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.     

Dissolved and particulate metals and arsenic species mobility along a stream affected by Acid Mine Drainage in the Iberian Pyrite Belt (SW Spain)

Intensive mining has taken place in the Iberian Pyrite Belt since 3000 B.C. generating Acid Mine Drainage (AMD) and releasing high amounts of SO₄, acidity, metals and metalloids into surface water. Concentrations of elements in AMD-impacted waters are regulated by the precipitation of Fe-rich materials and particulate matter can influence the mobility and the bioavailability of metals. In this paper a study on the dissolved As species concentration along a polluted stream has been performed. Two sampling campaigns were conducted during the dry and the rainy seasons. Concentrations of dissolved elements are higher during the dry season and increase progressively along the water course in both seasons. Concentrations up to 80 μg L⁻¹ of As³⁺ and 5 mg L⁻¹ of As⁵⁺ were determined. The concentration of As species increases and the As³⁺/As⁵⁺ ratio decreases downstream. The Fe²⁺/Fe³⁺ and As³⁺/As⁵⁺ ratios show the same pattern with respect to pH for all the examined samples, except those taken from Au cyanidation wastes. The particulate phase is mainly composed of Fe, As and Pb, with As being associated with the Fe minerals while Pb seems to be associated with the clay colloids.     

Irrigation produces elevated arsenic in the underlying groundwater of a semi-arid basin in Southwestern Idaho

The shallow aquifer beneath the Western Snake River Plain (Idaho, USA) exhibits widespread elevated arsenic concentrations (up to 120 μg L⁻¹). While semi-arid, crop irrigation has increased annual recharge to the aquifer from approximately 1 cm prior to a current rate of >50 cm year⁻¹. The highest aqueous arsenic concentrations are found in proximity to the water table (all values >50 μg L⁻¹ within 50 m) and concentrations decline with depth. Despite strong vertical redox stratification within the aquifer, spatial distribution of aqueous species indicates that redox processes are not primary drivers of arsenic mobilization. Arsenic release and transport occur under oxidizing conditions; groundwater wells containing dissolved arsenic at >50 μg L⁻¹ exhibit elevated concentrations of O₂ (average 4 mg L⁻¹) and NO₃ (average 8 mg L⁻¹) and low concentrations of dissolved Fe (<20 μg L⁻¹). Sequential extractions and spectroscopic analysis of surficial soils and sediments indicate solid phase arsenic is primarily arsenate and is present at elevated concentrations (4–45 mg kg⁻¹, average: 17 mg kg⁻¹) relative to global sedimentary abundances. The highest concentrations of easily mobilized arsenic (up to 7 mg kg⁻¹) are associated with surficial soils and sediments visibly stained with iron oxides. Batch leaching experiments on these materials using irrigation waters produce pore water arsenic concentrations approximating those observed in the shallow aquifer (up to 152 μg L⁻¹). While As:Cl aqueous phase relationships suggest minor evaporative enrichment, this appears to be a relic of the pre-irrigation environment. Collectively, these data indicate that infiltrating irrigation waters leach arsenic from surficial sediments to the underlying aquifer.     

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 formation, structure, and ageing of As-rich hydrous ferric oxide at the abandoned Sb deposit Pezinok (Slovakia)

