Perfluorinated compounds in water and sediment from coastal regions of the northern Bohai Sea,China

Concentrations of perfluorooctanesulfonate (PFOS), perfluorooctanoic acid (PFOA) and other perfluorinated compounds (PFCs) were measured in water and sediment from coastal Bohai Bay and surrounding rivers flowing into the bay. Of the 15 PFCs measured, PFOS and PFOA were detected with the greatest frequency. Concentrations in water ranged from<0.2 to 31 ng·L^?1 and<1.0 to 82 ng·L^?1 for PFOS and PFOA, respectively. Concentrations of PFOS and PFOA in sediments ranged from<0.1 to 2.0 ng·g^?1 dw and<0.1 to 0.5 ng·g^?1 dw, respectively. Concentrations of PFCs in Bohai Bay were less than those observed in other areas in Asia, but greater concentrations of ∑PFCs were observed in the Dalin River with concentrations increasing from upstream to downstream, and the greatest concentrations in sediment were observed in tidal flats. The ratio of ∑PFCs in sediment and water indicated that sediment could serve as a significant sink for PFUnA.     

Exceptionally high concentrations of the insect repellent N,N-diethyl-m-toluamide (DEET) in surface waters from Jakarta,Indonesia

Jakarta is a booming coastal megacity in Indonesia with over 10 million inhabitants. The rivers flowing through the city district receive enormous amounts of untreated wastewaters from households and industries and discharge high pollutant loads into Jakarta Bay. Applying a screening approach for the identification of characteristic site-specific and harmful organic contaminants, we frequently found the insect repellent N,N-diethyl-m-toluamide (DEET) in river water and seawater samples from Jakarta. The compound was previously reported as persistent aquatic contaminant in industrial countries, and we present here the first data set from a tropical megacity. Concentrations in river water and seawater from Jakarta were exceptionally high, up to 24,000 ng L^?1, and exceeded by far all published concentrations in surface waters worldwide. We explained this with massive usage of the compound, lack of wastewater treatment and low average river flow as compared to rivers in other tropical megacities. The usage and properties of DEET indicate its suitability as molecular marker of municipal wastewaters. Such markers are useful to trace emissions from specific pollution sources in aquatic systems as a basis for the investigation of related impacts. We show here that DEET is in particular useful to trace the long-range distribution of municipal wastewaters in tropical freshwater and coastal systems. This application is of great value for tracing such inputs in tropical coastal habitats which are sensitive to changing water quality like coral reefs. This assists to uncover whether specific conditions in these systems could be related to pollutant inputs from land.     

Sources and spatial distribution of polycyclic aromatic hydrocarbons in coastal sediments of the Basque Country (Bay of Biscay)

This contribution characterises the sources and distribution of polycyclic aromatic hydrocarbons (PAHs) in sediments of the Basque coast (Bay of Biscay). Different source characterisation approaches (i.e. GIS assisted-chemometrics, PAH diagnostic ratios and analyses of composition profiles) were used in combination to successfully identify the factors determining the origin and distribution of PAHs. Urban/industrial combustion processes were identified as the main PAH source. However, the analysis of PAH composition patterns and diagnostic ratios identified secondary natural and petrogenic PAH sources on small spatial scales. The median ∑18PAH concentration ranged from 66 μg kg^?1 (d.w.) to 7021 μg kg^?1 (d.w.). The Ibaizabal estuary, which supports most of the anthropogenic pressure in the region (i.e. urban development, industrialisation, commercial and recreational harbours), also showed the highest PAH concentrations. On the shelf, human activities, hydrodynamic conditions and geomorphological features led to spatial differences in the PAH concentrations among sectors: the offshore and west sectors were characterised by higher concentrations, while the lowest values were found in the mid and east sectors. The results enhance the knowledge on PAH-related contamination processes and could be used to support the environmental assessment process required under current European marine legislation.     

