Assessment of Clam Ruditapes philippinarum as Heavy Metal Bioindicators Using NMR‐Based Metabolomics

There are mainly distributed three pedigrees (White, Liangdao Red, and Zebra) of Manila clam Ruditapes philippinarum in Yantai population along the Bohai marine and coast. However, the biological differences to environmental stressors have been ignored in toxicology studies, which could lead to the distortion of biological interpretations of toxicological effects induced by environmental contaminants. In this study, we applied a system biology approach, metabolomics to compare the metabolic profiles in digestive gland from three pedigrees of clam and characterize and compare the metabolic responses induced by mercury in clam digestive gland tissues to determine a sensitive pedigree of clam as a preferable bioindicator for metal pollution monitoring and toxicology research. The most abundant metabolites, respectively, included branched‐chain amino acids, alanine, and arginine in White samples, glutamate, dimethylglycine, and glycine in Zebra clams and acetylcholine, betaine, glucose, and glycogen in Liangdao Red clams. After 48 h exposure of 20 µg L^?1 Hg²⁺, the metabolic profiles from the three pedigrees of clams showed differentially significant changes in alanine, glutamate, succinate, taurine, hypotaurine, glycine, arginine, glucose, etc. Our findings indicate the toxicological effects of mercury exposure in Manila clams including the neurotoxicity, disturbances in energetic metabolisms and osmoregulation in the digestive glands and suggest that Liangdao Red pedigree of clam could be a preferable bioindicator for the metal pollution monitoring based on the more sensitive classes of metabolic changes from digestive glands compared with other two (White and Zebra) pedigrees of clams.     

Removal of Heavy Metals from Synthetic Mixture as well as Pharmaceutical Sample Via Cation Exchange Resin Modified with Rhodamine B: Its Thermodynamic and Kinetic Studies

A new sorbent was prepared by loading rhodamine B on Amberlite IR‐120. Various physico‐chemical parameters such as effects of adsorbate concentration, contact time, pH, and temperature on the sorption of the dye have been studied. Thermodynamic parameters (ΔH° and ΔS°) were also evaluated for the sorption of dye. Kinetic studies revealed that the sorption of the dye was best fit for pseudo‐second‐order kinetic. The metal ion uptake in different solvent systems has been explored through column studies. On the basis of distribution coefficient (K_d), some heavy metal ions of analytical interest from binary mixtures have been separated. The limit of detection (LOD) for the Ni²⁺ and Fe³⁺ metal ions was 0.81 and 0.60 µg L^?1, and the limit of quantification (LOQ) was found to be 2.72 and 2.0 µg L^?1. This sorbent has also been successfully applied in the analysis of multivitamin formulation. The applicability of the modified resin in the separation of heavy metals constituting real and synthetic samples has been explored.     

Distribution Study of U,V, Mo,and Zr in Different Sites of Lakes Van and Hazar,River and Seawater Samples by ICP‐MS

The aim of this study is to investigate the concentrations of U, Th, V, Mo, and Zr in natural waters taken from Turkey. Among these water species, Lake Van is the largest soda lake and the fourth largest closed basin on Earth. The water samples were collected from 51 locations between 2008 and 2009. The inductively coupled plasma‐MS was used for determinations. The obtained U and Zr concentrations are in the range of 37–110 µg L^?1 and 17–78 µg L^?1 in Lake Van and 0.53–0.81 µg L^?1 and 0.15–0.19 µg L^?1 in Lake Hazar, respectively. The concentration of uranium in other studied waters varies from the lowest 0.09 µg L^?1 in Tigris (Dicle) river to the highest 4.0 µg L^?1 in Mediterranean Sea water. Mean Mo and V concentrations in the studied water samples were found to be in ranges of 0.1–17 and 2.7–113 µg L^?1, respectively. The obtained highest U concentration in Lake Van correlates with the highest Mo and Zr levels compared to the Lake Hazar and river waters. These results imply that there is a young occurrence of uranium minerals around Lake Van. It is concluded that there is about 50.000 ton of uranium in Lake Van water.     

Determination of Sulfamethoxazole and Trimethoprim and Their Metabolites in Hospital Effluent

In this work, an analytical methodological study was carried out to determine the antimicrobials sulfamethoxazole and trimethoprim, as well as their metabolites, in hospital effluent. The determinations were conducted by liquid chromatography tandem mass spectrometry using a hybrid triple quadrupole‐linear ion trap mass spectrometer (LC‐QqLIT‐MS). The data acquisition was made in selected reaction monitoring (SRM) mode, in which two SRM transitions were monitored to ensure that the target compounds were accurately identified by the information dependent acquisition (IDA) function. The limits of detection (LOD) and quantification (LOQ) were 0.25 and 0.80 µg L^?1 for sulfamethoxazole and 0.15 and 0.50 µg L^?1 for trimethoprim. The linear range for the SMX was 0.8–100.0 µg L^?1 and TMP was 0.5–100.0 µg L^?1 on the basis of six‐point calibration curves generated by means of linear regression analysis. The coefficients of the correlation were higher than 0.999, which ensured the linearity of the method. The average concentration of sulfamethoxazole and trimethoprim found in hospital effluent was 27.8 and 6.65 µg L^?1, respectively. The analytical methodology employed allowed two metabolites to be identified, N4‐acetyl‐sulfamethoxazole and α‐hydroxy‐trimethoprim. Fragmentation pathways were proposed.     