The abandoned Sb deposit Pezinok in Slovakia is a significant source of As and Sb pollution that can be traced in the upper horizons of soils kilometers downstream. The source of the metalloids are two tailing impoundments which hold ∼380,000 m³ of mining waste. The tailings and the discharged water have circumneutral pH values (7.0 ± 0.6) because the acidity generated by the decomposition of the primary sulfides (pyrite, FeS₂; arsenopyrite, FeAsS; berthierite, FeSb₂S₄) is rapidly neutralized by the abundant carbonates. The weathering rims on the primary sulfides are iron oxides which act as very efficient scavengers of As and Sb (with up to 19.2 wt% As and 23.7 wt% Sb). In-situ μ-XANES experiments indicate that As in the weathering rims is fully oxidized (As⁵⁺). The pore solutions in the impoundment body contain up to 81 ppm As and 2.5 ppm Sb. Once these solutions are discharged from the impoundments, they precipitate or deposit masses of As-rich hydrous ferric oxide (As-HFO) with up to 28.3 wt% As₂O₅ and 2.7 wt% Sb. All As-HFO samples are amorphous to X-rays. They contain Fe and As in their highest oxidation state and in octahedral and tetrahedral coordination, respectively, as suggested by XANES and EXAFS studies on Fe K and As K edges. The iron octahedra in the As-HFO share edges to form short single chains and the chains polymerize by sharing edges or corners with the adjacent units. The arsenate ions attach to the chains in a bidentate-binuclear and monodentate fashion. In addition, hydrogen-bonded complexes may exist to satisfy the bonding requirements of all oxygen atoms in the first coordination sphere of As⁵⁺. Structural changes in the As-HFO samples were traced by chemical analyses and Fe EXAFS spectroscopy during an ageing experiment. As the samples age, As becomes more easily leachable. EXAFS spectra show a discernible trend of increasing number of Fe-Fe pairs at a distance of 3.3-3.5 Å, that is, increasing polymerization of the iron octahedra to form larger units with fewer adsorption sites. Therefore, although ferrihydrite is an excellent material for capturing arsenic, its use as a medium for a long-term storage of As has to be considered with a great caution because it will tend to release arsenic as it ages.     

Downstream changes in antimony and arsenic speciation in sediments at a mesothermal gold deposit in British Columbia,Canada

This study investigates Sb speciation in sediments along the drainage of the Upper Peter adit at the Bralorne Au mine in southern British Columbia, Canada, and compares the behavior of Sb with that of As. The Upper Peter mineralization consists of native Au in quartz-carbonate veins with 1 wt.% sulfides dominated by pyrite and arsenopyrite although stibnite, the primary Sb-bearing sulfide mineral, can be locally significant. Dissolved Sb concentrations can reach up to 349 μg L⁻¹ in the mine pool. Sediments were collected for detailed geochemical and mineralogical characterization at locations along the 350-m flow path, which includes a 100-m shallow channel within the adit, a sediment settling pond about 45 m beyond the adit portal and an open wetland another 120 m farther downstream. From the mine pool to the wetland outlet, dissolved Sb in the drainage drops from 199 μg L⁻¹ to below the detection limit due to the combined effect of dilution and removal from solution. Speciation analyses using X-ray absorption near-edge structure (XANES) spectroscopy indicate that Sb(III)–S accounts for around 70% of total Sb in the sediments in the main pool at the far end of the adit. At a short distance (24 m) downstream of the main adit pool, however, Sb(III)–O and Sb(V)–O species represent ?50% of total Sb in the bulk sediments, indicating significant oxidation of the primary sulfides inside the adit. Although Sb appears largely oxidized in the bulk samples collected near the portal, Sb(III)–S species are nevertheless present in the <53-μm fraction, suggesting a higher oxidation rate for stibnite in the coarser grains, possibly due to galvanic interaction with pyrite. Secondary Sb species released from the sulfide oxidation are most likely sorbed/co-precipitated with Fe-, Mn-, and Al-oxyhydroxides along the flow channel in the adit and in the sediment settling pond, with the Fe phase being the dominant sink for Sb.     

