The influence of the abandoned Kalecik Hg mine on water and stream sediments (Karaburun,Izmir, Turkey)

This study covers the geochemical investigations on water and stream sediments to evaluate the influence from the abandoned Kalecik Hg mine. The groundwater samples (S5, S8, S9, WW10) are neutral, slightly alkaline waters which have pH values varying between 7.3 and 7.5. Electrical conductivity (EC) values of groundwaters for spring samples are low (250-300 microS/cm). However, groundwater obtained from a deep well has a higher EC value of 950 microS/cm. Hg concentrations of groundwater samples vary between 0.01 and 0.13 microg/l. Hg concentrations of other water samples taken from mining area from surface waters and adits are between 0.10 and 0.99 microg/l. Adit water (A4) collected at the mine has the highest Hg content of 0.99 microg/l and a pH of 4.4. Trace element concentrations of mine water samples show variable values. As is observed only in MW1 (310 microg/l). A4 was enriched in Cd, Co and Cr and exceed the Turkish drinking water standards (Türk Standartlari Enstitüsü, 1997). Cu concentrations vary between 6.0 and 150 microg/l and are below the Turkish water standards. Mn concentrations in mine waters are between 0.02 and 4.9 mg/l. Only for sample A4 Mn value (4.9 mg/l) exceeds the standard level. Ni was enriched for all of the mine water samples and exceeds the safe standard level (20 microg/l) for drinking water. Of the major ions SO(4) shows a notable increase in this group reaching 650 mg/l that exceeds the drinking water standards. Stream sediment samples have abnormally high values for especially Hg and As, Sb, Ni, Cr metals. With the exception of sample Ss6 of which Hg concentration is 92 mg/kg, all the other samples have Hg contents of higher than 100 mg/kg. Pollution index values are significantly high and vary between 69 and 82 for stream sediment samples.     

Geochemistry of some rare earth elements in groundwater,Vierlingsbeek, The Netherlands

Groundwater samples were taken from seven bore holes at depths ranging from 2 to 41m nearby drinking water pumping station Vierlingsbeek, The Netherlands and analysed for Y, La, Ce, Pr, Nd, Sm and Eu. Shale-normalized patterns were generally flat and showed that the observed rare earth elements (REE) were probably of natural origin. In the shallow groundwaters the REEs were light REE (LREE) enriched, probably caused by binding of LREEs to colloids. To improve understanding of the behaviour of the REE, two approaches were used: calculations of the speciation and a statistical approach.For the speciation calculations, complexation and precipitation reactions including inorganic and dissolved organic carbon (DOC) compounds, were taken into account. The REE speciation showed REE(3+), REE(SO(4))(+), REE(CO(3))(+) and REE(DOC) being the major species. Dissolution of pure REE precipitates and REE-enriched solid phases did not account for the observed REEs in groundwater. Regulation of REE concentrations by adsorption-desorption processes to Fe(III)(OH)(3) and Al(OH)(3) minerals, which were calculated to be present in nearly all groundwaters, is a probable explanation.The statistical approach (multiple linear regression) showed that pH is by far the most significant groundwater characteristic which contributes to the variation in REE concentrations. Also DOC, SO(4), Fe and Al contributed significantly, although to a much lesser extent, to the variation in REE concentrations. This is in line with the calculated REE-species in solution and REE-adsorption to iron and aluminium (hydr)oxides. Regression equations including only pH, were derived to predict REE concentrations in groundwater. External validation showed that these regression equations were reasonably successful to predict REE concentrations of groundwater of another drinking water pumping station in quite different region of The Netherlands.     

