Temporal variations in arsenic uptake by rice plants in Bangladesh: The role of iron plaque in paddy fields irrigated with groundwater

The transfer of arsenic to rice grains is a human health issue of growing relevance in regions of southern Asia where shallow groundwater used for irrigation of paddy fields is elevated in As. In the present study, As and Fe concentrations in soil water and in the roots of rice plants, primarily the Fe plaque surrounding the roots, were monitored during the 4-month growing season at two sites irrigated with groundwater containing ∼ 130 μg l^− 1 As and two control sites irrigated with water containing < 15 μg l^− 1 As. At both sites irrigated with contaminated water, As concentrations in soil water increased from < 10 μg l^− 1 to > 1000 μg l^− 1 during the first five weeks of the growth season and then gradually declined to < 10 μg l^− 1 during the last five weeks. At the two control sites, concentrations of As in soil water never exceeded 40 µg l^− 1. At both contaminated sites, the As content of roots and Fe plaque rose to 1000-1500 mg kg^− 1 towards the middle of the growth season. It then declined to ∼ 300 mg kg^− 1 towards the end, a level still well above As concentration of ∼ 100 mg kg^− 1 in roots and plaque measured throughout the growing season at the two control sites. These time series, combined with simple mass balance considerations, demonstrate that the formation of Fe plaque on the roots of rice plants by micro-aeration significantly limits the uptake of As by rice plants grown in paddy fields. Large variations in the As and Fe content of plant stems at two of the sites irrigated with contaminated water and one of the control sites were also recorded. The origin of these variations, particularly during the last month of the growth season, needs to be better understood because they are likely to influence the uptake of As in rice grains.     

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.     

Manganese concentrations in Scottish groundwater

Groundwater is increasingly being used for public and private water supplies in Scotland, but there is growing evidence that manganese (Mn) concentrations in many groundwater supplies exceed the national drinking water limit of 0.05 mg l^− 1. This study examines the extent and magnitude of high Mn concentrations in groundwater in Scotland and investigates the factors controlling Mn concentrations. A dataset containing 475 high quality groundwater samples was compiled using new data from Baseline Scotland supplemented with additional high quality data where available. Concentrations ranged up to 1.9 mg l^− 1; median Mn concentration was 0.013 mg l^− 1 with 25th and 75th percentiles 0.0014 and 0.072 mg l^− 1 respectively. The Scottish drinking water limit (0.05 mg l^− 1) was exceeded for 30% of samples and the WHO health guideline (0.4 mg l^− 1) by 9%; concentrations were highest in the Carboniferous sedimentary aquifer in central Scotland, the Devonian sedimentary aquifer of Morayshire, and superficial aquifers. Further analysis using 137 samples from the Devonian aquifers indicated strong redox and pH controls (pH, Eh and dissolved oxygen accounted for 58% of variance in Mn concentrations). In addition, an independent relationship between Fe and Mn was observed, suggesting that Fe behaviour in groundwater may affect Mn solubility. Given the redox status and pH of Scottish groundwaters the most likely explanation is sorption of Mn to Fe oxides, which are released into solution when Fe is reduced.Since the occurrence of elevated Mn concentrations is widespread in groundwaters from all aquifer types, consideration should be given to monitoring Mn more widely in both public and private groundwater supplies in Scotland and by implication elsewhere.     

Geochemistry of redox-sensitive elements and sulfur isotopes in the high arsenic groundwater system of Datong Basin, China

