Speciation of As(III) and As(V) in water and sediment using reverse-phase ion-pair high-performance liquid chromatography-neutron activation analysis (HPLC-NAA)

Total As content and the As species distribution in water and sediments from the Kwabrafo stream, a major water body draining the Obuasi gold mining community in southwestern Ghana, have been investigated. Total As content was determined by instrumental neutron activation analysis (INAA). Ion-pair reverse phase high-performance liquid chromatography-neutron activation analysis (HPLC-NAA) was used for speciation of As species. Solid phase extraction with phosphate buffer was used to extract soluble As species from lyophilized sediment. The mass balance after phosphate extraction of soluble As species in sediment varied from 89 to 96 %. Compositionally appropriate reference material International Atomic Energy Agency (IAEA)-Lake Sediment (SL)-1 was used to check the validity of INAA method for total As determination. The measured values are in good agreement with the IAEA recommended value and also within the 95 % confidence interval. The accuracy of the measurement in terms of relative deviation from the IAEA recommended value was ±0.83 %. “In-house” prepared As(III) and As(V) standards were used to validate the HPLC-INAA method used for the As species determination. Total As concentration in the water samples ranged from 1.15 to 9.20 mg/L. As(III) species in water varied from 0.13 to 0.7 mg/L, while As(V) species varied from 0.79 to 3.85 mg/L. Total As content in sediment ranged from 2,134 to 3,596 mg/kg dry mass. The levels of As(III) and As(V) species in the sediment ranges from 138 to 506 mg/kg dry mass and 156 to 385 mg/kg dry mass, respectively.     

Measurements of dissolved methylmercury in natural waters using diffusive gradients in thin film (DGT)

A diffusive gradient in thin films (DGT) technique for measuring methylmercury (MeHg) concentrations in natural waters was developed using 3-mercaptopropyl-functionalized silica gel to preconcentrate the methylmercury. The new resin was characterized and calibrated. Methylmercury is efficiently accumulated at a pH range of 3-9. Basic performance tests of the new DGT device confirmed the applicability of Fick's first law for such DGT measurements. The diffusion coefficient of methylmercury in polyacrylamide gel was 5 x 10(-6) cm(2) s(-1). Methylmercury concentrations determined by DGT deployed for different time periods in the field are statistically not different from results obtained through direct measurements. The DGT technique represents therefore an alternative in situ sampling method for methylmercury. The detection limit of the overall method is 1 pg of MeHg, which correspond to approximately 30 pg L(-1) of MeHg in a water sample, when deploying a typical DGT device for 24 hours. Lower MeHg concentrations are measurable using longer deployment times or thinner diffusive gel layers.     

Monitoring of eutrophication by microbial uptake kinetics of dissolved organic matter in waters

The monitoring of eutrophication can be performed by measuring the turnover times of amino acids in watermasses using the Wright-Hobbie uptake kinetics approach.The substrate specificity of amino acids varies greater with turnover times than with sampling location in watermasses with a certain water type. Thus a specific substrate among the essential amino acids should be selected to use for measuring the turnover time, in order to monitor precisely the state of trophic excitation within the steady-state oscillation in a certain aquatic system. On the other hand, either singular or plural substrates among the essential amino acids can be used for measuring the turnover time for the identification of a watermass, relevant to eutrophication.     

Simultaneous quantification of Bi(III) and U(VI) in environmental water samples with a complicated matrix containing organic compounds

Trace amounts of bismuth(III) and uranium(VI) can be simultaneously determined in a single scan by adsorptive cathodic stripping voltammetry in the presence of cupferron as a complexing agent. Optimal conditions were found to be: 0.1 mol?L^?1 acetate buffer (pH 5.3), 5?×?10^?5?mol?L^?1 cupferron, accumulation potential of ?0.25 V, and accumulation time of 30 s. The linear range of Bi(III) and U(VI) was observed over the concentration range from 2?×?10^?9 to 2?×?10^?7?mol?L^?1 and from 1?×?10^?8 to 5?×?10^?7?mol?L^?1, respectively. The influence of the main components of real water samples such as foreign ions and organic substances (surface active substances, humic substances) was precisely investigated. The method was applied to the simultaneous measurements of bismuth and uranium in natural water samples.     