Impact of irrigating rice paddies with groundwater containing arsenic in Bangladesh

Soil and soil-water As profiles were obtained from 4 rice paddies in Bangladesh during the wet growing season (May-November), when surface water with little arsenic is used for irrigation, or during the dry season (January-May), when groundwater elevated in arsenic is used instead. In the upper 5 cm of paddy soil, accumulation of 13+/-12 mg/kg acid-leachable As (n=11) was observed in soil from 3 sites irrigated with groundwater containing 80-180 microg/L As, whereas only 3+/-2 mg/kg acid-leachable As (n=8) was measured at a control site. Dissolved As concentrations averaged 370+/-340 microg/L (n=7) in the upper 5 cm of the soil at the 3 sites irrigated with groundwater containing 80-180 microg/L As, contrasting with soil water As concentrations of only 18+/-7 microg/L (n=4) over the same depth interval at the control site. Despite the accumulation of As in soil and in soil water attributable to irrigation with groundwater containing elevated As levels, there is no evidence of a proportional transfer to rice grains collected from the same sites. Digestion and analysis of individual grains of boro winter rice from the 2 sites irrigated with groundwater containing 150 and 180 microg/L As yielded concentrations of 0.28+/-0.13 mg/kg (n=12) and 0.44+/-0.25 mg/kg (n=12), respectively. The As content of winter rice from the control site was not significantly different though less variable (0.30+/-0.07; n=12). The observations suggest that exposure of the Bangladesh population to As contained in rice is less of an immediate concern than the continued use of groundwater containing elevated As levels for drinking or cooking, or other potential consequences of As accumulation in soil and soil-water.     

Arsenic speciation and uranium concentrations in drinking water supply wells in Northern Greece: correlations with redox indicative parameters and implications for groundwater treatment

The cities in the Aksios and Kalikratia areas in Northern Greece rely on arsenic contaminated groundwater for their municipal water supply. As remedial action strongly depends on arsenic speciation, the presence of other possible contaminants, and on the general water composition, a detailed study with samples from 21 representative locations was undertaken. Arsenic concentrations were typically 10-70 microg/L. In the groundwaters of the Aksios area with lower Eh values (87-172 mV), pH 7.5-8.2 and 4-6 mM HCO(3) alkalinity, As(III) predominated. Manganese concentrations were mostly above the EC standard of 0.05 mg/L (0.1-0.7 mg/L). In groundwaters of the Kalikratia area with higher Eh values (272-352 mV), pH 6.7-7.5 and 6-12 mM HCO(3) alkalinity, As(V) was the main species. Uranium in the groundwaters was also investigated and correlations with total arsenic concentrations and speciation were examined to understand more of the redox chemistry of the examined groundwaters. Uranium concentrations were in the range 0.01-10 microg/L, with the higher concentrations to occur in the oxidizing groundwaters of the Kalikratia area. Uranium and total arsenic concentrations showed no correlation, whereas uranium concentrations correlated strongly with As(III)/As(tot) ratios, depicting their use as a possible indicator of groundwater redox conditions. Finally, boron was found to exceed the EC drinking water standard of 1 mg/L in some wells in the Kalikratia area and its removal should also be considered in the design of a remedial action.     

The potential for methane emissions from groundwaters of the UK

Methane (CH4) is only a trace constituent of the atmosphere but an important greenhouse gas. Although groundwater is unlikely to be a major source of atmospheric CH4, its contribution to the CH4 budget of the UK has up to now been poorly characterised. Groundwater CH4 concentrations have been measured on 85 samples from water-supply boreholes and a further eight from other miscellaneous water sources. Concentrations in abstracted groundwaters ranged from <0.05-42.9 microg/l for Chalk, <0.05-22 microg/l for the Lower Greensand, 0.05-21.2 microg/l for the Lincolnshire Limestone and from <0.05-465 microg/l for the Triassic sandstone. Having the largest abstraction volume, the Chalk is likely to be the main UK groundwater contributor to global CH4 emissions. A calculation to estimate the total emissions of CH4 from water-supply groundwater sources based on the median and the maximum CH4 concentrations gave values of 2.2x10(-6) and 3.3x10(-4) Tg/year. Estimates show groundwater contributes a maximum of 0.05% of all UK CH4 emissions and a further two orders of magnitude less in terms of the global CH4 budget. Other groundwater sources such as inflows to tunnels may have significantly higher CH4 concentrations, but the volume of water discharged is much lower and the overall amount of CH4 outgassed is likely to be of the same order as the aquifer release. The generally low concentrations of CH4 in groundwater supplies suggest no threat of explosion, although groundwater released by excavations remains a hazard.     