Partitioning geochemistry of arsenic and antimony,El Tatio Geyser Field,Chile

The abundance of As and Sb in aqueous, mineral and biological reservoirs was examined at El Tatio Geyser Field, a unique hydrothermal basin located in the Atacama Desert region of Chile. Here the concentration of total As and Sb in hydrothermal springs and discharge streams are the highest reported for a natural surface water, and the geyser basin represents a significant source of toxic elements for downstream users across Region II, Chile. The geyser waters are near neutral Na:Cl type with ∼0.45 and 0.021 mmol L⁻¹ total As and Sb, respectively, primarily in the reduced (III) redox state at the discharge with progressive oxidation downstream. The ferric oxyhydroxides associated with the microbial mats and some mineral precipitates accumulate substantial As that was identified as arsenate by XAS analysis (>10 wt% in the mats). This As is easily mobilized by anion exchange or mild dissolution of the HFO, and the ubiquitous microbial mats represent a significant reservoir of As in this system. Antimony, in contrast, is not associated with the mineral ferric oxides or the biomats, but is substantially enriched in the silica matrix of the geyserite precipitates, up to 2 wt% as Sb₂O₃. Understanding the mobility and partitioning behavior of these metalloids is critical for understanding their eventual impact on regional water management.     

50-year record and solid state speciation of mercury in natural and contaminated reservoir sediment

Contaminated fluvial sediments represent both temporary sinks for river-borne pollutants and potential sources in case of natural and/or anthropogenic resuspension. Reservoir lakes play a very important role in sediment dynamics of watersheds and may offer great opportunities to study historical records of river-borne particles and associated elements transported in the past. The fate and potential environmental impact of Hg depends on its abundance, its carrier phases and its chemical speciation. Historical Hg records and solid state Hg speciation were compared in sediments from two contrasting reservoirs of the Lot River (France) upstream and downstream from a major polymetallic pollution (e.g. Cd, Zn) source. Natural (geochemical background) and anthropogenic Hg concentrations and their relationships with predominant carrier phases were determined. The results reveal important historical Hg contamination (up to 35 mg kg⁻¹) of the downstream sediment, reflecting the historical evolution of industrial activity at the point source, i.e. former coal mining, Zn ore treatment and post-industrial remediation work. Single chemical extractions (ascorbate, H₂O₂, KOH) suggest that at both sites most (∼75%) of the Hg is bound to organic and/or reactive sulphide phases. Organo-chelated (KOH-extracted) Hg, representing an important fraction in the uncontaminated sediment, shows similar concentrations (∼0.02 mg kg⁻¹) at both sites and may be mainly attributed to natural inputs and/or processes. Although, total Hg concentrations in recent surface sediments at both sites are still very different, similar mono-methylmercury concentrations (up to 4 μg kg⁻¹) and vertical distributions were observed, suggesting comparable methylation-demethylation processes. High mono-methylmercury concentrations (4–15 μg kg⁻¹) in 10–40 a-old, sulphide-rich, contaminated sediment suggest long-term persistence of mono-methylmercury. Beyond historical records of total concentrations, the studied reservoir sediments provided new insights in solid state speciation and carrier phases of natural and anthropogenic Hg. In case of sediment resuspension, the major part of the Hg historically stored in the Lot River sediments will be accessible to biogeochemical recycling in the downstream fluvial-estuarine environment.     

Rhizosphere and flooding regime as key factors for the mobilisation of arsenic and potentially harmful metals in basic,mining-polluted salt marsh soils

The occurrence of mining areas in the vicinities of salt marshes may affect their ecological functions and facilitate the transfer of pollutants into the food chain. The mobilisation of metals in salt marsh soils is controlled by abiotic (pH, redox potential) and biotic (influence of rhizosphere) factors. The effect of the rhizosphere of two plant species (Sarcocornia fruticosa and Phragmites australis) and different flooding regimes on potentially harmful metals and As mobilisation from salt marsh soil polluted by mining activities were investigated (total concentrations: 536 mg kg⁻¹ As, 37 mg kg⁻¹ Cd, 6746 mg kg⁻¹ Pb, 15,320 mg kg⁻¹ Zn). The results show that the changes in redox conditions (from 300 mV to −100 mV) and pH after flooding and rewetting periods may mobilise the contaminant elements into soil solution (e.g., 100 μg L⁻¹ Cd, 30 μg L⁻¹ Pb, 7 mg L⁻¹ Zn), where they are available for plants or may be leached from the soil. Drying periods generated peaks of concentrations in the soil solution (up to 120 μg L⁻¹ Cd and 50 μg L⁻¹ Pb). The risk assessment of As and metal-polluted salt marshes should take into account flood dynamics in order to prevent metal(loid) mobilisation.     