Trace element concentration in fine particulate matter (PM<Subscript>2.5</Subscript>) and their bioavailability in different microenvironments in Agra,India: a case study

Exposure to airborne particulate matter results in the deposition of millions of particle in the lung; consequently, there is need for monitoring them particularly in indoor environments. Case study was conducted in three different microenvironments, i.e., urban, rural and roadside to examine the elemental bioavailability in fine particulate matter and its potential health risk. The samples were collected on polytetrafluoroethylene filter paper with the help of fine particulate sampler during August–September, 2012. The average mass concentration of PM_2.5 was 71.23 µg m^?3 (rural), 45.33 µg m^?3 (urban) and 36.71 µg m^?3 (roadside). Elements in PM_2.5 were analyzed by inductively coupled plasma atomic emission spectroscopy. Percentage bioavailability was determined to know the amount of soluble fraction that is actually taken across the cell membrane through inhalation pathway. Cadmium and lead were found to have cancer risk in a risk evaluation using an Integrated Risk Information system.     

Metal contamination recorded in the sediment of the semi-closed Bakar Bay (Croatia)

This study presents metal levels in the sediments of the Bakar Bay, with its main goal to evaluate recent anthropogenic influence, as well as over previous decades. Sediment profiles at 7 sampling points were taken. Chemical contents in bulk sediment were obtained using ICP, ICP-MS, and AAS methodologies, and 20 most significant elements were presented. Concentrations of selected elements were evaluated by factor statistical analyses to identify their source. Also, metal enrichment factor and geoaccumulation index were calculated, and spatial distribution maps for three sediment layers were constructed. Measured metal concentrations in sediment were compared with concentrations in other sediments from the Adriatic Sea. In addition, a set of sediment quality guidelines were also applied in order to predict the probability of adverse biological effects on the benthic community: This was found not to be very serious. Factor analysis clearly demonstrates the segregation between metals of natural origin resulted from soil and bedrock weathering (Li, Al, Cr, Sc), and with two anthropogenic sources originating from the city of Bakar and bulk cargo terminal (Hg, Pb, Zn, Ag, Sn, and Fe). Mercury (max 0.65 μg g^?1) is found to be the heaviest contaminant, followed by lead (max 71.5 μg g^?1), copper (89.3 μg g^?1), and zinc (156 μg g^?1). However, this study shows that Bakar Bay is considerably less polluted with toxic metals than it was believed.     

Determination of polychlorinated biphenyl and polycyclic aromatic hydrocarbon marine regional Sediment Quality Guidelines within the European Water Framework Directive

Marine regional Sediment Quality Guidelines (SQG) for polychlorinated biphenyls (PCB) and polycyclic aromatic hydrocarbons (PAH) from the Basque coast (SE Bay of Biscay) were determined, on the basis of sediment chemistry, toxicity and benthic community disturbance from analysis of 756 estuarine and coastal samples. The SQG were calculated using a percentile approach (based upon effect and non-effect data), using non-normalised and normalised concentration, by total organic carbon. However, normalisation by total organic carbon did not result in any improvement in accuracy compared with non-normalised values. Hence, this study proposes non-normalised SQG values for assessment of the chemical and physicochemical status in marine waters in the Basque Country, within the Water Framework Directive: 24.6–29 μg kg^?1 for total PCBs; 164–285 μg kg^?1 for low molecular weight PAH; 922–1537 μg kg^?1 for high molecular weight PAH; and 1607–2617 μg kg^?1 for total PAH.     

Concentration of arsenic in water, sediments and fish species from naturally contaminated rivers

Arsenic (As) may occur in surface freshwater ecosystems as a consequence of both natural contamination and anthropogenic activities. In this paper, As concentrations in muscle samples of 10 fish species, sediments and surface water from three naturally contaminated rivers in a central region of Argentina are reported. The study area is one of the largest regions in the world with high As concentrations in groundwater. However, information of As in freshwater ecosystems and associated biota is scarce. An extensive spatial variability of As concentrations in water and sediments of sampled ecosystems was observed. Geochemical indices indicated that sediments ranged from mostly unpolluted to strongly polluted. The concentration of As in sediments averaged 6.58 μg/g ranging from 0.23 to 59.53 μg/g. Arsenic in sediments barely followed (r = 0.361; p = 0.118) the level of contamination of water. All rivers showed high concentrations of As in surface waters, ranging from 55 to 195 μg/L. The average concentration of As in fish was 1.76 μg/g. The level of contamination with As differed significantly between species. Moreover, the level of bioaccumulation of As in fish species related to the concentration of As in water and sediments also differed between species. Whilst some fish species seemed to be able to regulate the uptake of this metalloid, the concentration of As in the large catfish Rhamdia quelen mostly followed the concentration of As in abiotic compartments. The erratic pattern of As concentrations in fish and sediments regardless of the invariable high levels in surface waters suggests the existence of complex biogeochemical processes behind the distribution patterns of As in these naturally contaminated ecosystems.     