Different hydrodynamic processes regulated on water quality (nutrients,dissolved oxygen,and phytoplankton biomass) in three contrasting waters of Hong Kong

The subtropical Hong Kong (HK) waters are located at the eastern side of the Pearl River Estuary. Monthly changes of water quality, including nutrients, dissolved oxygen (DO), and phytoplankton biomass (Chl-a) were routinely investigated in 2003 by the Hong Kong Environmental Protection Department in three contrasting waters of HK with different prevailing hydrodynamic processes. The western, eastern, and southern waters were mainly dominated by nutrient-replete Pearl River discharge, the nutrient-poor coastal/shelf oceanic waters, and mixtures of estuarine and coastal seawater and sewage effluent of Hong Kong, respectively. Acting in response, the water quality in these three contrasting areas showed apparently spatial–temporal variation pattern. Nutrients usually decreased along western waters to eastern waters. In the dry season, the water column was strongly mixed by monsoon winds and tidal currents, which resulted in relatively low Chl-a (<5 μg l^?1) and high bottom DO (>4 mg l^?1), suggesting that mixing enhanced the buffering capacity of eutrophication in HK waters. However, in the wet season, surface Chl-a was generally >10 μg l^?1 in southern waters in summer due to halocline and thermohaline stratification, adequate nutrients, and light availability. Although summer hypoxia (DO <2 mg l^?1) was episodically observed near sewage effluent site and in southern waters induced by vertical stratification, the eutrophication impacts in HK waters were not as severe as expected owing to P limitation and short water residence time in the wet season.     

Behaviors of dissolved antimony in the Yangtze River Estuary and its adjacent waters

Antimony is a naturally occurring and cumulatively toxic element. With increasing concern as an inorganic contaminant, research on its environmental behavior is becoming a necessity. However, very little is known about this element. To further understand its biogeochemical behaviors and roles in the ecosystem, the main species of dissolved inorganic antimony (Sb(iii) and Sb(v)) in Yangtze River Estuary and its adjacent waters were determined by hydride generation and atomic fluorescence (HG-AFS) in our study. Results show that in surface water, the concentration for Sb(iii) and Sb(v) were in the range 0.029 μg L(-1)～ 0.736 μg L(-1) and 0.121 μg L(-1)～ 2.567 μg L(-1), with averages of 0.152 μg L(-1) and 0.592 μg L(-1), respectively. While concentrations of Sb(iii) and Sb(v) in the bottom layer were much lower, ranging from 0.023 μg L(-1) to 0.116 μg L(-1) (average of 0.050 μg L(-1)) and from 0.047 μg L(-1) to 0.441 μg L(-1) (average of 0.194 μg L(-1)), respectively. Data analysis further demonstrates that the major processes controlling antimony geochemistry in the area are riverine input, atmospheric deposition, incursion of Taiwan Warm Current, and release from particulate phase. The surface-enrichment and bottom-depletion depth profile reveals it does appear as a mildly scavenged element but is less like arsenic than previously believed. Sb(v) was the predominant speciation in aquatic environment of our research, and Sb(iii) was a minor constituent of the total antimony. Regarding the adsorption-desorption process onto SPM, Sb(iii) has a higher affinity to particulate phase than Sb(v). Furthermore, the significant correlation between antimony and nutrients indicates it is an element with great biological potential, which is also an important behavior for antimony.     

The development of a chemical 'fingerprint' to characterise dissolved organic matter in natural waters