High arsenic groundwater in the Quaternary aquifers of Datong Basin, northern China contain As up to 1820 µg/L and the high concentration plume is located in the slow flowing central parts of the basin. In this study we used hydrochemical data and sulfur isotope ratios of sulfate to better understand the conditions that are likely to control arsenic mobilization. Groundwater and spring samples were collected along two flow paths from the west and east margins of the basin and a third set along the basin flow path. Arsenic concentrations range from 68 to 670 µg/L in the basin and from 3.1 to 44 µg/L in the western and eastern margins. The margins have relatively oxidized waters with low contents of arsenic, relatively high proportions of As(V) among As species, and high contents of sulfate and uranium. By contrast, the central parts of the basin are reducing with high contents of arsenic in groundwater, commonly with high proportions of As(III) among As species, and low contents of sulfate and uranium. No statistical correlations were observed between arsenic and Eh, sulfate, Fe, Mn, Mo and U. While the mobility of sulfate, uranium and molybdenum is possibly controlled by the change in redox conditions as the groundwater flows towards central parts of the basin, the reducing conditions alone cannot account for the occurrence of high arsenic groundwater in the basin but it does explain the characteristics of arsenic speciation. With one exception, all the groundwaters with As(III) as the major As species have low Eh and those with As(V) have high Eh. Reductive dissolution of Fe-oxyhydroxides or reduction of As(V) are consistent with the observations, however no increase in dissolved Fe concentration was noted. Furthermore, water from the well with the highest arsenic was relatively oxidizing and contained mostly As(V). From previous work Fe-oxyhydroxides are speculated to exist as coatings rather than primary minerals.The wide range of δ³⁴S_[SO4] values (from − 2.5 to + 36.1‰) in the basin relative to the margins (from + 8‰ to + 15‰) indicate that sulfur is undergoing redox cycling. The highly enriched values point to sulfate reduction that was probably mediated by bacteria. The presence of monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA) is also evidence of microbial reactions. The depleted signatures indicate that some oxidation of depleted sulfide occurred in the basin. It must be noted that the samples with depleted sulfur isotope values have very low sulfate concentrations and therefore even a small amount of sulfide oxidation will bias the ratio. No significant correlation was observed between δ³⁴S_[SO4] values and total arsenic contents when all the samples were considered. However, the wells in the central basin do appear to become enriched in δ³⁴S_[SO4] as arsenic concentration increases. Although there is evidence for sulfate reduction, it is clear that sulfate reduction does not co-precipitate or sequester arsenic. The one sample with high arsenic that is oxidizing cannot be explained by oxidation of pyrite and is likely an indication that there are multiple redox zones that control arsenic speciation but not necessarily its mobilization and contradict the possibility that Fe-oxyhydroxides sorb appreciable amounts of arsenic in this study area. It is evident that this basin like other two young sedimentary basins (Huhhot and Hetao in Inner Mongolia) of northern China with high arsenic groundwater is transporting arsenic at a very slow rate. The data are consistent with the possibility that the traditional models of arsenic mobilization, namely reductive dissolution of Fe-oxyhydroxides, reduction of As(V) to more mobile As(III), and bacteria mediated reactions, are active to varying degrees. It is also likely that different processes control arsenic mobilization at different locations of the basin and more detailed studies along major flow paths upgradient of the high arsenic aquifers will shed more light on the mechanisms.     

Assessment of arsenic exposure from groundwater and rice in Bengal Delta Region, West Bengal, India

Arsenic (As) induced identifiable health outcomes are now spreading across Indian subcontinent with continuous discovery of high As concentrations in groundwater. This study deals with groundwater hydrochemistry vis-à-vis As exposure assessment among rural population in Chakdaha block, West Bengal, India. The water quality survey reveals that 96% of the tubewells exceed WHO guideline value (10 μg/L of As). The groundwaters are generally anoxic (−283 to −22 mV) with circum-neutral pH (6.3 to 7.8). The hydrochemistry is dominated by HCO₃⁻ (208 to 440 mg/L), Ca²⁺ (79 to 178 mg/L) and Mg²⁺ (17 to 45 mg/L) ions along with high concentrations of As_T (As total, below detection limit to 0.29 mg/L), Fe_T (Fe total, 1.2 to 16 mg/L), and Fe(II) (0.74 to 16 mg/L). The result demonstrates that Fe(II)-Fe(III) cycling is the dominant process for the release of As from aquifer sediments to groundwater (and vice versa), which is mainly controlled by the local biogeochemical conditions. The exposure scenario reveals that the consumption of groundwater and rice are the major pathways of As accumulation in human body, which is explained by the dietary habit of the surveyed population. Finally, regular awareness campaign is essential as part of the management and prevention of health outcomes.     