Contamination levels and state assessment in the lakes of the Oliveri-Tindari Lagoon (North-Eastern Sicily,Italy)

The Oliveri-Tindari Lagoon, located in North-Eastern Sicily (Italy) and composed of six lakes, is subject to continuous environmental changes. An integrated study focusing on sediment features and levels of contamination was carried out for three of the six lakes, which are of ancient origin: Verde, Mergolo della Tonnara and Marinello. A high primary production (26.89 μg l^?1) was detected at Lake Verde; texture classification showed a typical grain size in the sediments of all lakes; the study of macronutrients highlighted 17.08 of total carbon in sediments from Lake Mergolo della Tonnara; toxic elements were detected at higher concentrations in the sediments of Lake Marinello in comparison to the others, while arsenic was found in high concentrations in all the samples tested, especially in Lake Verde, with a mean value of 17.25 mg kg^?1 dry weight (d.w.). All the organic contaminants, except 4, 4′-dichlorodiphenyldichloroethylene, were below the detection limits in the sediments. Minimal microbiological contamination was found in both water and sediment samples. In the latter, we isolated several bacterial strains thriving in the presence of arsenic, which play a role in the biogeochemical cycle of arsenic. These preliminary results, obtained for the first time using a multidisciplinary approach, provide general information about the Oliveri-Tindari Lagoon area.     

Heavy metals in the polychaete Glycera longipinnis from the southwest of India

Metal concentrations in sediment and in whole tissue of the benthic polychaete Glycera longipinnis collected along the southwest coast of India were analysed. Relative seasonal accumulation of metals (Cu, Pb, Cr, Ni, Zn, Cd, Hg) was studied by categorising the habitat as less polluted or highly polluted based on metal contamination routed through industrial and urban sources. The metal content in tissues varied seasonally in the ranges, Cu: 2.21–27.08 μg·g^?1, Pb: 0.06–4.92 μg·g^?1, Cr: 1.73–29.20 μg·g^?1, Ni: 1.60–4.61 μg·g^?1, Zn: 14.72–82.30 μg·g^?1, Cd: 0.04–1.38 μg·g^?1and Hg: below decetable limits to 0.86 μg·g^?1. Concentration of heavy metals was found to be high in the whole body of G. longipinnis pooled from the polluted transects. The results of this study suggest that G. longipinnis may act as a useful biological indicator for heavy metal pollution along the southwest coast of India.     

太湖胥口湾表层水和沉积物中多环芳烃的浓度水平及生态风险

多环芳烃(polycyclic aromatic hydrocarbons,PAHs)是环境中普遍存在的稠环类化合物,由于其对人体健康和生态环境产生较大危害,美国环保局将16种PAHs列为优先控制的污染物。PAHs也是太湖流域的主要污染物之一。作为华东地区的重要水系和水源地,研究太湖环境质量的变化对改善太湖流域水生生态系统和提高沿岸居民身体健康具有重要意义。论文研究了太湖胥口湾水域表层水和沉积物的PAHs。结果显示,表层水和沉积物的PAHs总浓度分别为7.2~83 ng·L~(-1)和66~620ng·g~(-1)干重;年均值为29 ng·L~(-1)和218 ng·g~(-1)干重;年均毒性当量浓度为2.4 ng·L~(-1)和28 ng·g~(-1)干重。沉积物中的主要污染物为荧蒽、芘和,影响毒性当量浓度的主要是苯并(a)芘和二苯并(a,h)蒽。4环PAHs在沉积物中占主要,其浓度百分比为44%~48%,而5环PAHs则占毒性当量总浓度的90%以上,说明其危害主要来自5环PAHs。PAHs特征化合物比值分析表明,胥口湾沉积物中PAHs主要来源于煤和木材燃烧,表层水大部分为燃烧和石油的混合来源。污染水平的时空变化特点为丰水期(8月)表层水PAHs浓度偏高,沉积物偏低。湖区和湖岸的PAHs浓度只在丰水期有显著差异,表层水PAHs浓度湖区高于湖岸,沉积物相反;其他时期湖区和湖岸PAHs浓度无显著差异。根据加拿大沉积物环境质量标准,胥口湾整体生态风险水平较低。从时空分布特征来看,个别生态风险较高的点主要分布在湖岸,5月平水期可能是沉积物中PAHs生态风险较高的频发期。     