Arsenic pollution in groundwater: a self-organizing complex geochemical process in the deltaic sedimentary environment,Bangladesh

The presence of considerable concentrations of As (Sonargon: below detection limit (bdl)-1.46 mg/l; Faridpur: bdl-1.66 mg/l) and some other elements (like B, F, U) in groundwater of the Ganges-Meghna-Brahmaputra (G-M-B) rivers flood plain indicate that several millions of people are consuming contaminated water. Conditions regulating the mobilization and diagenetic behavior of arsenic in sediments are not well characterized, although understanding these conditions is essential in order to predict the modes of transfer of this contaminant from sediments to groundwater. Analyses of vertical profiles of total arsenic and iron as well as easily soluble As and reducible (reactive) iron concentrations in sediments of the Ganges and Meghna flood plains show no arsenic-enriched layer up to 36-m depth. However, arsenic content in sediments is relatively higher than mean crustal concentration, showing some peaks (Sonargaon: 27.9 mg/kg; 3 m, 31.5 mg/kg; 9 m, 27.30 mg/kg; 16 m, 37.70 mg/kg; 29.5 m, Faridpur: 19.80 mg/kg; 6 m, 26.60 mg/kg; 14.5 m, 29.40 mg/kg; 25 m) depending on the periodical differences in sedimentary cycling of arsenic, metal (hydr)oxides and organic matter. Seasonal changes have no clear or consistent effect on the groundwater arsenic concentrations; with the exception of a small-scale localized irregular change (10-16%). However, easily reducible metal oxides and hydroxides were significant factors affecting the retention of arsenic by sediments during leaching. The biogeochemical cycling of arsenic and iron is closely coupled in deltaic systems where iron oxy-hydroxides provide a carrier phase for the deposition of arsenic in sediments. Analytical results of mimic leaching experiments strongly supported the reduction (Fe oxy-hydroxides) mechanism for arsenic mobilization in alluvial aquifer of deltaic sedimentary environment of G-M-B rivers flood plain.     

Groundwater nitrogen composition and transformation within a moorland catchment, mid-Wales

The importance of upland groundwater systems in providing a medium for nitrogen transformations and processes along flow paths is investigated within the Afon Gwy moorland catchment, Plynlimon, mid-Wales. Dissolved organic nitrogen (DON) was found to be the most abundant form of dissolved nitrogen (N) in most soils and groundwaters, accounting for between 47 and 72% of total dissolved nitrogen in shallow groundwater samples and up to 80% in deeper groundwaters. Groundwater DON may also be an important source of bio-available N in surface waters and marine systems fed by upland catchments. A conceptual model of N processes is proposed based on a detailed study along a transect of nested boreholes and soil suction samplers within the interfluve zone. Shallow groundwater N speciation reflects the soilwater N speciation implying a rapid transport mechanism and good connectivity between the soil and groundwater systems. Median nitrate concentrations were an order of magnitude lower within the soil zone (<5-31 microg/L) than in the shallow groundwaters (86-746 microg/L). Given the rapid hydrostatic response of the groundwater level within the soil zone, the shallow groundwater system is both a source and sink for dissolved N. Results from dissolved N(2)O, N(2)/Ar ratios and dissolved N chemistry suggests that microbial N transformations (denitrification and nitrification) may play an important role in controlling the spatial variation in soil and groundwater N speciation. Reducing conditions within the groundwater and saturated soils of the wet-flush zones on the lower hillslopes, a result of relatively impermeable drift deposits, are also important in controlling N speciation and transformation processes.     