Enrichment processes of arsenic in oxidic sedimentary rocks - From geochemical and genetic characterization to potential mobility

Sedimentary marine iron ores of Jurassic age and Tertiary marine sandy sediments containing iron hydroxides concretions have been sampled from boreholes and outcrops in two study areas in Germany to examine iron and arsenic accumulation processes. Samples were analyzed for bulk rock geochemistry (INAA/ICP-OES), quantitative mineralogy (XRD with Rietveld analysis), element distribution (electron microprobe) and arsenic fractionation (sequential extraction). Bulk Jurassic ores contain an average arsenic content of 123 μg g⁻¹ hosted in mainly goethite ooids which slowly formed in times of condensed sedimentation. Enrichment occurred syndepositionally and is therefore characterized as primary. Iron concretions in Tertiary sediments mainly consist of goethite and yield arsenic up to 1860 μg g⁻¹. The accumulation process is secondary as it took place in the course of oxidation of the originally reduced marine sediments under terrestrial conditions, leading to element redistribution and local enrichment in the near-surface part. The scale of enrichment was assessed calculating Enrichment Factors, indicating that arsenic accumulation was favoured over other potential contaminants. In spite of higher bulk arsenic contents in the oxidic rocks, the mainly pyrite-hosted As pool within the reduced deeper part of the Tertiary sediments is shown to have a higher potential for remobilization and creation of elevated arsenic concentrations in groundwater.     

Antimony, arsenic and mercury in the aquatic environment and fish in a large antimony mining area in Hunan, China

Antimony (Sb) has received increasing attention recently due to its toxicity and potential human carcinogenicity. In the present work, drinking water, fish and algae samples were collected from the Xikuangshan (XKS) Sb mine area in Hunan, China. Results show that serious Sb and moderate arsenic (As) contamination is present in the aquatic environment. The average Sb concentrations in water and fish were 53.6 ± 46.7 μg L^− 1 and 218 ± 113 μg kg^− 1 dry weight, respectively. The Sb concentration in drinking water exceeded both Chinese and WHO drinking water guidelines by 13 and 3 times, respectively. Antimony and As concentrations in water varied with seasons. Fish gills exhibited the highest Sb concentrations but the extent of accumulation varied with habitat. Antimony enrichment in fish was significantly lower than that of As and Hg.     

Mineralogical and geochemical controls of arsenic speciation and mobility under different redox conditions in soil, sediment and water at the Mokrsko-West gold deposit, Czech Republic

Naturally contaminated soil, sediment and water at the Mokrsko-West gold deposit, Central Bohemia, have been studied in order to determine the processes that lead to release of As into water and to control its speciation under various redox conditions. In soils, As is bonded mainly to secondary arseniosiderite, pharmacosiderite and Fe oxyhydroxides and, rarely, to scorodite; in sediments, As is bonded mainly to Fe oxyhydroxides and rarely to arsenate minerals.The highest concentrations of dissolved As were found in groundwater (up to 1141 μg L^− 1), which mostly represented a redox transition zone where neither sulphide minerals nor Fe oxyhydroxide are stable. The main processes releasing dissolved As in this zone are attributed to the reductive dissolution of Fe oxyhydroxides and arsenate minerals, resulting in a substantial decrease in their amounts below the groundwater level. Some shallow subsurface environments with high organic matter contents were characterized by reducing conditions that indicated a relatively high amount of S^− 2,0 in the solid phase and a lower dissolved As concentration (70-80 μg L^− 1) in the pore water. These findings are attributed to the formation of Fe(II) sulphides with the sorbed As. Under oxidizing conditions, surface waters were undersaturated with respect to arsenate minerals and this promoted the dissolution of secondary arsenates and increased the As concentrations in the water to characteristic values from 300 to 450 μg L^− 1 in the stream and fishpond waters. The levels of dissolved As(III) often predominate over As(V) levels, both in groundwaters and in surface waters. The As(III)/As(V) ratio is closely related to the DOC concentration and this could support the assumption of a key role of microbial processes in transformations of aqueous As species as well as in the mobility of As.     

Manganese and lead in children's blood and airborne particulate matter in Durban, South Africa

Despite the toxicity and widespread use of manganese (Mn) and lead (Pb) as additives to motor fuels and for other purposes, information regarding human exposure in Africa is very limited. This study investigates the environmental exposures of Mn and Pb in Durban, South Africa, a region that has utilized both metals in gasoline. Airborne metals were sampled as PM_2.5 and PM₁₀ at three sites, and blood samples were obtained from a population-based sample of 408 school children attending seven schools. In PM_2.5, Mn and Pb concentrations averaged 17 ± 27 ng m^− 3 and 77 ± 91 ng m^− 3, respectively; Mn concentrations in PM₁₀ were higher (49 ± 44 ng m^− 3). In blood, Mn concentrations averaged 10.1 ± 3.4 μg L^− 1 and 8% of children exceeded 15 μg L^− 1, the normal range. Mn concentrations fit a lognormal distribution. Heavier and Indian children had elevated levels. Pb in blood averaged 5.3 ± 2.1 μg dL^− 1, and 3.4% of children exceeded 10 μg dL^− 1, the guideline level. Pb levels were best fit by a mixed (extreme value) distribution, and boys and children living in industrialized areas of Durban had elevated levels. Although airborne Mn and Pb concentrations were correlated, blood levels were not. A trend analysis shows dramatic decreases of Pb levels in air and children's blood in South Africa, although a sizable fraction of children still exceeds guideline levels. The study's findings suggest that while vehicle exhaust may contribute to exposures of both metals, other sources currently dominate Pb exposures.     