Spatial distribution of copper in relation to recreational boating in a California shallow-water basin

The overall effect of the number of boats on the copper (Cu) levels in the water column and sediment, along with their spatial variability within Shelter Island Yacht Basin (SIYB), San Diego Bay, California was examined. We identified a horizontal gradient of increasing dissolved Cu and Cu in sediment from outside to the head of SIYB which was coincident with the increasing number of boats. Spatial models of Cu distribution in water and sediment indicated the presence of ‘hotspots’ of Cu concentration. From outside to the head of SIYB, dissolved Cu ranged from 1.3 μ g L^?1 to 14.6 μ g L^?1 in surface water, and 2.0 μ g L^?1 to 10.2 μ g L^?1 in bottom water. Cu in sediment exceeded the Effect Range Low of 34 mg kg^?1 (i.e. where adverse effects to fauna may occur), with a peak concentration of 442 mg kg^?1 at the head of the basin. Free Cu⁺⁺ in surface water was several orders of magnitude higher than in sediment porewater. High-resolution data of Cu species together with probability maps presented in this paper will allow managers to easily visualise and localise areas of impaired quality and to prioritise which areas should be targeted to improve Cu-related conditions.     

In vivo uptake of iodine from a <Emphasis Type="Italic">Fucus serratus</Emphasis> Linnaeus seaweed bath: does volatile iodine contribute?

Seaweed baths containing Fucus serratus Linnaeus are a rich source of iodine which has the potential to increase the urinary iodide concentration (UIC) of the bather. In this study, the range of total iodine concentration in seawater (22–105 µg L^?1) and seaweed baths (808–13,734 µg L^?1) was measured over 1 year. The seasonal trend shows minimum levels in summer (May–July) and maximum in winter (November–January). The bathwater pH was found to be acidic, average pH 5.9 ± 0.3. An in vivo study with 30 volunteers was undertaken to measure the UIC of 15 bathers immersed in the bath and 15 non-bathers sitting adjacent to the bath. Their UIC was analysed pre- and post-seaweed bath and corrected for creatinine concentration. The corrected UIC of the population shows an increase following the seaweed bath from a pre-treatment median of 76 µg L^?1 to a post-treatment median of 95 µg L^?1. The pre-treatment UIC for both groups did not indicate significant difference (p = 0.479); however, the post-treatment UIC for both did (p = 0.015) where the median bather test UIC was 86 µg L^?1 and the non-bather UIC test was 105 µg L^?1. Results indicate the bath has the potential to increase the UIC by a significant amount and that inhalation of volatile iodine is a more significant contributor to UIC than previously documented.     

Seasonal Variations of Trace Metal Chemical Forms in Bed Sediments of a Karstic River in Lebanon: Implications for Self-purification

Although Lebanon has abundant water, its rivers are polluted and aquifer water mismanaged. Effective river water usage requires an understanding of the geochemistry of polluting metals in catchments. Climate is “Mediterranean”: wet winters and dry summers. Active sediment flushing is restricted to winter high discharge episodes. Except in winter, water column pollutants are removed by precipitation or sorption to the surface of static bed sediments. Hence (1) does winter flushing of contaminated sediment and replacement by clean sediment favour self purification? (2) does the distribution of metals between extractable fractions change seasonally and thereby affect metal bioavailability ? Results on the distribution of metals are reported for Fe, Pb, Zn, Cu and Cd in bed sediments from Nahr Ibrahim (a karstic river) for summer and winter. A Tessier-like sequential extraction scheme was applied to samples (< 75 μm) for five locations along a 13 km stretch to the sea. Water pH was above 8.2 at all locations implying a very low solubility for Fe. Sediment was derived from catchment soils and limestone. Total sediment Fe increased in winter at all sites following deposition of eroded soil from upstream. Cadmium, Cu and Pb derived from polluting sources; the sources of Zn were more complex. Dilution by clean sediment explained winter reductions in total Cd, Cu and Pb; Zn changes were less consistent. Iron occurred mostly (> 77 sum of fractions) in the residual fraction compared with 6– 31 for pollutants; residual Cu and Zn showed a small increase in winter whereas Cd and Pb did not change. All readily exchangeable metals decreased in winter and the carbonate bound forms predominated in both seasons. Nahr Ibrahim has a high capacity for self purification and metal resolubilisation from sediment will be limited by the solubility of carbonate forms.     