A suite of twelve assays has been used to 'fingerprint' dissolved organic matter (DOM). The assays were applied directly to filtered natural water samples. Temperature, pH and conductivity accounted for the environmental conditions on-site. Bulk carbon characteristics were assayed by measuring UV absorbance at 200 and 240 nm, colour in grade Hazen, DOC (dissolved organic carbon), fluorescence (excitation 370 nm, emission 450 nm) and the complexation of phenol itself. Measuring hydroxybenzenes ('monophenolics'), polyhydroxybenzenes ('polyphenolics') and total phenolics with the Gibbs, Prussian Blue and Folin-Ciocalteau assays, respectively, determined the phenolics pool. The methodology was tested on six freshwater sites in North Wales chosen to provide differences in vegetation, land-use and water chemistry and sampled once during each season. A novel approach for the presentation of the data has been developed that combines all range normalised assay results for each site and each season within one polar plot, hence the term 'fingerprint'. The data was also analysed using principal component factor analysis. Assays characterised as determining the chemical properties of DOM contributed to Factor 1 and explained 59% of the variation in the data. Assays apparently determined by the water matrix, contributed to Factor 2 and explained 20% of the variation within the data. The factor scores obtained for each site showed more variation for assays relating to the chemical properties of DOM than to the surrounding water matrix. The methodology was found to detect chemical changes within DOM for each site throughout the year and different responses for different sites.     

Copper fractionation with dissolved organic matter in natural waters and wastewater--a mixed micelle mediated methodology (cloud point extraction) employing flame atomic absorption spectrometry

A cloud point extraction-preconcentration methodology for the speciation analysis of free and organically complexed metal species in natural waters is presented. The method is based on the neutralization of the electrostatic charge of the humate-metal complexes with a positively charged surfactant in a high ionic strength solution environment. The resulting complexes are conveniently solubilized in the micelles of a non-ionic surfactant medium and are thus separated from the bulk aqueous phase. Free metal species are also determined by complexation with a conventional chelating agent under mild conditions. The overall procedure is easy, rapid and allows for a high sample throughput in terms of massive analysis of many samples in the same time period. The method offers substantially low detection limits of 8.5 and 0.9 micrograms l-1 for bound and labile species respectively, with a calibration curve rectilinear in the wide range 40-150 micrograms l-1 for the humate associated and 4-40 micrograms l-1 for the free metal species. The method is free from interferences yielding recoveries in the range 97-102% for various samples of different matrixes.     

Lead (Pb) and arsenic (As) bioaccessibility in various soils from south China

Serious problems are faced in several parts of the world due to the presence of high concentration of fluoride in drinking water which causes dental and skeletal fluorosis to humans. Nalgonda district in Andhra Pradesh, India is one such region where high concentration of fluoride is present in groundwater. Since there are no major studies in the recent past, the present study was carried out to understand the present status of groundwater quality in Nalgonda and also to assess the possible causes for high concentration of fluoride in groundwater. Samples from 45 wells were collected once every 2 months and analyzed for fluoride concentration using an ion chromatograph. The fluoride concentration in groundwater of this region ranged from 0.1 to 8.8 mg/l with a mean of 1.3 mg/l. About 52% of the samples collected were suitable for human consumption. However, 18% of the samples were having less than the required limit of 0.6 mg/l, and 30% of the samples possessed high concentration of fluoride, i.e., above 1.5 mg/l. Weathering of rocks and evaporation of groundwater are responsible for high fluoride concentration in groundwater of this area apart from anthropogenic activities including irrigation which accelerates weathering of rocks.     

Spatial and temporal patterns of dissolved nitrogen and phosphorus in surface waters of a multi-land use basin

Research on relationships between dissolved nutrients and land-use at the watershed scale is a high priority for protecting surface water quality. We measured dissolved nitrogen (DN) and ortho-phosphorus (P) along 130 km of the Calapooia River (Oregon, USA) and 44 of its sub-basins for 3 years to test for associations with land-use. Nutrient concentrations were analyzed for spatial and seasonal patterns and for relationships with land-use and stream discharge. Ortho-P and DN were higher in lower-elevation sub-basins dominated by poorly drained soils and agricultural production compared with higher-elevation sub-basins dominated by well-drained soils and forests. Eight lower basins had at least one sample period with nitrate-N?>?10 mg L^?1. The Calapooia River had lower concentrations of dissolved nutrients compared with lower sub-basins, often by an order of magnitude. Dissolved organic N represented a greater proportion of DN in the upper forested sub-basins. Seasonal nutrient concentrations had strong positive correlations to the percent of a sub-basin that was managed for agriculture in all seasons (p?values?≤?0.019) except summer. Results suggest that agricultural lands are contributing to stream nutrient concentrations. However, poorly drained soils in agricultural areas may also contribute to the strong relationships that we found between dissolved nutrients and agriculture.     

