Seasonality of diel cycles of dissolved trace-metal concentrations in a Rocky Mountain stream

Substantial diel (24-h) cycles in dissolved (0.1-m filtration) metal concentrations were observed during summer low flow, winter low flow, and snowmelt runoff in Prickly Pear Creek, Montana. During seven diel sampling episodes lasting 34–61.5 h, dissolved Mn and Zn concentrations increased from afternoon minimum values to maximum values shortly after sunrise. Dissolved As concentrations exhibited the inverse timing. The magnitude of diel concentration increases varied in the range 17–152% for Mn and 70–500% for Zn. Diel increases of As concentrations (17–55%) were less variable. The timing of minimum and maximum values of diel streamflow cycles was inconsistent among sampling episodes and had little relation to the timing of metal concentration cycles, suggesting that geochemical rather than hydrological processes are the primary control of diel metal cycles. Diel cycles of dissolved metal concentrations should be assumed to occur at any time of year in any stream with dissolved metals and neutral to alkaline pH.Electronic Supplementary Material Supplementary material is available for this article if you access the article at . A link in the frame on the left on that page takes you directly to the supplementary material.     

Dissolved and particulate trace metals and their partitioning in a hypoxic estuary: The Tanshui Estuary in Northern Taiwan

The distribution and partitioning of trace metals (Co, Cu, Fe, Mn, Ni, and Zn) between dissolved and particulate phases were studied in the Tanshui Estuary. The upper reach of the estuary is hypoxic and heavily polluted due to domestic and industrial discharges. The concentration ranges of dissolved and leachable particulate trace metals in the Tanshui Estuary were: Co: 0.3–6.1 nM, 1.8–18.6 mg kg⁻¹; Cu: 5–53 nM, 22–500 mg kg⁻¹; Fe: 388–3,364 nM, 1.08–6.67%; Mn: 57–2,914 nM, 209–1,169 mg kg⁻¹; Ni: 7–310 nM, 6–108 mg kg⁻¹; and Zn: 12–176 nM, 62–1,316 mg kg⁻¹; respectively. The dissolved concentrations of the metals were 2–35 times higher than the average values of the world river water. The distributions of dissolved and particulate studied metals, except Mn, in the estuary showed scattering, which could be attributed to the discharges from many industrial wastewater disposal works located in the upper tributaries. The daily input of dissolved metals from the disposal works to the Tanshui Estuary ranged from 0.1–0.4 tons. Dissolved Mn was nearly conservative in the region with salinity higher than 10 psu, while particulate Mn decreased in the region with salinity of 10–15 psu. The concentration increased significantly seawards, corresponding with the distribution of dissolved oxygen. The distribution coefficient (K_D) for Mn in the lower estuary was nearly three orders of magnitude higher than in the upper estuary. This phenomenon may be attributed to the diffusion of Mn from the anoxic sediment in the upper estuary and gradual oxidation into particulate Mn in the middle and lower estuary as the estuarine water became more oxygenated. The distribution coefficient for Cu decreased with increasing salinity. The percentages of trace metals bound by suspended particulate matter decreased in the following order: Fe>Zn, Cu>Co>Mn>Ni.     

Heavy meals in urban roadside soils, part 1: effect of particle size fractions on heavy metals partitioning