Rapid liquid–liquid extraction for the reliable GC/MS analysis of volatile priority pollutants

Mass spectrometry is a powerful tool for the analysis of organic pollutants in the environment. Nevertheless, sample preparation for GC/MS analysis is often criticized for being too laborious and requiring expensive equipment. Thus, purge-and-trap or headspace devices are the most popular nowadays to investigate volatile organic pollutants. At the same time, modern commercial high-resolution mass spectrometers allow for the significant simplification of the sample preparation procedures due to better acquisition rate, accurate mass measurements, and improved sensitivity. Here, we used a time-of-flight high-resolution mass spectrometer Pegasus GC-HRT (LECO, USA) to identify and quantify 47 volatile priority organic pollutants in water. The developed accelerated water sample preparation approach requires just 1 mL of water and 1 mL of dichloromethane. The detection limits of the analytes are about 1 μg L^?1, while the quantification limits are approximately 5 μg L^?1. These limits correspond to those required by Method 8260C of the United States Environmental Protection Agency. Here, we demonstrate that sample preparation for the reliable and sensitive GC/MS analysis of volatile organic priority pollutants may be achieved in 5 min in 5-mL vials in the field or just prior to GC/MS analysis in the laboratory without the use of any expensive equipment.     

Ecotoxicological risks of the abandoned F–Ba–Pb–Zn mining area of Osor (Spain)

Due to its potential toxic properties, metal mobilization is of major concern in areas surrounding Pb–Zn mines. In the present study, metal contents and toxicity of soils, aqueous extracts from soils and mine drainage waters from an abandoned F–Ba–Pb–Zn mining area in Osor (Girona, NE Spain) were evaluated through chemical extractions and ecotoxicity bioassays. Toxicity assessment in the terrestrial compartment included lethal and sublethal endpoints on earthworms Eisenia fetida, arthropods Folsomia candida and several plant species, whereas aquatic tests involved bacteria Vibrio fischeri, microalgae Raphidocelis subcapitata and crustaceans Daphnia magna. Total concentrations of Ba (250–5110 mg kg^?1), Pb (940 to >5000 mg kg^?1) and Zn (2370–11,300 mg kg^?1) in soils exceeded intervention values to protect human health. Risks for the aquatic compartment were identified in the release of drainage waters and in the potential leaching and runoff of metals from contaminated soils, with Cd (1.98–9.15 µg L^?1), Pb (2.11–326 µg L^?1) and Zn (280–2900 µg L^?1) concentrations in filtered water samples surpassing US EPA Water Quality Criteria (2016a, b). Terrestrial ecotoxicity tests were in accordance with metal quantifications and identified the most polluted soil as the most toxic. Avoidance and reproduction tests with earthworms showed the highest sensitivity to metal contamination. Aquatic bioassays performed in aqueous extracts from soils confirmed the results from terrestrial tests and also detected toxic effects caused by the mine drainage waters. Algal growth inhibition was the most sensitive aquatic endpoint. In view of the results, the application of a containment or remediative procedure in the area is encouraged.     