Size and resin fractionations of dissolved organic matter and trihalomethane precursors from four typical source waters in China

Dissolved organic matter (DOM) and its potential to form disinfection by-products (DBPs) during drinking water treatment raise challenges to water quality control. Understanding both chemical and physical characteristics of DOM in source waters is key to better water treatment. In this study, the DOM from four typical source waters in China was fractionated by XAD resin adsorption (RA) and ultrafiltration (UF) techniques. The trihalomethane formation potential (THMFP) of all fractions in the DOM were investigated to reveal the major THM precursors. The fraction distributions of DOM could be related to their geographical origins in a certain extent. The dominant chemical fraction as THM precursors in the DOM from south waters (East-Lake reservoir in Shenzhen and Peal rivers in Guangzhou) was hydrophobic acid (HoA). The size fraction with molecular weight (MW) <1 kDa in both south waters had the highest THMFP. The results of cluster analysis showed that the parameters of fractions including DOC percentage (DOC%), UV₂₅₄%, SUVA₂₅₄ (specific UV₂₅₄ absorbance) and THMFP were better for representing the differences of DOM from the studied waters than specific THMFP (STHMFP). The weak correlation between SUVA₂₅₄ and STHMFP for either size or XAD fractions suggests that whether SUVA₂₅₄ can be used as an indicator for the reactivity of THM formation is highly dependent on the nature of organic matter.     

The effect of light and iron(II)/iron(III) on the distribution of Tl(I)/Tl(III) in fresh water systems

The distribution of aqueous Tl(I)/Tl(III) as a function of light exposure and solution properties was studied by quantifying the oxidation states after separation with ion chromatography and on-line detection with ICP-MS. Ultraviolet irradiation of aqueous solutions containing 1 microg l(-1) Tl(III) and in equilibrium with the atmosphere increases the reduction rate. In systems with photoreduction of Fe(III)(aq) a quantitative oxidation of Tl(I)(aq) was observed, notably at low pH. The process is reversible, as indicated by formation of Tl(I) when the irradiated systems were kept in the dark. In systems with colloidal silica-stabilised ferrihydrite, UV irradiation also leads to oxidation of Tl(I)(aq), but not quantitatively. It is suggested that adsorption of thallium to the ferrihydrite determines the rate of oxidation. Detectable, but not quantitative, oxidation of Tl(I)(aq) took place when natural water samples with 1 microg l(-1) Tl(I)(aq) were exposed to either sunlight or UV-light. For these samples, the reduction was not quantitative when they were kept in the dark for 24 h. The results suggest that the light dependent iron cycle in fresh water systems strongly influences the redox state of thallium.     

Release of arsenic (As) and lead (Pb) from quicklime-sulfate stabilized/solidified soils under diffusion-controlled conditions

A quicklime-sulfate-based stabilization/ solidification (S/S) process for arsenic (As) and lead (Pb) immobilization was evaluated under “semi-dynamic” leaching conditions. In order to simulate aggressive leaching conditions the semi-dynamic leaching tests was modified by using 0.014 N of acetic solution instead of distilled water. Kaolinite-sand and montmorillonite-sand soil samples were artificially contaminated with As and Pb, compacted and cured for 28 days. The semi-dynamic leaching tests were then conducted for 90 days. The effectiveness of the S/S treatment was evaluated by assessing the cumulative release of As and Pb as well as by determining the diffusion coefficients (D _eff) and leachability indices (LX). The release of As and Pb was greatly reduced by quicklime-sulfate treatment as compared to untreated samples. Moreover, the quicklime-sulfate treatment was more effective than the quicklime-only treatment in reducing both As and Pb release. The controlling leaching mechanisms were determined using a diffusion theory model. Upon S/S treatment, As and Pb release was diffusion controlled. The LX of all the treated samples were greater than nine, suggesting that S/S treated samples were suitable for “controlled utilization”.     