Urban roadside soils are important environmental media for assessing heavy metal concentrations in urban environment. However, among other things, heavy metal concentrations are controlled by soil particle grain size fractions. In this study, two roadside sites were chosen within the city of Xuzhou (China) to reflect differences in land use. Bulk soil samples were collected and then divided by particle diameter into five physical size fractions, 500–250, 250–125, 125–74, 74–45, < 45 μm. Concentrations of metals (Ti, Cr, Al, Ga, Pb, Ba, Cd, Co, Cu, Mn, Ni, V, Zn, Mo, As, Sb, Se, Hg, Bi, Ag) were determined for each individual fraction. These metals could be roughly classified into two groups: anthropogenic element (Pb, Ba, Cd, Cu, Zn, Mo, As, Sb, Se, Hg, Bi, Ag) and lithophile element (Ti, Cr, Al, Ga, Co, Mn, Ni, V) in terms of values of enrichment factor. As expected, higher concentrations of anthropogenic heavy metals (Cu, Zn, Mo, As, Hg, Bi, Ag) are observed in the finest particle grain size fraction (i.e. < 45 μm). However, heavy metals Se, Sb and Ba behave independently of selected grain size fractions. From the viewpoint of mass loading, more than 30% of the concentrations for all anthropogenic heavy metals are contributed by the particle grain size fractions of 45–74 μm at site 1 and more than 70% of the concentrations for all heavy metals are contributed by the particle grain size fractions of 45–74 and 74–125 μm at site 2. These results are important for transport of soil-bound heavy metals and pollution control by various remedial options.     

Arsenic in mine waters: an international study

 Hydrochemical data are presented for arsenic (As) in the mine waters of 34 gold and base-metal mining localities in seven countries of south-east Asia, Africa and Latin America, encompassing contrasting climatic settings and at least eight discrete styles of primary mineralization. Peak dissolved As concentrations at these sites range from 0.005–72 mg/l, with the United States Environmental Protection Agency (US-EPA) potable water threshold of 50 μg/l exceeded in 25 cases. Arsenate (As⁵⁺) constitutes the dominant species at over 80% of sites. Very high dissolved As concentrations (>1 mg/l) show no systematic between-site relationship with mine water pH/Eh regime. Important determinants of mine water As fluxes include iron hydrochemistry, the presence of cyanic ore processing effluents, site geology, the paragenetic sequence that follows sulphide oxidation, climate and mine management. Human toxicological impacts of As contamination have been recognized at only one case-study site, with a further four considered to warrant more detailed risk assessment. Received: 2 November 1999 · Accepted: 21 March 2000     

Arsenic, antimony and other toxic elements in the drinking water of Eastern Thessaly in Greece and its possible effects on human health

Twenty-six groundwater samples were collected from the Eastern Thessaly region and analysed by ICP-ES for these elements: Al, As, P, Pb, Zn, Mn, Fe, Cr, Sb, Cu, Na, Br, Cl, Si, Mg, Ag, Be, Bi, Dy, Er, Eu, Au, Ge, Ho, In, Ir, Os, Pt, Re, Rh, Ru, Lu, Hf, Hg, Tm, Zr and Nb. The objectives of the study were to assess the level of water contamination with respect to the EC and the USEPA health-based drinking water criteria. The geology of the studied area includes schists, amphibolites, marbles of Palaeozoic age, ophiolites, limestones of Triassic and Cretaceous age, Neogene and Quaternary deposits. The element ranges for groundwater samples are: Al 7–56 μg l⁻¹, As 1–125 μg l⁻¹, Br 6–60 μg l⁻¹, Cl 500–25,000 μg l⁻¹, Cr 1–6 μg l⁻¹, Cu 1–15 μg l⁻¹, Fe 10–352 μg l⁻¹, Mg 2,940–40,100 μg l⁻¹, Mn 0–8 μg l⁻¹, Na 3,650–13,740 μg l⁻¹, P 20–48 μg l⁻¹, Pb 0–7 μg l⁻¹, Sb 0–21 μg l⁻¹, Si 3,310–13,240 μg l⁻¹ and Zn 7–994 μg l⁻¹. The results of groundwater analyses from the region of Eastern Thessaly showed elevated concentrations of As and Sb. Factor analysis explained 77.8% of the total variance of the data through five factors. Concentration of Br, Cl, Mg, Na and Si is directly related to the presence of saltwater in the aquifer, so grouping of these variables in factor 1 probably reflects the seawater intrusion. Al, As and Sb are known to form complexes in the environment, so grouping of these elements in factor 2 indicates their similar geochemical behaviour in the environment. The high negative loading of Mn in factor 2 indicates the presence of manganese oxides–hydroxides in the study area. Pb and Zn are associated together in sulphide mineralisation; so grouping of these elements in factor 3 reflects the sulphide mineralization paragenesis in the Melivoia area. P and Cu are associated together in phosphate fertilizers; so grouping of these variables in factor 4 could be related to agricultural practices. Cr, Fe, Mn and Mg are associated together in iron and manganese oxides–hydroxides and the weathering products of the olivine of the ultrabasic rocks; so grouping of these elements in factor 5 reflects the lithology of the area. There is a natural contamination of groundwaters with elevated concentrations of As and Sb due to the presence of the arsenopyrite and stibnite mineralisation in the Melivoia, Sotiritsa and Ano Polydendri areas. Contamination over the health-based drinking water guidelines given by EC and EPA has been investigated from nine sampling sites out of 26 of Eastern Thessaly region.     