Environmental impact of mining activities in the Lousal area (Portugal): chemical and diatom characterization of metal-contaminated stream sediments and surface water of Corona stream

Lousal mine is a typical “abandoned mine” with all sorts of problems as consequence of the cessation of the mining activity and lack of infrastructure maintenance. The mine is closed at present, but the heavy metal enriched tailings remain at the surface in oxidizing conditions. Surface water and stream sediments revealed much higher concentrations than the local geochemical background values, which the “Contaminated Sediment Standing Team” classifies as very toxic. High concentrations of Cu, Pb, Zn, As, Cd and Hg occurred within the stream sediments downstream of the tailings sites (up to: 817 mg kg⁻¹ As, 6.7 mg kg⁻¹ Cd, 1568 mg kg⁻¹ Cu, 1059 mg kg⁻¹ Pb, 82.4 mg kg⁻¹ Sb, 4373 mg kg⁻¹ Zn). The AMD waters showed values of pH ranging from 1.9 to 2.9 and concentrations of 9249 to 20,700 mg L⁻¹ SO₄⁻², 959 to 4830 mg L⁻¹ Fe and 136 to 624 mg L⁻¹ Al. Meanwhile, the acid effluents and mixed stream waters also carried high contents of SO₄^2−, Fe, Al, Cu, Pb, Zn, Cd, and As, generally exceeding the Fresh Water Aquatic Life Acute Criteria. Negative impacts in the diatom communities growing at different sites along a strong metal pollution gradient were shown through Canonical Correspondence Analysis: in the sites influenced by Acid Mine Drainage (AMD), the dominant taxon was Achnanthidium minutissimum. However, Pinnularia acoricola was the dominant species when the environmental conditions were extremely adverse: very low pH and high metal concentrations (sites 2 and 3). Teratological forms of Achnanthidium minutissimum (Kützing) Czarnecki, Brachysira vitrea (Grunow) Ross in Hartley, Fragilaria rumpens (Kützing) G. W. F. Carlson and Nitzschia hantzschiana Rabenhorst were found. A morphometric study of B. vitrea showed that a decrease in size was evident at the most contaminated sites. These results are evidence of metal and acidic pollution.     

Assessment of the solubility and bioaccessibility of arsenic in realgar wine using a simulated gastrointestinal system

Consumption of arsenic (As) wine is a traditional activity during the classic Chinese festival of Duanwu, colloquially known worldwide as the Dragon Boat Day. Arsenic wine is drunk on the morning of the fifth day of the fifth lunar calendar month to commemorate the death of Qu Yuan, a famed Chinese poet who drowned himself in protest of a corrupt government, and to protect against ill fortune. Although realgar minerals are characteristically composed of sparingly soluble tetra-arsenic tetra-sulfides (As₄S₄), purity does vary with up to 10% of As being present as non-sulfur bound species, such as arsenate (As^V) and arsenite (As^III). Despite, the renewed interest in As speciation and the bioaccessibility of the active As components in realgar based Chinese medicines, little is known about the safety surrounding the cultural practice of drinking As wine. In a series of experiments the speciation and solubility of As in a range of wines were investigated. Furthermore, a simulated gastrointestinal system was employed to predict the impact of digestive processes on As bioavailability. The predominant soluble As species found in all the wines were As^III and As^V. Based on typical As wine recipes employing 0.1 g realgar mL^− 1 wine, the concentration of dissolved As ranged from ca. 100 to 400 mg L^− 1 depending on the ethanol content of the preparation: with the As solubility found to be higher in wines with a lower proportion of ethanol. Based on a common 100 mL measure of wine with a concentration of 400 mg As L^− 1, the amount of soluble As would equate to around half of the acute minimal lethal dose for adults. This is likely an underestimate of the bioaccessible concentration, as a three-fold increase in bioaccessibility could be observed in the intestinal phase based on the results from the stimulated gastrointestinal system.     