Arsenic and Antimony in Groundwater Flow Systems: A Comparative Study

Arsenic (As) and antimony (Sb) concentrations and speciation were determined along flow paths in three groundwater flow systems, the Carrizo Sand aquifer in southeastern Texas, the Upper Floridan aquifer in south-central Florida, and the Aquia aquifer of coastal Maryland, and subsequently compared and contrasted. Previously reported hydrogeochemical parameters for all three aquifer were used to demonstrate how changes in oxidation–reduction conditions and solution chemistry along the flow paths in each of the aquifers affected the concentrations of As and Sb. Total Sb concentrations (Sb_T) of groundwaters from the Carrizo Sand aquifer range from 16 to 198 pmol kg⁻¹; in the Upper Floridan aquifer, Sb_T concentrations range from 8.1 to 1,462 pmol kg⁻¹; and for the Aquia aquifer, Sb_T concentrations range between 23 and 512 pmol kg⁻¹. In each aquifer, As and Sb (except for the Carrizo Sand aquifer) concentrations are highest in the regions where Fe(III) reduction predominates and lower where SO₄ reduction buffers redox conditions. Groundwater data and sequential analysis of the aquifer sediments indicate that reductive dissolution of Fe(III) oxides/oxyhydroxides and subsequent release of sorbed As and Sb are the principal mechanism by which these metalloids are mobilized. Increases in pH along the flow path in the Carrizo Sand and Aquia aquifer also likely promote desorption of As and Sb from mineral surfaces, whereas pyrite oxidation mobilizes As and Sb within oxic groundwaters from the recharge zone of the Upper Floridan aquifer. Both metalloids are subsequently removed from solution by readsorption and/or coprecipitation onto Fe(III) oxides/oxyhydroxides and mixed Fe(II)/Fe(III) oxides, clay minerals, and pyrite. Speciation modeling using measured and computed Eh values predicts that Sb(III) predominate in Carrizo Sand and Upper Floridan aquifer groundwaters, occurring as the Sb(OH)₃⁰ species in solution. In oxic groundwaters from the recharge zones of these aquifers, the speciation model suggests that Sb(V) occurs as the negatively charged Sb(OH)₆⁻ species, whereas in sufidic groundwaters from both aquifers, the thioantimonite species, HSb₂S₄ ⁻ and Sb₂S₄ ²⁻, are predicted to be important dissolved forms of Sb. The measured As and Sb speciation in the Aquia aquifer indicates that As(III) and Sb(III) predominate. Comparison of the speciation model results based on measured Eh values, and those computed with the Fe(II)/Fe(III), S(-II)/SO₄, As(III)/As(V), and Sb(III)/Sb(V) couples, to the analytically determined As and Sb speciation suggests that the Fe(II)/Fe(III), S(-II)/SO₄ couples exert more control on the in situ redox condition of these groundwaters than either metalloid redox couple.     

Comparison of arsenic geochemical evolution in the Datong Basin (Shanxi) and Hetao Basin (Inner Mongolia), China

Insightful knowledge of geochemical processes controlling As mobility is fundamental to understanding the occurrence of elevated As in groundwater. A comparative study of As geochemistry was conducted in the Datong Basin (Shanxi) and Hetao Basin (Inner Mongolia), two strongly As-enriched areas in China. The results show that As concentrations ranged from <1–1160 μg L⁻¹ (n = 37) in the Datong Basin and <1–804 μg L⁻¹ (n = 62) in the Hetao Basin. The groundwater is of the Na-HCO₃ type in the Datong Basin and Na-Cl-HCO₃ type in the Hetao Basin. Silicate mineral weathering and cation exchange processes dominated the groundwater geochemistry in the two study areas. Principal component analysis of 99 groundwater samples using 12 geochemical parameters indicated positive correlations between concentrations of As and Fe/Mn in the Datong Basin, but no correlation of As and Fe/Mn in the Hetao Basin. Phosphate correlated well with As in the Datong Basin and Hetao Basin, suggesting phosphate competition might be another process affecting As concentrations in groundwater. High concentrations of As, Fe, and Mn occurred in the pe range −2 to −4. The results of this study further understanding of the similarities and differences of As occurrence and mobility at various locations in China.     