Hydrological and geochemical control of metals and arsenic in a Mediterranean river contaminated by acid mine drainage (the Amous River,France); preliminary assessment of impacts on fish (Leuciscus cephalus)

Dissolved and particulate concentrations of metals (Fe, Al, Mn, Co, Ni, Cu, Zn, Cd, Tl, Pb) and As were monitored over a 5 year period in the Amous River downstream of its confluence with a creek severely affected by acid mine drainage (AMD) originating from a former Pb–Zn mine. Water pH ranged from 6.5 to 8.8. Metals were predominantly in dissolved form, except Fe and Pb, which were in particulate form. In the particulate phase, metals were generally associated with Al oxides, whereas As was linked to Fe oxides. Metal concentrations in the dissolved and/or particulate phase were generally higher during the wet season due to higher generation of AMD. Average dissolved (size < 0.22 μm) metal concentrations (μg/L) were 1 ± 4 (Fe), 69 ± 49 (Al), 140 ± 118 (Mn), 4 ± 3 Co, 6 ± 4 (Ni), 1.3 ± 0.8 (Cu), 126 ± 81 (Zn), 1.1 ± 0.7 (Cd), 0.9 ± 0.5 (Tl), 2 ± 3 (Pb). Dissolved As concentrations ranged from 5 to 134 μg/L (30 ± 23 μg/L). During the survey, the concentration of colloidal metals (5 kDa < size < 0.22 μm) was less than 25% of dissolved concentrations. Dissolved metal concentrations were generally higher than the maximum concentrations allowed in European surface waters for priority substances (Ni, Cd and Pb) and higher than the environmental quality standards for other compounds. Using Diffusion Gradient in Thin Film (DGT) probes, metals were shown to be in potentially bioavailable form. The concentrations in Leuciscus cephalus were below the maximum Pb and Cd concentrations allowed in fish muscle for human consumption by the European Water Directive. Amongst the elements studied, only As, Pb and Tl were shown to bioaccumulate in liver tissue (As, Pb) or otoliths (Tl). Bioaccumulation of metals or As was not detected in muscle.     

Transport and sediment–water partitioning of trace metals in acid mine drainage: an example from the abandoned Kwangyang Au–Ag mine area, South Korea

Transport and sediment–water partitioning of trace metals (Cr, Co, Fe, Pb, Cu, Ni, Zn, Cd) in acid mine drainage were studied in two creeks in the Kwangyang Au–Ag mine area, southern part of Korea. Chemical analysis of stream waters and the weak acid (0.1 N HCl) extraction, strong acid (HF–HNO₃–HClO₄) extraction, and sequential extraction of stream sediments were performed. Heavy metal pollution of sediments was higher in Chonam-ri creek than in Sagok-ri creek, because there is a larger source of base metal sulfides in the ores and waste dump upstream of Chonam-ri creek. The sediment–water distribution coefficients (K _d) for metals in both creeks were dependent on the water pH and decreased in the order Pb ≈ Al > Cu > Mn > Zn > Co > Ni ≈ Cd. K _d values for Al, Cu and Zn were very sensitive to changes in pH. The results of sequential extraction indicated that among non-residual fractions, Fe–Mn oxides are most important for retaining trace metals in the sediments. Therefore, the precipitation of Fe(–Mn) oxides due to pH increase in downstream sites plays an important role in regulating the concentrations of dissolved trace metals in both creeks. For Al, Co, Cu, Mn, Pb and Zn, the metal concentrations determined by 0.1 N HCl extraction (Korean Standard Method for Soil Pollution) were almost identical to the cumulative concentrations determined for the first three weakly-bound fractions (exchangeable + bound to carbonates + bound to Fe–Mn oxides) in the sequential extraction procedure. This suggests that 0.1 N HCl extraction can be effectively used to assess the environmentally available and/or bioavailable forms of trace metals in natural stream sediments.     