Health risk assessment of inorganic arsenic intake of Cambodia residents through groundwater drinking pathway

In order to compare the magnitudes and health impacts of arsenic and other toxic trace elements in well water, groundwater and hair samples were collected from three areas with different arsenic exposure scenarios in the Mekong River basin of Cambodia. Ampil commune in Kampong Cham province was selected as an uncontaminated area, Khsarch Andaet commune in Kratie province was selected as a moderately contaminated area, and Kampong Kong commune in Kandal Province was selected as an extremely contaminated area. Results of ICP-MS analyses of the groundwater samples revealed that As, Mn, Fe and Ba concentrations were significantly different among the three study areas (Kruskal-Wallis test, p < 0.0001). Out of 46 observed wells in the Kandal province study area, 100% detected As > 50 μg L⁻¹ and Fe > 300 μg L⁻¹; 52.17% had Mn > 400 μg L⁻¹ and 73.91% found Ba > 700 μg L⁻¹. In the Kratie province study area (n = 12), 25% of wells showed elevated arsenic levels above 10 μg L⁻¹ and 25% had Mn > 400 μg L⁻¹, whereas samples from Kampong Cham province study area (n = 18) were relatively clean, with As < 10 μg L⁻¹. A health risk assessment model derived from the USEPA was applied to calculate individual risks resulting from drinking groundwater. Computational results indicated that residents from Kandal Province study area (n = 297) confronted significantly higher non-carcinogenic and carcinogenic risks than those in Kratie (n = 89) and Kampong Cham (n = 184) province study areas (Kruskal-Wallis test, p < 0.0001). 98.65% of respondents from the Kandal province study area were at risk for the potential non-cancer effect and an average cancer risk index was found to be 5 in 1000 exposure. The calculations also indicated that, in the Kratie province study area, 13.48% of respondents were affected by non-cancer health risks and 33.71% were threatened by cancer, whereas none of respondents in the Kampong Cham province study area appeared to have non-carcinogenic effect. Positively significant correlations of the arsenic content in scalp hair (As_h) with both arsenic levels in groundwater (As_w) (r_s (304) = 0.757, p < 0.0001) and individual average daily doses (ADD) of arsenic (r_s (304) = 0.763, p < 0.0001) undoubtedly indicated that arsenic accumulation in the bodies of Cambodia residents in the Mekong River basin was mainly through a groundwater drinking pathway. To the best of our knowledge, this is the first comprehensive report comparing individual health risk assessments of arsenic exposure through a groundwater drinking pathway to enriched arsenic levels from groundwater in the Mekong River basin, Cambodia. This study indicates that elevated arsenic concentrations in groundwater may lead to thousands of cases of arsenicosis in the near future if mitigating actions are not taken.     

Using magnetic seeds to improve the aggregation and precipitation of nanoparticles from backside grinding wastewater

Backside grinding (BG) wastewater treatment typically requires large quantities of chemicals, i.e. polyaluminum chloride (PAC) coagulant and produces considerable amounts of sludge, increasing the loading and cost of subsequent sludge treatment and disposal processes. This study investigated the effects of the addition of magnetic seeds (FeO*Fe₂O₃) of selected particle sizes and of optimized combinations of magnetic seeds and PAC on the aggregation of silica nanoparticles from BG wastewater and on the sedimentation time at various pH values (5-9). The results show that the turbidity of BG wastewater was significantly reduced by the magnetic aggregation treatment. The dosage of PAC combined with 2.49 g L⁻¹ or 1.24 g L⁻¹ of magnetic seeds was reduced by 83% (from 60 to 10 mg L⁻¹) compared to the conventional process of using only PAC as a coagulant. The turbidity of the BG wastewater, initially 1900-2500 NTU, could also be successfully decreased about to 23 NTU by the addition of 3.74 g L⁻¹ magnetite (FeO*Fe₂O₃) only at pH 5 with an applied magnetic field of 1000 G. Different coagulation conditions using magnetic seeds combined with coagulant resulted in different aggregation performances. The treatment performance was more effective by using two-stage dosing, in which magnetic seeds and PAC were added separately, than that with one-stage dosing, where the magnetic seeds and PAC were added simultaneously during rapid mixing. The two-stage dosing allowed for a reduction in the optimum dosage of magnetic seeds from 3.74 g L⁻¹ to 2.49 g L⁻¹ or 1.24 g L⁻¹ without affecting performance when coupled with 0.01 g L⁻¹ of PAC coagulant. The developed method effectively reduced the production of waste sludge.     