Coordination chemistry and hydrolysis of Fe(III) in a peat humic acid studied by X-ray absorption spectroscopy

The speciation of iron (Fe) in soils, sediments and surface waters is highly dependent on chemical interactions with natural organic matter (NOM). However, the molecular structure and hydrolysis of the Fe species formed in association with NOM is still poorly described. In this study extended X-ray absorption fine structure (EXAFS) spectroscopy was used to determine the coordination chemistry and hydrolysis of Fe(III) in solution of a peat humic acid (5010-49,200 μg Fe g⁻¹ dry weight, pH 3.0-7.2). Data were analyzed by both conventional EXAFS data fitting and by wavelet transforms in order to facilitate the identification of the nature of backscattering atoms. Our results show that Fe occurs predominantly in the oxidized form as ferric ions and that the speciation varies with pH and Fe concentration. At low Fe concentrations (5010-9920 μg g⁻¹; pH 3.0-7.2) mononuclear Fe(III)-NOM complexes completely dominates the speciation. The determined bond distances for the Fe(III)-NOM complexes are similar to distances obtained for Fe(III) complexed by desferrioxamine B and oxalate indicating the formation of a five-membered chelate ring structure. At higher Fe concentrations (49,200 μg g⁻¹; pH 4.2-6.9) we detect a mixture of mononuclear Fe(III)-NOM complexes and polymeric Fe(III) (hydr)oxides with an increasing amount of Fe(III) (hydr)oxides at higher pH. However, even at pH 6.9 and a Fe concentration of 49,200 μg g⁻¹ our data indicates that a substantial amount of the total Fe (>50%) is in the form of organic complexes. Thus, in environments with significant amounts of organic matter organic Fe complexes will be of great importance for the geochemistry of Fe. Furthermore, the formation of five-membered chelate ring structures is in line with the strong complexation and limited hydrolytic polymerization of Fe(III) in our samples and also agrees with EXAFS derived structures of Fe(III) in organic soils.     

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.     

Benthic fluxes of mercury species in a lagoon environment (Grado Lagoon,Northern Adriatic Sea,Italy)