Environmental geochemistry of high arsenic groundwater at western Hetao plain, Inner Mongolia

Environmental geochemistry of high arsenic groundwater at Hetao plain was studied on the basis of geochemical survey of the groundwater and a core sediment. Arsenic concentration in groundwater samples varies from 76 to 1093 μg/L. The high arsenic groundwater mostly appears to be weakly alkaline. The concentrations of NO₃⁻ and SO₄²⁻ are relatively low, while the concentrations of DOC, NH₄⁺, dissolved Fe and sulfide are relatively great. Analysis of arsenic speciation in 21 samples shows that arsenic is present in the solution predominantly as As(III), while particulate arsenic constitutes about 10% of the total arsenic. Methane is detected in five samples with the greatest content being 5107 μg/L. The shallow aquifer in Hangjinhouqi of western Hetao plain is of strongly reducing condition. The arsenic content in 23 core sediment samples varies from 7.7 to 34.6 mg/kg, with great value in clay and mild clay layer. The obvious positive relationship in content between Fe₂O₃, Mn, Sb, B, V and As indicates that the distribution of arsenic in the sediments may be related to Fe and Mn oxides, and the mobilization of Sb, B and V may be affected by similar geochemical processes as that of As.     

Arsenic mobility in fluvial environment of the Ganga Plain,northern India

In the northern part of the Indian sub-continent, the Gomati River (a tributary of the Ganga River) was selected to study the dynamics of Arsenic (As) mobilization in fluvial environment of the Ganga Plain. It is a 900-km-long, groundwater-fed, low-gradient, alluvial river characterized by monsoon-controlled peaked discharge. Thirty-six water samples were collected from the river and its tributaries at low discharge during winter and summer seasons and were analysed by ICP-MS. Dissolved As and Fe concentrations were found in the range of 1.29–9.62 and 47.84–431.92 μg/L, respectively. Arsenic concentration in the Gomati River water has been detected higher than in its tributaries water and characteristically increases in downstream, attributed to the downstream increasing of Fe₂O₃ content, sedimentary organic carbon and silt-clay content in the river sediments. Significant correlation of determination (r ² = 0.68) was also observed between As and Fe concentrations in the river water. Arsenic concentrations in the river water are likely to follow the seasonal temperature variation and reach the level of World Health Organization’s permissible limit (10 μg/L) for drinking water in summer season. The Gomati River longitudinally develops reducing conditions after the monsoon season that mobilize As into the river water. First, dissolved As enters into pore-water of the river bed sediments by the reductive dissolution of Fe-oxides/hydroxides due to microbial degradation of sedimentary organic matter. Thereafter, it moves upward as well as down slope into the river water column. Anthropogenically induced biogeochemical processes and tropical climatic condition have been considered the responsible factors that favour the release of As in the fluvial environment of the Ganga Plain. The present study can be considered as an environmental alarm for future as groundwater resources of the Ganga–Brahmaputra Delta are seriously affecting the human–environment relationship at present.     