Glyphosate transport through weathered granite soils under irrigated and non-irrigated conditions — Barcelona, Spain

The transport of Glyphosate ([N-phosphonomethyl] glycine), AMPA (aminomethylphosphonic acid, CH₆NO₃P), and Bromide (Br⁻) has been studied, in the Mediterranean Maresme area of Spain, north of Barcelona, where groundwater is located at a depth of 5.5 m. The unsaturated zone of weathered — granite soils was characterized in adjacent irrigated and non-irrigated experimental plots where 11 and 10 boreholes were drilled, respectively. At the non irrigated plot, the first half of the period was affected by a persistent and intense rainfall. After 69 days of application residues of Glyphosate up to 73.6 μgg^− 1 were detected till a depth of 0.5 m under irrigated conditions, AMPA, analyzed only in the irrigated plot was detected till a depth of 0.5 m. According to the retardation coefficient of Glyphosate as compared to that of Br⁻ for the topsoil and subsoil (80 and 83, respectively) and the maximum observed migration depth of Br⁻ (2.9 m) Glyphosate and AMPA should have been detected till a depth of 0.05 m only. Such migration could be related to the low content of organic matter and clays in the soils; recharge generated by irrigation and heavy rain, and possible preferential solute transport and/or colloidal mediated transport.     

Occurrence of matrix-bound phosphine in polar ornithogenic tundra ecosystems: Effects of alkaline phosphatase activity and environmental variables

Phosphine (PH₃), a reduced phosphorus compound, is a highly toxic and reactive atmospheric trace gas. In this study, a total of ten ornithogenic soil/sediment profiles were collected from tundra ecosystems of east Antarctica and Arctic, and matrix-bound phosphine (MBP), the phosphorus fractions and alkaline phosphatase activity (APA) were analyzed. High MBP concentrations were found in these profiles with the range from 39.59 ng kg^− 1 dw to 11.77 μg kg^− 1 dw. MBP showed a consistent vertical distribution pattern in almost all the soil profiles, and its concentrations increased at soil surface layers and then decreased with depths. MBP levels in the ornithogenic soils were two to three orders of magnitude lower than those in ornithogenic sediments. The yield of PH₃ as a fraction of total P in all the profiles ranged from 10^− 5 to 10^− 9 mgPH₃ mg^− 1P with higher mean PH₃ yield in the ornithogenic sediments. The ornithogenic soils showed high concentrations of total phosphorus (TP), organic phosphorus (OP), inorganic phosphorus (IP) and metal elements (Cu, Zn, Mn, Fe, Al and Ca) but low MBP levels, vice versa for the ornithogenic sediments. No correlation had been obtained between MBP concentrations and IP, OP and TP. There existed an exponential correlation (r = 0.67, p < 0.01) between MBP and soil/sediment moisture. MBP concentrations showed a significant positive correlation with APA (r = 0.668, p < 0.0001), total organic carbon (r = 0.501, p < 0.0001), total hydrogen (r = 0.483, p < 0.0001) and total sulfur (r = 0.398, p < 0.001), indicating that the production of MBP is associated with microbially mediated factors rather than the contents of TP, IP and OP in the P-enriched ornithogenic soils/sediments. Our results indicated that MBP is an important gaseous link in the phosphorus biogeochemical cycles of ornithogenic tundra ecosystems in Antarctica and Arctic.     

The Posidonia oceanica marine sedimentary record: A Holocene archive of heavy metal pollution

The study of a Posidonia oceanica mat (a peat-like marine sediment) core has provided a record of changes in heavy metal abundances (Fe, Mn, Ni, Cr, Cu, Pb, Cd, Zn, As and Al) since the Mid-Holocene (last 4470 yr) in Portlligat Bay (NW Mediterranean). Metal contents were determined in P. oceanica. Both, the concentration records and the results of principal components analysis showed that metal pollution in the studied bay started ca. 2800 yr BP and steadily increased until present. The increase in Fe, Cu, Pb, Cd, Zn and As concentrations since ca. 2800 yr BP and in particular during Greek (ca. 2680-2465 cal BP) and Roman (ca. 2150-1740 cal BP) times shows an early anthropogenic pollution rise in the bay, which might be associated with large- and short-scale cultural and technological development. In the last ca. 1000 yr the concentrations of heavy metals, mainly derived from anthropogenic activities, have significantly increased (e.g. from ~ 15 to 47 μg g^− 1 for Pb, ~ 23 to 95 μg g^− 1 for Zn and ~ 8 to 228 μg g^− 1 for As). Our study demonstrates for the first time the uniqueness of P. oceanica meadows as long-term archives of abundances, patterns, and trends of heavy metals during the Late Holocene in Mediterranean coastal ecosystems.     