A decade of investigations on groundwater arsenic contamination in Middle Ganga Plain,India

Groundwater arsenic (As) load in excess of drinking limit (50 µg L^?1) in the Gangetic Plains was first detected in 2002. Though the menace was known since about two decades from the downstream part of the plains in the Bengal Basin, comprising of Lower Ganga Plain and deltaic plains of Ganga–Brahmaputra–Meghna River system, little thought was given to its possible threat in the upstream parts in the Gangetic Plains beyond Garo-Rajmahal Hills. The contamination in Bengal Basin has become one of the extensively studied issues in the world and regarded as the severest case of health hazard in the history of mankind. The researches and investigations in the Gangetic Plains during the last decade (2003–2013) revealed that the eastern half of the plains, also referred as Middle Ganga Plain (MGP), is particularly affected by contamination, jeopardising the shallow aquifer-based drinking water supply. The present paper reviews researches and investigations carried out so far in MGP by various research institutes and government departments on wide array of issues of groundwater As such as its spatio-temporal variation, mobilisation paths, water level behaviour and flow regime, configuration of contaminated and safe aquifers and their recharge mechanism. Elevated conc. of groundwater As has been observed in grey and dark grey sediments of Holocene age (Newer Alluvium) deposited in a fluvio-lacustrine environment in the floodplain of the Ganga and most of its northern tributaries from Himalayas. Older Alluvium, comprising Pleistocene brownish yellow sediment, extending as deeper aquifers in Newer Alluvium areas, is low in groundwater As. Similarities and differences on issues between the MGP and the Bengal Basin have been discussed. The researches point towards the mobilisation process as reductive dissolution of iron hydroxide coating, rich in adsorbed As, mediated by microbial processes. The area is marked with shallow water level (<8.0 m below ground) with ample monsoonal recharge. The infiltrated rainwater and percolating water from surface water bodies carry organic carbon from sediments (particularly from the clay plugs in abandoned channels), abetting microbial processes, spread of anoxic front and release of As.     

Tributyltin pollution in sediments from Alexandria's coastal areas

Presence of Tributyltin (TBT) in Alexandria’s coastal water areas has been demonstrated by measuring concentrations of this compound. The TBT was measured in sediments from three docking areas namely: Western Harbour, Eastern Harbour and Abu Qir Bay. The sediment of those areas has been affected by marine traffic and other industrial activities. This is reflected by the distribution of TBT in the sediments nearby the shipyards in the three docking areas of the region where the average values of 258.6 ηg TBT/g for Western Harbour; 126.4 ηg TBT/g dw for Abu Qir Bay and 42.3 ηg TBT/g dw for the Eastern Harbour were recorded. This fact reflects the effect of industry and marine traffic on the marine environments of the Alexandria region.     

Anthropogenic metal pollution in surface sediments of the Tambaraparni River Estuary

Estuarine sediments in the<63 μm size fraction were collected from 15 stations within the Tambaraparni River Estuary, located on the east coast of India. The distribution of the heavy metals Cd, Co, Cr, Cu, Ni, Pb and Zn was recorded. Our analysis distinguished two groups of elements. First, Cd, Pb and Zn, which occurred in higher than expected concentrations indicative of pollution, and second, Co, Cr, Cu and Ni, which occurred at background levels. The highest metal concentration found in the study area was for Zn (1200 μ g·g^?1), and the lowest was for Cd (0.42 μ g·g^?1). It is presumed that river run-off, industrial waters and untreated domestic waters are major contributors to heavy metal pollution in the Tambaraparni River Estuary. The concentrations of heavy metal species in surface sediments (<2 m water depth) of the Tambaraparni Estuary were studied to determine the extent of anthropogenic inputs from catchment areas and to understand anthropogenic effects on geochemical process in this tropical estuarine system.     