Seasonal variations of Zn, Cu, As and Mo in arsenic-rich stream at the Mokrsko gold deposit, Czech Republic

Monthly sampling of slightly alkaline arsenic-rich stream in the Mokrsko gold deposit revealed seasonal variations in dissolved Zn, Cu, As and Mo. Concentrations of trace metal cations (Zn, Cu) increased as much as 330 and 178%, respectively, from minimum mean values at autumn to maximum mean values at spring. In contrast, concentrations of trace element oxyanions (As, Mo) revealed opposite seasonal pattern with increase to 189% (As) and 123% (Mo) during summer–autumn, indicating that in-stream biogeochemical process(es) played the main role in controlling the seasonal variations of these trace elements. The trace elements were mainly scavenged by low crystalline Mn oxyhydroxide and Fe oxyhydroxide (ferrihydrite). Results are consistent with sorption and coprecipitation processes controlling seasonal variations of dissolved Zn and Cu, while As and Mo dynamics appear linked to Mn redox reactions. The sorption processes and Mn redox processes are attributed to the changes of pH and oxic/anoxic conditions on the surface of oxyhydroxides, respectively, which are themselves controlled by the balance between photosynthesis and respiration. Under the geochemical conditions of the stream, inferred Mn redox reactions can only be explained by microbial activity.     

Particulate Thiol Peptides Along a Salinity Gradient of a Metal-Contaminated Estuary

The thiol peptide phytochelatins (PC2; the polymer with n = 2) are efficient metal-chelating compounds produced by phytoplankton and higher plants. Both PC2 and their precursor glutathione (GSH) are related to detoxification mechanisms. GSH and PC2 were quantified using liquid chromatography with fluorescent detection and observed in the particulate phase along a salinity gradient of the Tamar Estuary (SW UK), a heavily metal impacted site, at concentrations up to 274 and 16.5 μmol (g chl a)⁻¹, respectively. The peptides predominated within low (0–5) and mid-salinities (5–20). Down-estuary, at sites farther from metal sources and salinities higher than 20, PC2 showed a sharp decrease or were not detected. High PC2/GSH ratios indicated areas with augmented concentrations of bioavailable metals at the tidal limit, near Cu mines and the mid-estuary where resuspension of sediments occurs. By following typical partitioning patterns previously reported for dissolved Cu and Zn, the production of thiol peptides, notably PC2, reflected a rapid interaction between the particulate and dissolved phases.     

Geochemical study of arsenic and other trace elements in groundwater and sediments of the Old Brahmaputra River Plain,Bangladesh

The geochemical study of groundwaters and core sediments from the Old Brahmaputra plain of Bangladesh was conducted to investigate the distribution of arsenic and related trace elements. Groundwaters from tube wells are characterized by pH of 6.4–7.4, dissolved oxygen (DO) of 0.8–1.8 mg/l, Ca contents of 5–50 mg/l, and Fe contents of 0.2–12.9 mg/l. Arsenic concentrations ranged from 8 to 251 μg/l, with an average value of 63 μg/l. A strong positive correlation exists between As and Fe (r ² = 0.802; p = 0.001) concentrations in groundwater. The stratigraphic sequences in the cores consist of yellowish silty clays at top, passing downward into grayish to yellowish clays and sands. The uppermost 3 m and lower parts (from 13 to 31 m) of the core sediments are oxidized (average oxidation reduction potential (ORP) +170 and +220 mV, respectively), and the ORP values gradually become negative from 3 to 13 m depths (−35 to −180 mV), indicating that anoxic conditions prevail in the shallow aquifers of the Brahmaputra plain. Age determinations suggest that clay horizons at ~10 m depth were deposited at around 2,000 and 5,000 years BP (¹⁴C ages) during the transgressive phase of sea-level change. Elevated concentrations of As, Pb, Zn, Cu, Ni, Cr, and V are present in the silts and clays, probably due to adsorption onto clay particles. Significant concentrations of As occur in black peat and peaty sediments at depths between 9 and 13 m. A strong positive correlation between As and Fe was found in the sediments, indicating As may be adsorbed onto Fe oxides in aquifer sediments.     