Oxidation of Cr(III) to Cr(VI) during chlorination of drinking water

Drinking water treatment typically uses strong oxidants such as chlorine which are capable of converting Cr(III) to Cr(VI). The rates and extent of Cr(III) oxidation by chlorine are not well established. Cr(III) oxidation experiments were therefore conducted in distilled deionized water and New York City tap water dosed initially with Cr(III) and supplemented with sodium hypochlorite to increase free chlorine residual. Reaction progress was monitored using capillary electrophoresis which quenched reactions and allowed for quantification of Cr(VI). Three different forms of Cr(III) were used as reactants: a Cr(III) nitrate salt, Cr(III)-EDTA, and Cr(III) hydroxide. Rates of Cr(VI) production for all three forms of Cr(III) were rapid, on the order of hours. However, oxidation rates slowed and a plateau in Cr(VI) concentrations was reached. This resulted in less than 100% conversion of Cr(III) to Cr(VI) even at relatively high chlorine doses (10 to 100 mg L(-1) as Cl(2)). The loss of free chlorine due to a non-Cr chlorine demand, the precipitation of Cr(III) to Cr(OH)(3)(s), and the partial oxidation of Cr(III) to intermediate oxidation states (i.e. Cr(IV) and Cr(V)) were examined and eliminated as possible explanations for this behavior. Consumption of chlorine via reaction with intermediate oxidation states of Cr is therefore offered as a possible explanation for the plateau in Cr(VI) concentrations.     

Snapping Turtles (Chelydra serpentina) As Monitors for Mercury Contamination of Aquatic Environments

We assessed the distribution of mercury in snapping turtles(Chelydra serpentina) by analyzing front shoulder muscle,back leg muscle, tail muscle, blood, liver, and marginalcarapacial scute (shell) of 26 adult turtles from five smalllakes. Total mercury concentration in muscle ranged from 50 to500 ng g^–1 wet weight and was highly correlated among the threetissue locations. There was no relationship between musclemercury concentration and body size. Mercury concentration inblood was similar to muscle; the correlation with muscle mercuryconcentration was significant but there was some variability. Mercury concentration in shell was much higher than in muscle orblood, ranging from 500 to 3300 ng g^–1, and was highly correlatedwith muscle mercury concentration. Liver mercury concentrationwas similar to shell, but was highly variable and uncorrelatedwith any other tissue. We conclude that snapping turtlesaccumulate mercury from their environment and may be usefulmonitors of mercury contamination.     

Atmospheric arsenic (As) study at five characteristic sampling sites in Taiwan

The main purpose for this study is to observe the seasonal and monthly variations for arsenic (As) in total suspended particulates (TSP) concentration and dry deposition at five characteristic sampling sites during the years 2009 and 2010 in central Taiwan. The results show that the highest and lowest monthly average As concentrations in TSP occurred in January and May at Bei-shi (suburban/coastal) and Quan-xing (industrial) sampling sites. In addition, the results show that the highest and lowest monthly average As dry deposition occurred in October and May at Chang-hua (downtown) and Gao-mei (wetland) sampling sites. This study reflected that the mean highest As concentrations in TSP and mean highest As dry deposition occurred at Quan-xing (industrial). However, the mean lowest As concentrations in TSP and mean lowest As dry deposition also occurred at Gao-mei (wetland). Regarding seasonal variation, the results show that the As average seasonal concentration order in TSP was winter > spring > fall > summer, respectively, at Chang-hua (downtown) and He-mei (residential) sampling sites. Finally, the order of As average seasonal dry deposition was fall > winter > spring > summer, respectively, at Chang-hua (downtown), He-mei (residential), and Gao-mei (wetland) sampling sites.     

Uranium series radionuclides in surface waters from the Shu river (Kazakhstan)

The concentrations of (238)U, (234)U, (226)Ra, (210)Po and (210)Pb have been determined in surface waters collected along the course of the Shu River, lying on the border between Kazakhstan and Kyrgyzstan. In the study area, the river runs through some of the largest uranium deposits worldwide, which were actively exploited during the nuclear weapons and nuclear energy programmes of the former Soviet Union. The data show an increasing trend in uranium concentrations downstream the river from the city of Tokmak to the city of Shu, with good correlation between total uranium concentrations and total dissolved solids. Data on uranium isotopes disequilibrium show the presence of technogenic uranium inputs into the Shu River downstream from the city of Karasu, evidenced by a decrease in the measured (234)U/(238)U isotopic ratio from 1.63 in uncontaminated sites to 1.29 in sites affected by past mining activities.     