Development of Dispersive Liquid–Liquid Microextraction Based on Solidification of Floating Organic Drop for the Determination of Trace Lead in Water

A new method for determining lead (Pb) content was developed by dispersive liquid–liquid microextraction based on the solidification of floating organic droplets followed by flame atomic absorption spectrometry. Under optimum conditions, the calibration graph was linear within the Pb content range of 8.43–400 µg L^?1 with a detection limit of 2.53 µg L^?1. The relative standard deviation for 10 replicate measurements of 20 and 400 µg L^?1 of Pb were 3.41 and 2.78%, respectively. The proposed method was assessed through the analysis of certified reference water and recovery experiments.     

Quantification of Diclofenac in Hospital Effluent and Identification of Metabolites and Degradation Products

In this study the occurrence of diclofenac and sub‐products in effluent emerging from the University Hospital at the Federal University of Santa Maria was investigated. One metabolite was identified and, in aqueous solution, three degradation products. The quantification was conducted by means of HPLC‐DAD, and the determination of metabolite and degradation products by LC–ESI–MS/MS–QTrap. For the HPLC‐DAD method, a 70:30 mixture of methanol/sodium phosphate was used in isocratic mode. For the LC–ESI–MS/MS–QTrap determinations, a mobile phase, where phase A was an ammonium acetate solution 5 × 10^?3 mol L^?1, and phase B was methanol (5 × 10^?3 mol L^?1)/ammonium acetate (9:1, v/v), on gradient mode. The LDs for the HPLC and LC–MS/MS methods, respectively, were 2.5 and 0.02 µg L^?1, the LQs, 8.3 and 0.05 µg L^?1, and the linear range from 10 up to 2000 µg L^?1 and 0.05 up to 10 µg L^?1. As expected, the LC–ESI–MS/MS–QTrap method was more sensitive and less laborious. The metabolite 4′‐hydroxy‐diclofenac was identified. Photolysis was used for the degradation studies and three products of diclofenac were identified (m/z of 214, 286 and 303) in aqueous solution. These results notwithstanding, no degradation products of diclofenac were found in the hospital effluent.     

Spectrophotometric Determination of Cationic Surfactants Based on Their Effect on the Complexes of Chrome Azurol S with Be2+ and Al3+ Cations

Simple, rapid, and sensitive spectrophotometric methods have been proposed for the determination of cationic surfactants (CS) as cetyltrimethylammonium bromide (CTAB), dodecyltrimethylammonium (DTAB), and cetylpyridinium bromide (CPB). The methods are based on the effects of CSs on the complexes of Al³⁺ and Be²⁺ with Chrome Azurol S (CAS). The optimum reaction conditions such as CAS concentration, metal ion concentration, and pH have been studied and found to be 2.0 × 10^?4 mol L^?1 CAS, 0.5 mg L^?1 Al³⁺ or 0.4 mg L^?1 Be²⁺ and pH 5.4. The analytical characteristics of the methods such as limit of detections, limit of quantifications, and linear ranges have been obtained. CTAB, CPB, and DTAB could be determined by the Al–CAS complex in the ranges of 0.50–40.00, 0.20–10.00, and 0.40–10.00 µmol L^?1, and for the Be–CAS complex in the ranges of 0.08–5.00, 0.08–3.00, and 0.20–6.00 µmol L^?1, respectively. The limit of the detections of the method for the determination of CTAB, CPB, and DTAB for the Be–CAS complex has been found as 0.025, 0.024, and 0.061 µmol L^?1, respectively. The interfering effect of some anions and cations was also tested. The method was applied to the determination of CS CTAB in conditioner shampoo and water samples.     

Untersuchungen über die Beeinflussung der planktischen Photosynthese durch anorganische Metallsalze im eutrophen Alpnachersee und der mesotrophen Horwer Bucht

The effects on phytoplankton photosynthesis of inorganic metal salts HgCl₂, CuSO₄, Cd(NO₃)₂, ZnCl₂ and Pb(NO₃)₂ were studied over monthly intervals. In experiments with individual metals, phytoplankton photosynthesis was not adversely affected if the concentration increase above background levels did not exceed 10^?9 mole Hg/l, 5·10^?9 mole Cu/l, 2·10^?8 mole Cd/l, 5·10^?8 mole Zn/l and 2·10^?7 mole Pb/l, respectively. However when the concentration was increased by 5·10^?10 mole Hg/l+5·10^?9 mole Cu/l+5·10^?9 mole Cd/l+5·10^?8 mole Zn/l+5·10^?8 mole Pb/l photosynthesis was significantly reduced, due to a synergetic effect of the combined metals. The influence of phytoplankton density, pH-value concentration of calcium, dissolved organic nitrogen and allochthonous debris on heavy metal toxicity was investigated. Changes in phytoplankton composition are believed to the main reason for the seasonal variation in the toxic effects of heavy metals.     