Relationships Between Geochemical Parameters (pH, DOC, SPM, EDTA Concentrations) and Trace Metal (Cd, Co, Cu, Fe, Mn, Ni, Pb, Zn) Concentrations in River Waters of Texas (USA)

Water samples from eight major Texas rivers were collected at different times during 1997–1998 to determine the dissolved and particulate trace metal concentrations, expected to show differences in climate patterns, river discharge and other hydrochemical conditions, and human activities along the different rivers. Specifically, two eastern Texas rivers (Sabine, Neches) lie in a region with high vegetation, flat topography, and high rainfall rates, while four Central Texas rivers (Trinity, Brazos, Colorado, and San Antonio) flow through large population centers. Relatively high dissolved organic carbon (DOC) concentrations in the eastern Texas rivers and lower pH led to higher Fe and Mn concentrations in river waters. The rivers that flow through large population centers showed elevated trace metal (e.g., Cd, Pb, Zn) concentrations partly due to anthropogenically produced organic ligands such as ethylenediaminetetraacetic acid (EDTA) present in these rivers. Trace metal levels were reduced below dams/reservoirs along several Texas rivers. Statistical analysis revealed four major factors (suspended particulate matter [SPM], EDTA, pH, and DOC) that can explain most of the observed variability of trace metal concentrations in these rivers. SPM concentrations directly controlled particulate metal contents. Variation in pH correlated with changes of dissolved Co, Fe, Mn, and Ni, and particulate Mn concentrations, while DOC concentrations were significantly related to dissolved Fe concentrations. Most importantly, it was found that, more than pH, EDTA concentrations exerted a major control on dissolved concentrations of Cd and Zn, and, to a lesser extent, Cu, Ni, and Pb.     

Metal contamination of the environment by placer and primary gold mining in the Adola region of southern Ethiopia

Primary and placer gold mining sites in southern Ethiopia were studied to see the contribution of mining to the accumulation of metals in different environmental media. Sediment, water and plant samples were analyzed for Al, Mn, Fe, As, Ni, Cr, Cu, Co, Pb, W, Sb, Mo, Zn and V. Water parameters (pH, Eh, TDS, anions and cations) were also measured. The sediment analyses results show that the most abundant metals are Ni (average 224.7 mg/kg), Cr (199 mg/kg), Cu (174.2 mg/kg), V (167.3 mg/kg), Zn (105.5 mg/kg), Pb (61.5 mg/kg) and As (59.7 mg/kg) in the primary gold mining sites while the placer sites show high concentration of V (average 301.2 mg/kg), Cr (260.4 mg/kg), Zn (179 mg/kg), Ni (113.4 mg/kg), Cu (46.7 mg/kg), As (32.2 mg/kg) and Co (31 mg/kg). The metals Cu, Ni, W, Cr, As and Pb in primary and Sb, W, Cr, Ni, Zn, As and Mo in placer gold mining sites have geoaccumulation indexes (I _geo) from one to four indicating considerable accumulation of these metals. Waters from both primary and placer mining sites are near neutral to alkaline. Arsenic (average 92.8 μg/l), Ni (276.6 μg/l), Pb (18.7 μg/l), Sb (10.7 μg/l), Mn (1 mg/l), Fe (8.3 mg/l) and Al (23.8 mg/l) exceeded the guideline value for drinking water. Plants show high concentration of Cr (average 174.5 mg/kg), Ni (163.5 mg/kg), Zn (96 mg/kg) and W (48 mg/kg). Zinc, W, Mo, Ni and Cr show the maximum biological absorption coefficient (BAC) ranging 0.4–1.7, 0.1–104.6, 1.1–2.6, 0.2–1.6 and 0.2–3.6, respectively, and the results suggest bioaccumulation of these elements in plants. The minerals especially sulfides in the ore aggregate are the ultimate source of the metals. The release of the metals into the environmental media is facilitated (in addition to normal geologic processes) by human activities related to gold mining.     