Arsenic contamination of natural waters in San Juan and La Pampa, Argentina

Arsenic (As) speciation in surface and groundwater from two provinces in Argentina (San Juan and La Pampa) was investigated using solid phase extraction (SPE) cartridge methodology with comparison to total arsenic concentrations. A third province, Río Negro, was used as a control to the study. Strong cation exchange (SCX) and strong anion exchange (SAX) cartridges were utilised in series for the separation and preservation of arsenite (As^III), arsenate (As^V), monomethylarsonic acid (MA^V) and dimethylarsinic acid (DMA^V). Samples were collected from a range of water outlets (rivers/streams, wells, untreated domestic taps, well water treatment works) to assess the relationship between total arsenic and arsenic species, water type and water parameters (pH, conductivity and total dissolved solids, TDS). Analysis of the waters for arsenic (total and species) was performed by inductively coupled plasma mass spectrometry (ICP-MS) in collision cell mode. Total arsenic concentrations in the surface and groundwater from Encon and the San José de Jáchal region of San Juan (north-west Argentina within the Cuyo region) ranged from 9 to 357 μg l^?1 As. Groundwater from Eduardo Castex (EC) and Ingeniero Luiggi (LU) in La Pampa (central Argentina within the Chaco-Pampean Plain) ranged from 3 to 1326 μg l^?1 As. The pH range for the provinces of San Juan (7.2–9.7) and La Pampa (7.0–9.9) are in agreement with other published literature. The highest total arsenic concentrations were found in La Pampa well waters (both rural farms and pre-treated urban sources), particularly where there was high pH (typically > 8.2), conductivity (>2,600 μS cm^?1) and TDS (>1,400 mg l^?1). Reverse osmosis (RO) treatment of well waters in La Pampa for domestic drinking water in EC and LU significantly reduced total arsenic concentrations from a range of 216–224 μg l^?1 As to 0.3–0.8 μg l^?1 As. Arsenic species for both provinces were predominantly As^III and As^V. As^III and As^V concentrations in San Juan ranged from 4–138 μg l^?1 to <0.02–22 μg l^?1 for surface waters (in the San José de Jáchal region) and 23–346 μg l^?1 and 0.04–76 μg l^?1 for groundwater, respectively. This translates to a relative As^III abundance of 69–100% of the total arsenic in surface waters and 32–100% in groundwater. This is unexpected because it is typically thought that in oxidising conditions (surface waters), the dominant arsenic species is As^V. However, data from the SPE methodology suggests that As^III is the prevalent species in San Juan, indicating a greater influence from reductive processes. La Pampa groundwater had As^III and As^V concentrations of 5–1,332 μg l^?1 and 0.09–592 μg l^?1 for EC and 32–242 μg l^?1 and 30–277 μg l^?1 As for LU, respectively. Detectable levels of MA^V were reported in both provinces up to a concentration of 79 μg l^?1 (equating to up to 33% of the total arsenic). Previously published literature has focused primarily on the inorganic arsenic species, however this study highlights the potentially significant concentrations of organoarsenicals present in natural waters. The potential for separating and preserving individual arsenic species in the field to avoid transformation during transport to the laboratory, enabling an accurate assessment of in situ arsenic speciation in water supplies is discussed.     

Selenium speciation in wheat grain varies in the presence of nitrogen and sulphur fertilisers

This study investigated whether selenium species in wheat grains could be altered by exposure to different combinations of nitrogen (N) and sulphur (S) fertilisers in an agronomic biofortification experiment. Four Australian wheat cultivars (Mace, Janz, Emu Rock and Magenta) were grown in a glasshouse experiment and exposed to 3 mg Se kg^?1 soil as selenate (Se^VI). Plants were also exposed to 60 mg N kg^?1 soil as urea and 20 mg S kg^?1 soil as gypsum in a factorial design (N + S + Se; N + Se; S + Se; Se only). Plants were grown to maturity with grain analysed for total Se concentrations via ICP-MS and Se species determined via HPLC-ICP-MS. Grain Se concentrations ranged from 22 to 70 µg Se g^?1 grain (dry mass). Selenomethionine (SeMet), Se-methylselenocystine (MeSeCys), selenohomolanthionine (SeHLan), plus a large concentration of uncharacterised Se species were found in the extracts from grains. SeMet was the major Se species identified accounting for between 9 and 24 µg Se g^?1 grain. Exposure to different N and S fertiliser combinations altered the SeMet content of Mace, Janz and Emu Rock grain, but not that of Magenta. MeSeCys and SeHLan were found in far lower concentrations (<4 µg Se g^?1 grain). A large component of the total grain Se was uncharacterisable (>30 % of total grain Se) in all samples. When N fertiliser was applied (with or without S), the proportion of uncharacterisable Se increased between 60 and 70 % of the total grain Se. The data presented here indicate that it is possible to alter the content of individual Se species in wheat grains via biofortification combined with manipulation of N and S fertiliser regimes. This has potential significance in alleviating or combating both Se deficiency and Se toxicity effects in humans.