The role of the major biogeochemical processes in Hg cycling at the sediment–water interface was investigated in the Grado Lagoon (Northern Adriatic Sea). This wetland system has been extensively contaminated from the Idrija Hg Mine (Slovenia) through the Isonzo River suspended load carried by tidal fluxes. Three approaches were used to study the sediment–water exchange of total Hg (THg), methylmercury (MeHg), reactive Hg (RHg) and dissolved gaseous Hg (DGHg): (1) estimation of diffusive fluxes from porewater and overlying water concentrations, (2) measurements of benthic fluxes using a deployed light benthic chamber in situ and (3) measurements of benthic fluxes during oxic–anoxic transition with a laboratory incubation experiment. The THg solid phase, ranging between 9.5 and 14.4 μg g⁻¹, showed slight variability with depth and time. Conversely, MeHg contents were highest (up to 21.9 ng g⁻¹) at the surface; they tended to decrease to nearly zero concentration with depth, thus suggesting that MeHg production and accumulation occur predominantly just below the sediment–water interface. Porewater MeHg concentrations (0.9–7.9 ng L⁻¹, 0.15–15% of THg) varied seasonally; higher contents were observed in the warmer period. The MeHg diffusive fluxes (up to 17 ng m⁻² day⁻¹) were similar to those in the nearby Gulf of Trieste [Covelli, S., Horvat, M., Faganeli, J., Brambati, A., 1999. Porewater distribution and benthic flux of mercury and methylmercury in the Gulf of Trieste (Northern Adriatic Sea). Estuar. Coast. Shelf Sci. 48, 415–428], although the lagoon sediments contained four-fold higher THg concentrations. Conversely, the THg diffusive fluxes in the lagoon (up to 110 ng m⁻² day⁻¹) were one- to two-fold higher than those previously estimated for the Gulf of Trieste. The diurnal MeHg benthic fluxes were highest in summer at both sites (41,000 and 33,000 ng m⁻² day⁻¹ at the fishfarm and in the open lagoon, respectively), thus indicating the influence of temperature on microbial processes. The diurnal variations of dissolved THg and especially MeHg were positively correlated with O₂ and inversely with DIC, suggesting an important influence of benthic photosynthetic activities on lagoon benthic Hg cycling, possibly through the production of organic matter promptly available for methylation. The results from the dark chamber incubated in the laboratory showed that the regeneration of dissolved THg was slightly affected by the oxic–anoxic transition. Conversely, the benthic flux of MeHg was up to 15-fold higher in sediments overlain by O₂ depleted waters. In the anoxic phase, the MeHg fluxes proceeded in parallel with Fe fluxes and the methylated form reached approximately 100% of dissolved THg. The MeHg is mostly released into overlying water (mean recycling efficiency of 89%) until the occurrence of sulphide inhibition, due to scavenging of the available Hg substrate for methylation. The results suggest that sediments in the Grado Lagoon, especially during anoxic events, should be considered as a primary source of MeHg for the water column.     

Rare earth elements (REE) and yttrium in stream waters, stream sediments, and Fe-Mn oxyhydroxides: Fractionation, speciation, and controls over REE + Y patterns in the surface environment

We have collected ∼500 stream waters and associated bed-load sediments over an ∼400 km² region of Eastern Canada and analyzed these samples for Fe, Mn, and the rare earth elements (REE + Y). In addition to analyzing the stream sediments by total digestion (multi-acid dissolution with metaborate fusion), we also leached the sediments with 0.25 M hydroxylamine hydrochloride (in 0.05 M HCl), to determine the REE + Y associated with amorphous Fe- and Mn-oxyhydroxide phases. We are thus able to partition the REE into “dissolved” (<0.45 μm), labile (hydroxylamine) and detrital sediment fractions to investigate REE fractionation, and in particular, with respect to the development of Ce and Eu anomalies in oxygenated surface environments. Surface waters are typically LREE depleted ([La/Sm]_NASC ranges from 0.16 to 5.84, average = 0.604, n = 410; where the REE are normalized to the North America Shale Composite), have strongly negative Ce anomalies ([Ce/Ce^∗]_NASC ranges from 0.02 to 1.25, average = 0.277, n = 354), and commonly have positive Eu anomalies ([Eu/Eu^∗]_NASC ranges from 0.295 to 1.77, average = 0.764, n = 84). In contrast, the total sediment have flatter REE + Y patterns relative to NASC ([La/Sm]_NASC ranges from 0.352 to 1.12, average = 0.778, n = 451) and are slightly middle REE enriched ([Gd/Yb]_NASC ranges from 0.55 to 3.75, average = 1.42). Most total sediments have negative Ce and Eu anomalies ([Ce/Ce^∗]_NASC ranges from 0.097 to 2.12, average = 0.799 and [Eu/Eu^∗]_NASC ranges from 0.39 to 1.43, average = 0.802). The partial extraction sediments are commonly less LREE depleted than the total sediments ([La/Sm]_NASC ranges from 0.24 to 3.31, average = 0.901, n = 4537), more MREE enriched ([Gd/Yb]_NASC ranges from 0.765 to 6.28, average = 1.97) and Ce and Eu anomalies (negative and positive) are more pronounced.The partial extraction recovered, on average ∼20% of the Fe in the total sediment, ∼80% of the Mn, and 21-29% of the REEs (Ce = 19% and Y = 32%). Comparison between REEs in water, partial extraction and total sediment analyses indicates that REEs + Y in the stream sediments have two primary sources, the host lithologies (i.e., mechanical dispersion) and hydromorphically transported (the labile fraction). Furthermore, Eu appears to be more mobile than the other REE, whereas Ce is preferentially removed from solution and accumulates in the stream sediments in a less labile form than the other REEs + Y. Despite poor statistical correlations between the REEs + Y and Mn in either the total sediment or partial extractions, based on apparent distribution coefficients and the pH of the stream waters, we suggest that either sediment organic matter and/or possibly δ-MnO₂/FeOOH are likely the predominant sinks for Ce, and to a lesser extent the other REE, in the stream sediments.     