Evolution of anthropogenic aerosols in the coastal town of Salina Cruz, Mexico: part II particulate phase chemistry

An analysis of atmospheric gases and particles during periods of land and sea breezes in a coastal city in southwest Mexico indicates limited removal of total particle mass by deposition during periods when the air resides over the ocean. The average PM(2.5) mass concentrations for land and sea breeze samples were 25+/-1.0 and 26+/-1.0 microg m(-3), respectively. The average sum of the ion concentrations (NH(4)(+), SO(4)(2-), NO(3)(-), Na(+), Cl(-)) were 10 and 11.8 microg m(-3) for the samples taken during land and sea breeze periods. The average total carbon concentrations were 6.0 and 5.3 microg m(-3) for land and sea breeze periods. The mass of sulfate in particles of ocean origin, 3.3+/-2.8 microg m(-3), is marginally higher than those originating from the land, 2.0+/-0.8 microg m(-3), presumably as a result of the conversion of SO(2) recirculated from the city. The fraction of sulfate, nitrate and ammonium ions in rainwater samples is almost a factor of two higher than the fraction measured on filtered air samples. The rainwater also contains significant concentrations of elemental and organic carbon. This study, although extending over a period of only 15 days, with limited chemical samples, suggests that recirculation of anthropogenic particles from coastal cities should be taken into consideration when diagnosing and predicting air quality in such regions.     

Sources and controls for the mobility of arsenic in oxidizing groundwaters from loess-type sediments in arid/semi-arid dry climates - evidence from the Chaco-Pampean plain (Argentina)

In oxidizing aquifers, arsenic (As) mobilization from sediments into groundwater is controlled by pH-dependent As desorption from and dissolution of mineral phases. If climate is dry, then the process of evaporative concentration contributes further to the total concentration of dissolved As. In this paper the principal As mobility controls under these conditions have been demonstrated for Salí River alluvial basin in NW Argentina (Tucumán Province; 7000 km²), which is representative for other basins or areas of the predominantly semi-arid Chaco-Pampean plain (1,000,000 km²) which is one of the world’s largest regions affected by high As concentrations in groundwater. Detailed hydrogeochemical studies have been performed in the Salí River basin where 85 groundwater samples from shallow aquifers (42 samples), deep samples (26 samples) and artesian aquifers (17 samples) have been collected. Arsenic concentrations range from 11.4 to 1660 μg L⁻¹ leaving 100% of the investigated waters above the provisional WHO guideline value of 10 μg L⁻¹. A strong positive correlation among As, F, and V in shallow groundwaters was found. The correlations among those trace elements and U, B and Mo have less significance. High pH (up to 9.2) and high bicarbonate (HCO₃) concentrations favour leaching from pyroclastic materials, including volcanic glass which is present to 20-25% in the loess-type aquifer sediments and yield higher trace element concentrations in groundwater from shallow aquifers compared to deep and artesian aquifers. The significant increase in minor and trace element concentrations and salinity in shallow aquifers is related to strong evaporation under semi-arid climatic conditions. Sorption of As and associated minor and trace elements (F, U, B, Mo and V) onto the surface of Fe-, Al- and Mn-oxides and oxi-hydroxides, restricts the mobilization of these elements into groundwater. Nevertheless, this does not hold in the case of the shallow unconfined groundwaters with high pH and high concentrations of potential competitors for adsorption sites (HCO₃, V, P, etc.). Under these geochemical conditions, desorption of the above mentioned anions and oxyanions occurs as a key process for As mobilization, resulting in an increase of minor and trace element concentrations. These geochemical processes that control the concentrations of dissolved As and other trace elements and which determine the groundwater quality especially in the shallow aquifers, are comparable to other areas with high As concentrations in groundwater of oxidizing aquifers and semi-arid or arid climate, which are found in many parts of the world, such as the western sectors of the USA, Mexico, northern Chile, Turkey, Mongolia, central and northern China, and central and northwestern Argentina.     

Application of biological processes for the removal of arsenic from groundwaters

Bacteria are widespread, abundant, geochemically reactive components of aquatic environments. In particular, iron-oxidizing bacteria, are involved in the oxidation and subsequent precipitation of ferrous ions. Due to this property, they have been applied in drinking water treatment processes, in order to accelerate the removal of ferrous iron from groundwaters. Iron also exerts a strong influence on arsenic concentrations in groundwater sources, while iron oxides are efficient adsorbents in arsenic removal processes. In the present study, the removal of arsenic (III and V), during biological iron oxidation has been investigated. The results showed that both inorganic forms of arsenic could be efficiently treated, for the concentration range of interest in drinking water (50-200microg/L). In addition, the oxidation of trivalent arsenic was found to be catalyzed by bacteria, leading to enhanced overall arsenic removal, because arsenic in the form of arsenites cannot be efficiently sorbed onto iron oxides. This method comprises a cost competitive technology, which can find application in treatment of groundwaters with elevated concentrations of iron and arsenic.     