Long-range effect of cyanide on mercury methylation in a gold mining area in southern Ecuador

Small-scale gold mining in Portovelo-Zaruma, Southern Equador, performed by mercury amalgamation and cyanidation, yields 9-10 t of gold/annum, resulting in annual releases of around 0.65 t of inorganic mercury and 6000 t of sodium cyanide in the local river system. The release of sediments, cyanide, mercury, and other metals present in the ore such as lead, manganese and arsenic significantly reduces biodiversity downstream the processing plants and enriches metals in bottom sediments and biota. However, methylmercury concentrations in sediments downstream the mining area were recently found to be one order of magnitude lower than upstream or in small tributaries. In this study we investigated cyanide, bacterial activity in water and sediment and mercury methylation potentials in sediments along the Puyango river watershed, measured respectively by in-situ spectrophotometry and incubation with ³H-leucine and ²⁰³Hg²⁺.Free cyanide was undetectable (< 1 μg·L^− 1) upstream mining activities, reached 280 μg·L^− 1 a few km downstream the processing plants area and was still detectable about 100 km downstream. At stations with detectable free cyanide in unfiltered water, 50% of it was dissolved and 50% associated to suspended particles. Bacterial activity and mercury methylation in sediment showed a similar spatial pattern, inverse to the one found for free cyanide in water, i.e. with significant values in pristine upstream sampling points (respectively 6.4 to 22 μgC·mg wet weight^− 1·h^− 1 and 1.2 to 19% of total ²⁰³Hg·g dry weight^− 1·day^− 1) and undetectable downstream the processing plants, returning to upstream values only in the most distant downstream stations. The data suggest that free cyanide oxidation was slower than would be expected from the high water turbulence, resulting in a long-range inhibition of bacterial activity and hence mercury methylation. The important mercury fluxes resultant from mining activities raise concerns about its biomethylation in coastal areas where many mangrove areas have been converted to shrimp farming.     

Determination of arsenic leaching from glazed and non-glazed Turkish traditional earthenware

Glazed and non-glazed earthenware is traditionally and widely used in Turkey and most of the Mediterranean and the Middle East countries for cooking and conservation of foodstuff. Acid-leaching tests have been carried out to determine whether the use of glazed and non-glazed earthenware may constitute a human health hazard risk to the consumers. Earthenware was leached with 4% acetic acid and 1% citric acid solutions, and arsenic in the leachates was measured using hydride generation atomic absorption spectrometry. Arsenic concentrations in the leach solution of non-glazed potteries varied from 30.9 to 800 μg L^− 1, while the glazed potteries varied generally from below the limit of detection (0.5 μg L^− 1) to 30.6 μg L^− 1, but in one poorly glazed series it reached to 110 μg L^− 1. Therefore, the risk of arsenic poisoning by poorly glazed and non-glazed potteries is high enough to be of concern. It appears that this is the first study reporting arsenic release from earthenware into food.     

Phosphorus sorption experiments and the potential for internal phosphorus loading in littoral areas of a stratified lake

The exchange of phosphorus (P) during the resuspension of sediments into shallow (oxic) waters of deep stratified lakes is regulated by equilibrium dynamics. In this study, we compared the P-sorption characteristics of sediments from 17 shallow and deep littoral sites in an oligo-mesotrophic lake. Zero Equilibrium P Concentration (EPC₀) ranged from 0.2 to 5 μg P L⁻¹. EPC₀ did not vary with sediment characteristics, but increased with increasing sediment-to-water ratios (SWR). Buffering capacity also increased with increasing SWR up to 1 g L⁻¹, at which point P concentrations were buffered almost perfectly. Therefore, internal P loading in littoral areas may depend primarily on the intensity and duration of sediment resuspension instead of sediment composition, and is expected to be spatially and temporally patchy. Maximum P-sorption capacity (S_max) varied with chemical composition of the sediments, but was generally low, indicating a limited capacity of littoral sediments to retain external inputs of P.