污染。污染程度较大的元素均为Au、Sb、As、Cd、Hg、W等，与尾矿中元素的富集特征相一致。尾矿中重金属元素的水迁移能力由大到小顺序为Au、Cd、W、Sb、Pb、As、Zn、Cu。元素的生物吸收系数由大至小顺序为Cd、Au、Zn、Hg、Sb、Cu、Pb、As、W。植物中金属元素浓度主要受土壤中的浓度、植物种类和吸收的影响。     

Distribution and reactivity of oxyanions (Sb, As, V, Mo) in the surface freshwater reaches of the Gironde Estuary (France)

The present work reports on the temporal variations of Sb, As, V and Mo concentrations in the surface freshwater reaches of the Gironde Estuary (SW France). Dissolved (<0.2 and <0.02 μm) and particulate Sb, As, V and Mo concentrations were measured in samples collected with high temporal resolution (every 30 min) during two consecutive tides at a fixed station located upstream of the city of Bordeaux and the maximum turbidity zone (MTZ). In addition, measurements of suspended particulate matter concentration, physico-chemical parameters, Cl⁻ concentration, water depth, current velocity and particulate Th concentration were performed either at the same time resolution or continuously. The data obtained suggested that variations in particulate As, V and Mo concentrations were most probably related to tidal cycling near the sampling site of fine grained particles from the MTZ located downstream. Significant differences in the behavior of the dissolved target oxyanions, mostly present in the <0.02 μm fraction, occurred. The behavior of Sb was conservative. Variations of the dissolved As and V concentrations showed similar cycling trends, strongly related to tidal cycles. These As and V cycles were interpreted as a mixing between upstream freshwater and downstream water enriched in dissolved As and V by desorption from the MTZ particles. The observed trend in the variation of the dissolved Mo was more complex than that of As and Sb and attributed to the mixing of the water bodies mentioned above coupled to a point source input of dissolved Mo from an intra-estuarine source. The contribution of this suspected Mo source to the dissolved Mo concentrations measured at the sampling site was estimated from the ratio of dissolved Mo to dissolved As concentrations. The additional dissolved Mo signal, coupled to the monitored ebb and flood length and associated current velocities, suggested an anthropogenic input which may derive from industrial activity near the city of Bordeaux. Extrapolating these results to the annual scale suggested that this dissolved Mo may be equivalent to 45-90% of the annual dissolved Mo flux into the Garonne Branch, highlighting the importance to further investigate the origin and behavior of Mo in the fluvial estuary near Bordeaux.     

The transport and fate of Fe,Mn, Cu,Zn, Cd,Pb and SO4 in a groundwater plume and in downstream surface waters in the Coeur d'Alene Mining District,Idaho, U.S.A.

The controls on metal concentrations in a plume of acidic (pH 3.29–5.55) groundwater in the Moon Creek watershed in Idaho, U.S.A., were investigated with the use of property-property plots. A plot of Ca vs S demonstrated that a plume of contaminated groundwater was being diluted by infiltration of rain and creek water at shallow depths and by ambient groundwater near bedrock. The small amount of dissolved Fe (2.1 mg/l) was removed while dissolved Pb was added, reaching a maximum concentration of 0.37 mg/l. The other metals (Zn ≤ 16, Al ≤ 6.2, Cu ≤ 2.1 and Cd ≤ 0.077 mg/l) in the shallow groundwater were essentially conserved until they emerged as a seep along the creek bank. Upon mixing with the creek water, groundwater was diluted by factors between 11 and 50, and the pH of the mixture became neutral. Metals originating from the contaminated groundwater were removed in the creek in the following order: Fe > Al > Pb ≫ Cu > Mn > Zn = Cd.Pb and Cu continued to be removed from solution even as the creek passed adjacent to a tailings pile. In contrast, Zn concentrations in the creek increased adjacent to the tailings area, presumably as a result of the reemergence of the upgradient plume as the creek lost elevation.Below the tailings dam, contaminated creek water (400–800 μg Zn/l) was diluted by both smaller side streams and a creek of equal flow. The presence of 3 distinctive water masses required the use of two tracers (dissolved Si and S) to distinguish between mixing and geochemical reactions. The removal of metals was greater during low flow conditions. Pb was removed to the greatest extent, falling below detection limits (0.5 μ/l) at the first sampling location. Copper and Mn were removed to a lesser extent during low flow conditions and approached conservative behavior during high flow conditions. During a 5-km journey through two hydrological regimes, less than 10% of the dissolved Zn and Cd was lost.     

Sediment pore-water interactions associated with arsenic and uranium transport from the North Cave Hills mining region,South Dakota,USA

The extent of historical U mining impacts is well documented for the North Cave Hills region of Harding County, South Dakota, USA. While previous studies reported watershed sediment and surface water As and U concentrations up to 90× established background concentrations, it was unclear whether or how localized changes in sediment redox behavior may influence contaminant remobilization. Five pore-water equilibration samplers (peepers) were spatially and temporally deployed within the study area to evaluate seasonal solid–liquid As and U distributions as a function of sediment depth. Pore-water and solid phase As and U concentrations, Fe speciation, Eh and pH were measured to ascertain specific geochemical conditions responsible for As and U remobilization and transport behavior. At a mine overburden sedimentation pond adjacent to the mine sites, high total aqueous As and U concentrations (4920 and 674 μg/L, respectively) were found within surface water during summer sampling; however pond dredging prior to autumn sampling resulted in significantly lower aqueous As and U concentrations (579 and 108 μg/L, respectively); however, both As and U still exceeded regional background concentrations (20 and 18 μg/L, respectively). At a wetlands-dominated deposition zone approximately 2 km downstream of the sedimentation pond, pore-water geochemical conditions varied seasonally. Summer conditions promoted reducing conditions in pore water, resulting in active release of As(III) to the water column. Autumn conditions promoted oxidizing conditions, decreasing pore-water As (As_pw) 5× and increasing U_pw 10×. Peak U pore-water concentrations (781 μg/L) were 3.5× greater than determined for the surface water (226 μg/L), and approximately 40× background concentrations. At the Bowman–Haley reservoir backwaters 45 km downstream from the mine sites, As and U pore-water concentrations increased significantly between the summer and autumn deployments, attributed to increased Fe reduction processes. Geochemical modeling suggests solid-phase Fe reduction promotes the liberation of pore-water As and U via suppressing the formation of thioarsenite. Intermittent hydrological processes facilitate As and U transport and deposition throughout the watershed, while biogeochemical-influenced redox changes cycle As and U between pore and surface water within localized environments.     