Implications of organic matter on arsenic mobilization into groundwater: Evidence from northwestern (Chapai-Nawabganj), central (Manikganj) and southeastern (Chandpur) Bangladesh

Boreholes (50 m depth) and piezometers (50 m depth) were drilled and installed for collecting As-rich sediments and groundwater in the Ganges, Brahmaputra, and Meghna flood plains for geochemical analyses. Forty-one groundwater samples were collected from the three areas for the analyses of cations (Ca²⁺, Mg²⁺, K⁺, Na⁺), anions (Cl⁻, NO₃⁻, SO₄²⁻), total organic carbon (TOC), and trace elements (As, Mn, Fe, Sr, Se, Ni, Co, Cu, Mo, Sb, Pb). X-ray powder diffraction (XRD) and X-ray fluorescence (XRF) were performed to characterize the major mineral and chemical contents of aquifer sediments. In all three study areas, results of XRF analysis clearly show that fine-grained sediments contain higher amounts of trace element because of their high surface area for adsorption. Relative fluorescent intensity of humic substances in groundwater samples ranges from 30 to 102 (mean 58 ± 20, n = 20), 54-195 (mean 105 ± 48, n = 10), and 27-243 (mean 79 ± 71, n = 11) in the Ganges, Brahmaputra and Meghna flood plains, respectively. Arsenic concentration in groundwater (20-50 m of depth) ranges from 3 to 315 μg/L (mean 62.4 ± 93.1 μg/L, n = 20), 16.4-73.7 μg/L (mean 28.5 ± 22.4 μg/L, n = 10) and 4.6-215.4 μg/L (mean 30.7 ± 62.1 μg/L, n = 11) in the Ganges, Brahmaputra and Meghna flood plains, respectively. Specific ultra violet adsorption (SUVA) values (less than 3 m⁻¹ mg⁻¹ L) indicate that the groundwater in the Ganges flood plain has relatively low percentage of aromatic organic carbon compared to those in the Brahmaputra and Meghna flood plains. Arsenic content in sediments ranges from 1 to 11 mg/kg (mean 3.5 ± 2.7 mg/kg, n = 17) in the three flood plains. Total organic carbon content is 0.5-3.7 g/kg (mean 1.9 ± 1.1 g/kg) in the Ganges flood plain, 0.5-2.1 g/kg (mean: 1.1 ± 0.7 g/kg) in the Brahmaputra flood plain and 0.3-4.4 g/kg (mean 1.9 ± 1.9 g/kg) in the Meghna flood plain. Arsenic is positively correlated with TOC (R² = 0.50, 0.87, and 0.85) in sediments from the three areas. Fourier transform infrared (FT-IR) analysis of the sediments revealed that the functional groups of humic substances in three areas include amines, phenol, alkanes, and aromatic carbon. Arsenic and Fe speciation in sediments were determined using XANES and the results imply that As(V) and Fe(III) are the dominant species in most sediments. The results also imply that As (V) and Fe (III) in most of the sediment samples of the three areas are the dominant species. X-ray absorption fine structure (EXAFS) analysis shows that FeOOH is the main carrier of As in the sediments of three areas. In sediments, As is well correlated with Fe and Mn. However, there is no such correlation observed between As and Fe as well as As and Mn in groundwater, implying that mobilizations of Fe, Mn, and As are decoupled or their concentrations in groundwater have been affected by other geochemical processes following reductive dissolution of Fe or Mn-hydroxides. For example, dissolved Fe and Mn levels may be affected by precipitation of Fe- and Mn-carbonate minerals such as siderite, while liberated As remains in groundwater. The groundwaters of the Brahmaputra and Meghna flood plains contain higher humic substances in relative fluorescence intensity (or fluorescence index) and lower redox potential compared to the groundwater of Ganges flood plain. This leads to the release of arsenic and iron to groundwater of these three plains in considerable amounts, but their concentrations are distributed in spatial variations.     