Magnitudes, spatial scales and processes of environmental antimony mobility from orogenic gold–antimony mineral deposits, Australasia

Antimony (Sb) is strongly concentrated into hydrothermal mineral deposits, commonly with gold, in metasedimentary sequences around the Pacific Rim. These deposits represent potential point sources for Sb in the downstream environment, particularly when mines are developed. This study documents the magnitude and scale of Sb mobility near some mineral deposits in Australia and New Zealand. Two examples of New Zealand historic mining areas demonstrate that natural groundwater dissolution of Sb from mineral deposits dominates the Sb load in drainage waters, with Sb concentrations between 3 and 24 μg/L in major streams. Mine-related discharges can exceed 200 μg/L Sb, but volumes are small. Sb flux in principal stream waters is ca 1–14 mg/s, compared to mine tunnel fluxes of ca 0.001 mg/s. Dissolved Sb is strongly attenuated near some mine tunnels by adsorption on to iron oxyhydroxide precipitates. Similar Sb mobilisation and attenuation processes are occurring downstream of the historic/active Hillgrove antimony–gold mine of New South Wales, Australia, but historic discharges of Sb-bearing debris has resulted in elevated Sb levels in stream sediments (ca 10–100⁺ mg/kg) and riparian plants (up to 100 mg/kg) for ca 300 km downstream. Dissolution of Sb from these sediments ensures that river waters have elevated Sb (ca 10–1,000 μg/L) over that distance. Total Sb flux reaching the Pacific Ocean from the Hillgrove area is ca 8 tonnes/year, of which 7 tonnes/year is particulate and 1 tonne/year is dissolved.     

The hydrogeochemistry of a heavily used aquifer in the Mexican wine-producing Guadalupe Valley, Baja California

The Guadalupe Valley aquifer is the only water source for one of the most important wine industries in Mexico, and also the main public water supply for the nearby city of Ensenada. This groundwater is monitored for major ion, N-NO₃, P-PO₄, Fe, As, Se, Mo, Cd, Cu, Pb, Zn and Sb concentrations, as well as TDS, pH, dissolved oxygen and temperature. High concentrations of N-NO₃ (26 mg l⁻¹), Se (70 μg l⁻¹), Mo (18 μg l⁻¹) and Cu (4.3 μg l⁻¹) suggest that groundwater is being polluted by the use of fertilizers only in the western section of the aquifer, known as El Porvenir graben. Unlike the sites located near the main recharge area to the East of the aquifer, the water in El Porvenir graben has low tritium concentrations (<1.9 TU), indicating a pre-modern age, and thus longer water residence time. No significant variations in water quality (generally <10%) were detected throughout 2001–2002 in the aquifer, suggesting that reduced rainfall and recharge during this dry period did not significantly affect water quality. However, the wells nearest to the main recharge area in the Eastern aquifer show a slight but constant increase in TDS with time, probably as a result of the high (∼200 L S⁻¹) uninterrupted extraction of water at this specific recharge site. Relatively high As concentrations for the aquifer (10.5 μg l⁻¹) are only found near the northern limit of the basin associated with a geological fault.     

Determination of Free Cd,Cu and Zn Concentrations in Lake Waters by In Situ Diffusion Followed by Column Equilibration Ion-exchange

Combining in situ diffusion and column ion-exchange equilibration, we measured free metal ion concentrations (Cd, Cu and Zn) in water samples collected from the epilimnion of 14 lakes in the Rouyn-Noranda area (600 km north-west of Montreal, QC, Canada). Lakes were selected to represent a wide range of physico-chemical characteristics (hardness, pH, dissolved organic matter—DOM, degree of metal contamination), to determine the influence of these parameters on metal speciation. Total dissolved metal concentrations, as determined within the diffusion cells, varied over one to two orders of magnitude: [Cd] 0.19–2.9 nM; [Cu] 36–190 nM; [Zn] 7–2,800 nM. The proportion of total dissolved metal present as free Cd²⁺ and Zn²⁺ was relatively constant for the 14 selected lakes, despite the wide pH (4.5–8) and DOM (3–23 mg C/L) ranges, probably reflecting the inverse relationship observed between pH and DOM; this proportion did, however, vary with DOM and pH for Cu. Our experimental free metal ion concentrations were compared with those calculated with the thermodynamic models WHAM (Windermere Humic Aqueous Model VI) and ECOSAT 4.7 (incorporating the NICA-Donnan model). Measured and calculated values were in reasonable agreement for both Cd and Zn although measured values were generally slightly higher, i.e. less than one order of magnitude. For several lakes, measured free Cu concentrations were, however, much higher than the calculated values, suggesting that these models overestimate Cu complexation. The gap between measured and calculated free metal ion concentration becomes more important as the total metal concentration decreases and as pH increases.     