Arsenic in groundwater from mineralised Proterozoic basement rocks of Burkina Faso

This study describes the hydrogeochemistry and distributions of As in groundwater from a newly investigated area of Burkina Faso. Groundwaters have been sampled from hand-pumped boreholes and dug wells close to the town of Ouahigouya in northern Burkina Faso. Although most analysed groundwaters have As concentrations of less than 10 μg L⁻¹, they have a large range from <0.5 to 1630 μg L⁻¹. The highest concentrations are found in borehole waters; all dug wells analysed in this study have As concentrations of <10 μg L⁻¹. Skin disorders (melanosis, keratosis and more rare skin tumour) have been identified among the populations in three villages in northern Burkina Faso, two within the study area. Although detailed epidemiological studies have not been carried out, similarities with documented symptoms in other parts of the world suggest that these are likely to be linked to high concentrations of As in drinking water. The high-As groundwaters observed derive from zones of Au mineralisation in Birimian (Lower Proterozoic) volcano-sedimentary rocks, the Au occurring in vein structures along with quartz and altered sulphide minerals (pyrite, chalcopyrite, arsenopyrite). However, the spatial variability in As concentrations in the mineralised zones is large and the degree of testing both laterally and with depth so far is limited. Hence, concentrations are difficult to predict on a local scale. From available data, the groundwater appears to be mainly oxic and the dissolved As occurs almost entirely as As(V) although concentrations are highest in groundwaters with dissolved-O₂ concentrations <2 mg L⁻¹. The source is likely to be the oxidised sulphide minerals and secondary Fe oxides in the mineralised zones. Positive correlations are observed between dissolved As and both Mo and W which are also believed to be derived from ore minerals and oxides in the mineralised zones. The discovery of high As concentrations in some groundwaters from the Birimian rocks of northern Burkina Faso reiterates the need for reconnaissance surveys in mineralised areas of crystalline basement.     

Particulate air pollution in a small settlement: The effect of local heating

Mass concentrations of PM₁₀, PM_2.5, and black smoke (BS) were measured in April 2003 during a 3-week campaign in a small village and at a nearby background location in the central part of the Czech Republic. In a pilot analysis, concentrations of selected trace elements (Al, Ti, V, Cr, Mn, Co, Ni, Cu, Zn, As, Se, Sr, Cd, Sb, Cs, Pb) in the collected aerosol were determined by means of ICP-MS. Average concentrations of both PM fractions and BS were higher in the village (37, 26 and 26 μg m⁻³) than at the background location (26, 19 and 11 μg m⁻³) for PM₁₀, PM_2.5 and BS, respectively. Both PM₁₀ and PM_2.5 were reasonably correlated in the village (r = 0.80) and also at the background location (r = 0.79). Correlation between same fractions from the village and from the background site were even higher (r = 0.97 and r = 0.95 for the PM₁₀ and PM_2.5, respectively) suggesting that most of the aerosol in both locations may be influenced by similar sources. The ratio between PM₁₀ and PM_2.5 showed that sources in the village contributed about 33% and 35% to local aerosol concentration for PM₁₀ and PM_2.5, respectively. When the data from the two rural locations were compared with corresponding 24-h averages of PM₁₀ concentrations obtained for the period of the campaign from fixed site monitors situated near larger towns, the highest concentration was found in Prague the Czech capital (49 μg m⁻³) followed by a district town Beroun (41 μg m⁻³) and the village (37 μg m⁻³). The lowest PM₁₀ concentration was found in the village background (26 μg m⁻³). Elemental analysis revealed higher concentrations for most of the elements characteristic of combustion aerosol (namely Zn, Pb, As, Mn and Ti) in the PM collected in the village. The results support the idea that traditional heating in villages may contribute a great extent to local air pollution and may represent an important problem.     