Arsenic abundance and variation in golf course lakes

Monosodium methanearsonate (MSMA) is a commonly used herbicide on golf courses. To investigate the variation in abundance of arsenic (As) after MSMA application, 28 golf course lakes were monitored monthly for one year. The As concentrations varied substantially in and between individual lakes with values up to 124 microg/L (mean=10.9 microg/L, n=336). This is considerably higher than the As concentrations in comparable "non-golf course" lakes (up to 100-times) in the study area. The highest values of As in the lakes were generally observed in the late spring and early summer and corresponded to the intensity of MSMA applications. Arsenic seems to be sequestered by the golf course lake sediments with concentrations as high as 302 mg/kg, which were significantly higher than the 0.1 to 3 mg/kg expected for comparable sediments in central Florida. Arsenic correlates well with Fe in the top 15 cm of the lake sediments suggesting that As is sorbed by hydrous ferric oxides (HFO). As long as conditions are in favour of HFO stability, As is retained in the lake sediments preventing its migration into the Floridan aquifer systems. However, once the loading capacity of the sediment is reached or when as a result of changing physico-chemical conditions HFO may become unstable, As may enter the Floridan aquifer.     

Microbial transformations of arsenic: mobilization from glauconitic sediments to water

In the Inner Coastal Plain of New Jersey, arsenic (As) is released from glauconitic sediment to carbon- and nutrient-rich shallow groundwater. This As-rich groundwater discharges to a major area stream. We hypothesize that microbes play an active role in the mobilization of As from glauconitic subsurface sediments into groundwater in the Inner Coastal Plain of New Jersey. We have examined the potential impact of microbial activity on the mobilization of arsenic from subsurface sediments into the groundwater at a site on Crosswicks Creek in southern New Jersey. The As contents of sediments 33-90 cm below the streambed were found to range from 15 to 26.4 mg/kg, with siderite forming at depth. Groundwater beneath the streambed contains As at concentrations up to 89 μg/L. Microcosms developed from site sediments released 23 μg/L of As, and active microbial reduction of As(V) was observed in microcosms developed from site groundwater. DNA extracted from site sediments was amplified with primers for the 16S rRNA gene and the arsenate respiratory reductase gene, arrA, and indicated the presence of a diverse anaerobic microbial community, as well as the presence of potential arsenic-reducing bacteria. In addition, high iron (Fe) concentrations in groundwater and the presence of iron-reducing microbial genera suggests that Fe reduction in minerals may provide an additional mechanism for release of associated As, while arsenic-reducing microorganisms may serve to enhance the mobility of As in groundwater at this site.     

Processes releasing arsenic to groundwater in the Caldes de Malavella geothermal area, NE Spain

Arsenic concentrations exceeding the World Health Organization drinking water guideline (10 μg/L) have been measured in thermal and non-thermal groundwaters from the Caldes de Malavella geothermal area (La Selva graben, NE Spain). The CO₂-rich Na-HCO₃ thermal waters (up to 60 °C at the spring) have elevated arsenic concentrations ([As_T] from 50 to 80 μg/L). The non-thermal waters are of Ca-Na-HCO₃-Cl type and have [As_T] between <1 and 200 μg/L, defining a hot-spot distribution. The present-day contribution of As from CO₂-rich thermal waters to non-thermal aquifers is very limited, as shown by the concentration of geothermal tracers such as Li and B. Redox-controlling processes appear to govern the mobility of As in the non-thermal waters. Arsenate is clearly predominant in most oxidizing groundwaters (>85% of As(V) over total As), whereas reducing, high-As groundwater reaches up to 100% in arsenite. The reductive dissolution of Fe(III) oxyhydroxides and the coupled release and reduction of adsorbed As explain the elevated dissolved arsenite (up to 190 μg/L) and Fe (up to 14 mg/L) content in the more reducing non-thermal groundwater. Conversely, the high levels of nitrate (up to 136 mg/L) ensure an oxidizing environment in most non-thermal groundwaters ([As_T] between <1 and 60 μg/L). Under these conditions, Fe(III) oxyhydroxides are stable and As release to groundwater is not related to their dissolution. Instead, dissolved arsenate concentrations up to 60 μg/L are explained by a competition for sorption sites with other species, mainly bicarbonate and silicic acid, while arsenate desorption due to pH increase is not considered a major process.     