Heavy metal contamination of coastal lagoon sediments by anthropogenic activities: the case of Nador (East Morocco)

Nador lagoon sediments (East Morocco) are contaminated by industrial iron mine tailings, urban dumps and untreated wastewaters from surrounding cities. The lagoon is an ecosystem of biological, scientific and socio-economic interests but its balance is threatened by pollution already marked by biodiversity changes and a modification of foraminifera and ostracods shell structures. The aim of the study is to assess the heavy metal contamination level and mobility by identifying the trapping phases. The study includes analyses by ICP-AES and ICP-MS, of, respectively, major (Si, Al, Mg, Ca, Fe, Mn, Ti, Na, K, P) and trace elements (Sr, Ba, V, Ni, Co, Cr, Zn, Cu, As, Pb, Cd) in sediments and suspended matter, heavy metals enrichment factors calculations and sequential extractions. Results show that sediments contain Zn, Cu, Pb, V, Cr, Co, As, Ni with minimum and maximum concentrations, respectively, of 4–1190 μg/g, 4–466 μg/g, 11–297 μg/g, 11–194 μg/g, 9–139 μg/g, 1–120 μg/g, 4–76 μg/g, 2–62 μg/g. High concentrations in Zn are also present in suspended matter. The enrichment factors show contamination in Zn, Pb and As firstly induced by the mining industry and secondly by unauthorized dumps and untreated wastewaters. Cr and Ni are bound to clays, whereas V, Co, Cu and Zn are related to oxides. Thus, the risk in metal mobility is for the latter elements and lies in the oxidation–reduction-changing conditions of sediments.     

The Removal of Dissolved Metals by Hydroxysulphate Precipitates during Oxidation and Neutralization of Acid Mine Waters, Iberian Pyrite Belt

This study examines the removal of dissolved metals during the oxidation and neutralization of five acid mine drainage (AMD) waters from La Zarza, Lomero, Esperanza, Corta Atalaya and Poderosa mines (Iberian Pyrite Belt, Huelva, Spain). These waters were selected to cover the spectrum of pH (2.2–3.5) and chemical composition (e.g., 319–2,103 mg/L Fe; 2.85–33.3 g/L SO₄⁼) of the IPB mine waters. The experiments were conducted in the laboratory to simulate the geochemical evolution previously recognized in the field. This evolution includes two stages: (1) oxidation of dissolved Fe(II) followed by hydrolysis and precipitation of Fe(III), and (2) progressive pH increase during mixing with fresh waters. Fe(III) precipitates at pH < 3.5 (stages 1 and 2) in the form of schwertmannite, whereas Al precipitates during stage 2 at pH 5.0 in the form of several hydroxysulphates of variable composition (hydrobasaluminite, basaluminite, aluminite). During these stages, trace elements are totally or partially sorbed and/or coprecipitated at different rates depending basically on pH, as well as on the activity of the SO₄⁼ anion (which determines the speciation of metals). The general trend for the metals which are chiefly present as aqueous free cations (Pb²⁺, Zn²⁺, Cu²⁺, Cd²⁺, Mn²⁺, Co²⁺, Ni²⁺) is a progressive sorption at increasing pH. On the other hand, As and V (mainly present as anionic species) are completely scavenged during the oxidation stage at pH < 3.5. In waters with high activities (> 10⁻¹) of the SO ₄⁼ ion, some elements like Al, Zn, Cd, Pb and U can also form anionic bisulphate complexes and be significantly sorbed at pH < 5. The removal rates at pH 7.0 range from around 100% for As, V, Cu and U, and 60–80% for Pb, to less than 20% for Zn, Co, Ni and Mn. These processes of metal removal represent a significant mechanism of natural attenuation in the IPB.     

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.