Arsenic attenuation in tailings at a former Cu–W–As mine,SW Finland

Nearly half a century after mine closure, release of As from the Ylöjärvi Cu–W–As mine tailings in groundwater and surface water run-off was observed. Investigations by scanning electron microscopy (SEM), electron microprobe analysis (EMPA), synchrotron-based micro-X-ray diffraction (μ-XRD), micro-X-ray absorption near edge structure (μ-XANES) and micro-extended X-ray absorption fine structure (μ-EXAFS) spectroscopy, and a sequential extraction procedure were performed to assess As attenuation mechanisms in the vadose zone of this tailings deposit. Results of SEM, EMPA, and sequential extractions indicated that the precipitation of As bearing Fe(III) (oxy)hydroxides (up to 18.4 wt.% As₂O₅) and Fe(III) arsenates were important secondary controls on As mobility. The μ-XRD, μ-XANES and μ-EXAFS analyses suggested that these phases correspond to poorly crystalline and disordered As-bearing precipitates, including arsenical ferrihydrite, scorodite, kaňkite, and hydrous ferric arsenate (HFA). The pH within 200 cm of the tailings surface averaged 5.7, conditions which favor the precipitation of ferrihydrite. Poorly crystalline Fe(III) arsenates are potentially unstable over time, and their transformation to ferrihydrite, which contributes to As uptake, has potential to increase the As adsorption capacity of the tailings. Arsenic mobility in tailings pore water at the Ylöjärvi mine will depend on continued arsenopyrite oxidation, dissolution or transformation of secondary Fe(III) arsenates, and the As adsorption capacity of Fe(III) (oxy)hydroxides within this tailings deposit.     

Assessing the solubility controls on vanadium in groundwater,northeastern San Joaquin Valley,CA

The solubility controls on vanadium (V) in groundwater were studied due to concerns over possible harmful health effects of ingesting V in drinking water. Vanadium concentrations in the northeastern San Joaquin Valley ranged from <3 μg/L to 70 μg/L with a median of 21 μg/L. Concentrations of V were highest in samples collected from oxic groundwater (49% > 25 μg/L) and lowest in samples collected from anoxic groundwater (70% < 0.8 μg/L). In oxic groundwater, speciation modeling (SM) using PHREEQC predicted that V exists primarily as the oxyanion H₂VO₄⁻. Adsorption/desorption reactions with mineral surfaces and associated oxide coatings were indicated as the primary solubility control of V⁵⁺ oxyanions in groundwater. Environmental data showed that V concentrations in oxic groundwater generally increased with increasing groundwater pH. However, data from adsorption isotherm experiments indicated that small variations in pH (7.4–8.2) were not likely as an important a factor as the inherent adsorption capacity of oxide assemblages coating the surface of mineral grains. In suboxic groundwater, accurate SM modeling was difficult since Eh measurements of source water were not measured in this study. Vanadium concentrations in suboxic groundwater decreased with increasing pH indicating that V may exist as an oxycationic species [e.g. V(OH)₃⁺]. Vanadium may complex with dissolved inorganic and organic ligands under suboxic conditions, which could alter the adsorption behavior of V in groundwater. Speciation modeling did not predict the existence of V-inorganic ligand complexes and organic ligands were not collected as part of this study. More work is needed to determine processes governing V solubility under suboxic groundwater conditions. Under anoxic groundwater conditions, SM predicts that aqueous V exists as the uncharged V(OH)₃ molecule. However, exceedingly low V concentrations show that V is sparingly soluble in anoxic conditions. Results indicated that V may be precipitating as V³⁺- or mixed V³⁺/Fe³⁺-oxides in anoxic groundwater, which is consistent with results of a previous study. The fact that V appears insoluble in anoxic (Fe reducing) redox conditions indicates that the behavior of V is different than arsenic (As) in aquifer systems where the reductive dissolution of Fe-oxides with As adsorbed to the surface is a well-documented mechanism for increasing As concentrations in groundwater. This hypothesis is supported by the relation of V to As concentrations in oxic versus anoxic redox conditions.Sequential extraction procedures (SEP) applied to aquifer material showed that the greatest amount of V was recovered by the nitric acid (HNO₃) extract (37–71%), followed by the oxalate-ascorbic acid extract (19–60%) and the oxalate extract (3–14%). These results indicate that V was not associated with the solid phase as an easily exchangeable fraction. Although the total amount of V recovered was greatest for the HNO₃ extract that targets V adsorbed to sorption sites of crystalline Al, Fe and Mn oxides, the greatest V saturation of sorption sites appeared to occur on the amorphous and poorly crystalline oxide solid phases targeted by the oxalate and oxalate-ascorbic acid extracts respectively. Adsorption isotherm experiments showed no correlation between V sorption and any of the fractions identified by the SEP. This lack of correlation indicates the application of an SEP alone is not adequate to estimate the sorption characteristics of V in an aquifer system.