Arsenic in hair and nails of individuals exposed to arsenic-rich groundwaters in Kandal province, Cambodia

The health implications of the consumption of high arsenic groundwater in Bangladesh and West Bengal are well-documented, however, little is known about the level of arsenic exposure elsewhere in Southeast Asia, where widespread exploitation of groundwater resources is less well established. We measured the arsenic concentrations of nail and hair samples collected from residents of Kandal province, Cambodia, an area recently identified to host arsenic-rich groundwaters, in order to evaluate the extent of arsenic exposure. Nail and hair arsenic concentrations ranged from 0.20 to 6.50 microg g(-1) (n=70) and 0.10 to 7.95 microg g(-1) (n=40), respectively, in many cases exceeding typical baseline levels. The arsenic content of the groundwater used for drinking water purposes (0.21-943 microg L(-1) (n=31)) was positively correlated with both nail (r=0.74, p<0.0001) and hair (r=0.86, p<0.0001) arsenic concentrations. In addition, the nail and hair samples collected from inhabitants using groundwater that exceeded the Cambodian drinking water legal limit of 50 microg L(-1) arsenic contained significantly more arsenic than those of individuals using groundwater containing <50 microg L(-1) arsenic. X-ray absorption near edge structure (XANES) spectroscopy suggested that sulfur-coordinated arsenic was the dominant species in the bulk of the samples analysed, with additional varying degrees of As(III)-O character. Tentative linear least squares fitting of the XANES data pointed towards differences in the pattern of arsenic speciation between the nail and hair samples analysed, however, mismatches in sample and standard absorption peak intensity prevented us from unambiguously determining the arsenic species distribution. The good correlation with the groundwater arsenic concentration, allied with the relative ease of sampling such tissues, indicate that the arsenic content of hair and nail samples may be used as an effective biomarker of arsenic intake in this relatively recently exposed population.     

Preparation and evaluation of a novel Fe-Mn binary oxide adsorbent for effective arsenite removal

Arsenite (As(III)) is more toxic and more difficult to remove from water than arsenate (As(V)). As there is no simple treatment for the efficient removal of As(III), an oxidation step is always necessary to achieve higher removal. However, this leads to a complicated operation and is not cost-effective. To overcome these disadvantage, a novel Fe-Mn binary oxide material which combined the oxidation property of manganese dioxide and the high adsorption features to As(V) of iron oxides, were developed from low cost materials using a simultaneous oxidation and coprecipitation method. The adsorbent was characterized by BET surface areas measurement, powder XRD, SEM, and XPS. The results showed that prepared Fe-Mn binary oxide with a high surface area (265 m2 g(-1)) was amorphous. Iron and manganese existed mainly in the oxidation state +III and IV, respectively. Laboratory experiments were carried out to investigate adsorption kinetics, adsorption capacity of the adsorbent and the effect of solution pH values on arsenic removal. Batch experimental results showed that the adsorbent could completely oxidize As(III) to As(V) and was effective for both As(V) and As(III) removal, particularly the As(III). The maximal adsorption capacities of As(V) and As(III) were 0.93 mmol g(-1) and 1.77 mmol g(-1), respectively. The results compare favorably with those obtained using other adsorbent. The effects of anions such as SO4(2-), PO4(3-), SiO3(2-), CO3(2-) and humic acid (HA), which possibly exist in natural water, on As(III) removal were also investigated. The results indicated that phosphate was the greatest competitor with arsenic for adsorptive sites on the adsorbent. The presence of sulfate and HA had no significant effect on arsenic removal. The high uptake capability of the Fe-Mn binary oxide makes it potentially attractive adsorbent for the removal of As(III) from aqueous solution.     