Organic matter compositions and DOM release from the sediments of the shallow lakes in the middle and lower reaches of Yangtze River region, China

The contents of different organic matter components and dissolved organic matter (DOM) release kinetics of the sediments from the middle and lower reaches of the Yangtze River region were investigated, and their relationships discussed. The results show that organic C (OC) ranged from 8.14 to 43.65 g kg⁻¹, dissolved organic C (DOC) from 0.38 to 1.38 g kg⁻¹, active organic C (AOC) from 1.12 to 4.45 g kg⁻¹, heavy fraction organic C (HFOC) from 6.86 to 39.08 g kg⁻¹, accounting for 2.42-9.34%, 8.66-29.72% and 84.29-93.18% of OC, respectively. With increasing of OC content the ratios of DOC to OC and AOC to OC decreased. The contents of AOC, DOC, light fraction organic C (LFOC) and their contribution ratios to OC in studied sediments were higher than those reported in soils. The DOM release process of the studied sediments includes rapid and slow stages, and the rapid release occurred within 30 min, mainly in 5 min. The DOM release kinetic data in this investigation can be best fitted by the Power Function model. The correlations between total N (TN), total P (TP), OC, DOC, AOC, LFOC, HFOC and the DOM release kinetic parameters (k, c, a, b, rate₃₀) of the sediments were significant. There were also significant correlations between TN, TP, OC, DOC, LFOC and HFOC in sediments. So the DOM release from sediment was not only related to the OC content, but also related to the organic matter composition characteristics, especially the contents of DOC, AOC and LFOC.     

Transportation and evolution of trace element bearing phases in stream sediments in a mining – Influenced basin (Upper Isle River,France)

Arsenic-bearing stream sediments enter the Upper Isle River, an Au mining-influenced basin (France), by the discharge of mining sites, tailings runoff and weathering of mineralized veins in granites and gneiss. Some fresh ochreous As-rich deposits on the river banks and in floodplains are identified as additional As-rich point sources (As between 0.07 and 6.5 wt.%). The <63 μm fraction of stream sediments contains elevated As bulk concentrations, ranging from 160 to 890 mg/kg, compared to the geochemical background (70 mg/kg on average). It is also enriched in Cd, Hg and W. Spatial variations of these trace elements show 3 significant increases corresponding to the 3 drained mining districts. They decrease down river but are still enriched 30 km downstream of the mining districts due to downstream transportation. Three types of trace element-bearing phases have been identified as: (i) detrital primary sulfides, with high in situ As percentages (up to 43.7 wt.%). They also carry significant amounts of W according to the differences in chemical compositions of the total and light <63 μm fractions. These sulfide particles do not show any sign of alteration in the oxygenated stream sediments; (ii) Secondary Fe–Mn oxyhydroxides,some with very high in situ As₂O₅ concentrations (up to 59.8 wt.%) and with about 40% of the total Cd composition. They occur as fresh precipitates in the river banks and floodplains and as discrete particles in stream sediments and (iii) Al–Si fine-grained phases. Their major element composition is highly variable with in situ As₂O₅ concentrations ranging between 430 and 5020 mg/kg. This type of solid phase is also the major carrier of Hg.