Biomonitoring of heavy metals (Cd,Hg, and Pb) and metalloid (As) with the Portuguese common buzzard (Buteo buteo)

The accumulation of heavy metals in the environment may have a wide range of health effects on animals and humans. Thus, in this study, the concentrations of arsenic (As), cadmium (Cd), lead (Pb), and mercury (Hg) in the blood and tissues (liver and kidney) of Portuguese common buzzards (Buteo buteo) were determined by inductively coupled plasma-mass spectrometer (ICP-MS) in order to monitor environmental pollution to these elements. In general, Hg and As were the elements which appeared in the highest and lowest concentrations, respectively. A highest percentage of non-detected concentration was found for blood Cd (94.6 %) but, in turn, it was the only metal that was detected in all kidney samples. The kidney was the analyzed sample which showed the highest concentrations of each element evaluated. Statistically, significant differences among blood, liver, and kidney samples were observed for As and Cd (P?相似文献   

Biomarkers of environmental contaminants in the coastal waters of Estonia (Baltic Sea): effects on eelpouts (Zoarces viviparus)

The eastern Baltic Sea near the Estonian coast is heavily navigated by numerous cargo ships and oil tankers. Hundreds of accidents and oil spills happen yearly in this area. Yet, there is a lack of data concerning the distribution and effects of the environmental contaminants, especially polycyclic aromatic hydrocarbons (PAHs). Different parts of the Baltic Sea have different levels of contamination; therefore a wide range of monitoring stations in coastal areas in the Gulf of Finland and Gulf of Riga were chosen. The aim of the present research was to document the responses of chosen biomarkers of environmental contaminants in different unstudied areas of the Estonian coastal sea. During 2009 and 2010 we measured PAH metabolites, EROD activities, geno- and cytotoxicity, histology, parasites and other biomarkers from the eelpout (Zoarces viviparus), a resident benthic fish species. The results showed that fish from the Gulf of Riga emitted lower levels of fluorescence in fixed wavelength analyses (representing equivalents of PAH metabolites in bile and urine), and consistently, showed less geno- and cytotoxicity and parasite infection, higher liver somatic index (LSI) and a higher condition factor (CF) than fish inhabiting areas close to the Baltic proper and in the Gulf of Finland. The results point to the effect of long-range contaminant transportation, whether atmospheric or hydrodynamic, and also to the intensive shipping activity in international routes. This study fills the gap of knowledge in this area that has persisted until now. Nevertheless, more studies in this area on the different groups of contaminants are necessary, to specify the factors that are responsible for observed biological effects.     

The polycyclic aromatic hydrocarbon composition of mussels (Mytilus edulis) from Scottish coastal waters

Blue mussels (Mytilus edulis) were collected from coastal areas and voes in Shetland and Orkney during March and April 1998 and from various coastal locations around mainland Scotland and from the Islands during October and December 1999. The polycyclic aromatic hydrocarbon concentration and composition (2- to 6-ring parent and branched) were determined for all samples. Additional analysis, including sensory assessment and the determination of n-alkanes and geochemical biomarkers, was also undertaken on the Shetland and Orkney mussels collected in 1998. Mussels from Shetland and Orkney exhibited a wide range of total PAH concentration (14.7 to 7,177 ng g(-1) wet weight). Those mussels collected in 1999 exhibited a narrower concentration range. The lowest value (mussels from Loch Kentra) was 8.4 ng g(-1) wet weight while the maximum concentration was 344.1 ng g(-1) wet weight and was determined in mussels from Granton East in the Firth of Forth. The PAH concentration ratios in mussels from Dury Voe (Grunna), Long Hope and Kirkwall Bay were consistent with a predominately petrogenic source for these contaminants. This was supported by both the sensory assessment and the n-alkane and triterpane profiles. Comparisons of the PAH concentrations in mussels with sediments collected from the same locations around Shetland and Orkney showed that in areas of high sediment PAH concentration the bioavailability of these contaminants was limited.