Natural denitrification in the Kakamigahara groundwater basin,Gifu prefecture,central Japan

Although nitrate is recognized as the most common groundwater contaminant due to growing anthropogenic sources, such as agriculture in particular, its adverse effects on human and animal health are debatable. The current issue, however, is to control and reduce nitrate contamination with regards to the long residence time of groundwater within aquifers. Denitrification has recently been recognized for its ability to reduce high nitrate concentrations in groundwater. The Kakamigahara groundwater basin, Gifu prefecture, Japan, witnessed rising levels of nitrate (>12 mg/l NO(3)-N) originating from agricultural sources. Chemical analyses for the determination of major constituents of groundwater and delta(15)N of residual nitrate were performed on representative groundwater samples in order to fulfill two main objectives. One is to investigate the current situation of nitrate groundwater pollution. The second objective is to determine whether the denitrification is a potential natural mechanism, which eliminates nitrate pollution in the Kakamigahara aquifer. Agricultural nitrate contamination of groundwater was obvious from characteristically high concentrations of Ca(2+), Mg(2+), NO(3)(-) and SO(4)(2-). High nitrate concentrations were found on the eastern side of the basin in association with vegetable cultivation fields, and decreased gradually towards the west of the basin along the direction of groundwater flow. The decrease of nitrate concentration was conveniently coupled with increase of HCO(3)(-) (the heterotrophic denitrification product), pH and delta(15)N of residual nitrate (due to isotopic fractionation) from east to west. Therefore, denitrification in situ is continuously removing nitrate from the Kakamigahara groundwater system.     

Oxidation and removal of arsenic (III) from aerated groundwater by filtration through sand and zero-valent iron

Removing arsenic from contaminated groundwater in Bangladesh is challenging due to high concentrations of As(III), phosphate and silicate. Application of zero-valent iron as a promising removal method was investigated in detail with synthetic groundwater containing 500 microg/L As(III), 2-3mg/L P, 20mg/L Si, 8.2mM HCO3-, 2.5mM Ca2+, 1.6mM Mg2+ and pH 7.0. In a series of experiments, 1L was repeatedly passed through a mixture of 1.5 g iron filings and 3-4 g quartz sand in a vertical glass column (10mm diameter), allowing the water to re-aerate between each filtration. At a flow rate of 1L/h, up to 8 mg/L dissolved Fe(II) was released. During the subsequent oxidation of Fe(II) by dissolved oxygen, As(III) was partially oxidized and As(V) sorbed on the forming hydrous ferric oxides (HFO). HFO was retained in the next filtration step and was removed by shaking of the sand-iron mixture with water. Rapid phosphate removal provided optimal conditions for the sorption of As(V). Four filtrations lead to almost complete As(III) oxidation and removal of As(tot) to below 50 microg/L. In a prototype treatment with a succession of four filters, each containing 1.5 g iron and 60 g sand, 36 L could be treated to below 50 microg/L in one continuous filtration, without an added oxidant.     

Application of factor analysis in the assessment of groundwater quality in a blackfoot disease area in Taiwan

Factor analysis is applied to 28 groundwater samples collected from wells in the coastal blackfoot disease area of Yun-Lin, Taiwan. Correlations among 13 hydrochemical parameters are statistically examined. A two-factor model is suggested and explains over 77.8% of the total groundwater quality variation. Factor 1 (seawater salinization) includes concentrations of EC, TDS, Cl(-), SO(4)(2-), Na(+), K(+) and Mg(2+), and Factor 2 (arsenic pollutant) includes concentrations of Alk, TOC and arsenic. Maps are drawn to show the geographical distribution of the factors. These maps delineate high salinity and arsenic concentrations. The geographical distribution of the factor scores at individual wells does not reveal the sources of the constituents, which are instead, deduced from geological and hydrological evidence. The areas of high seawater salinization and arsenic pollution correspond well to the groundwater over-pumping area. Over-pumping of the local groundwater causes land subsidence and gradual salinization by seawater. The over-pumping also introduces excess dissolved oxygen that oxidizes the immobile minerals, releases arsenic by reductive dissolution of arsenic-rich iron oxyhydroxides and increases the arsenic concentration in water. The over-extraction of groundwater is the major cause of groundwater salinization and arsenic pollution in the coastal area of Yun-Lin, Taiwan.