Clam burrowing behaviour and mortality related to sediment copper

Gravel sediment freshly enriched with over 4.4 μg Cu g^?1 significantly increased the burrowing and reburrowing times of Littleneck marine clams (Protothaca staminea). Abnormal burrowing behaviour was observed with time-lapse video. Aged (1 day) copper-enriched sediment did not affect clam burrowing time. Copper in sediment porewater declined three days after sediment enrichment to background levels without change in total sediment copper. In a long-term experiment, clams with increased burrowing time into copper-enriched sediment had up to 25% mortality after 12–29 days burial in the sediment. The majority of clam mortality was found in clams burrowing within the first 48 h. Over 7 weeks there was blackening of sediment and clam shells proportional to sediment copper enrichment.     

Coprecipitation with Cu(II)‐4‐(2‐Pyridylazo)‐resorcinol for Separation and Preconcentration of Fe(III) and Ni(II) in Water and Food Samples

The coprecipitation method is widely used for the preconcentration of trace metal ions prior to their determination by flame atomic absorption spectrometry (FAAS). A simple and sensitive method based on coprecipitation of Fe(III) and Ni(II) ions with Cu(II)‐4‐(2‐pyridylazo)‐resorcinol was developed. The analytical parameters including pH, amount of copper (II), amount of reagent, sample volume, etc., were examined. It was found that the metal ions studied were quantitatively coprecipitated in the pH range of 5.0–6.5. The detection limits (DL) (n = 10, 3s/b) were found to be 0.68 µg L^?1 for Fe(III) and 0.43 µg L^?1 for Ni(II) and the relative standard deviations (RSD) were ≤4.0%. The proposed method was validated by the analysis of three certified reference materials (TMDA 54.4 fortified lake water, SRM 1568a rice flour, and GBW07605 tea) and recovery tests. The method was successfully applied to sea water, lake water, and various food samples.     

The effect of drawdown on suspended solids and phosphorus export from Columbia Lake,Waterloo, Canada

This study examines the effect of drawdown on the timing and magnitude of suspended solids and associated phosphorus export from a 12 ha reservoir located in an urbanized watershed in southern Ontario, Canada. Water level in Columbia Lake was lowered by 1·15 m over a 2‐week period in November 2001. The total phosphorus (TP) concentrations ranged from 63 to 486 µg L^?1 in Columbia Lake and 71 to 373 µg L^?1 at its outflow. All samples exceeded the Provincial Water Quality Objective of 30 µg TP L^?1. Outflow concentrations of suspended solids and TP increased significantly with decreasing lake level and were attributed to the resuspension of cohesive bottom sediments that occurred at a critical threshold lake level (0·65 m below summer level). Suspended solids at the outflow consisted of flocculated cohesive materials with a median diameter (D₅₀) of c. 5 µm. Particulate organic carbon accounted for 8·5% of the suspended solids export by mass. A total mass of 18·5 t of suspended solids and 62·6 kg TP was exported from Columbia Lake, which represents a significant pulse of sediment‐associated P to downstream environments each autumn during drawdown. The downstream impacts of this release can be minimized if the water level in Columbia Lake is lowered no more than 0·5 m below summer levels. Copyright © 2004 John Wiley & Sons, Ltd.     

Auswirkung von Schwermetallgemischen auf die biologische Behandlung naphthalinsulfonsäurehaltiger Abwässer

Effect of Mixtures of Heavy Metals on the Biological Treatment of Sewages Containing Naphthalenesulfonic Acid Biological wastewater treatment processes can be destabilized considerably by heavy metals. In this investigation, the effect of loadings of heavy metals on the degradation of naphthalene-2-sulfonic acid (2NS) by immobilized bacteria in continuously operated airlift-loop reactors was studied. Shock loadings with mixtures of cadmium and nickel, or cadmium and zinc, respectively, resulted in increases in inhibition compared to those observed with the single metals. In contrast, the 2NS-degradation was less inhibited by shock loadings with mixtures of nickel and zinc than by the single metal ions. Repeated shock loadings up to 100 mg L^?1 nickel and 1000 mg L^?1 zinc effected an adaptation of the microorganisms. Continuous loadings with up to 10 mg L^?1 cadmium and nickel each, or with 50 mg L^?1 nickel and 210 mg L^?1 zinc, respectively, did not inhibit the degradation of 2NS. The permanent loadings led to an adaptation of the bacteria with an increased biosynthesis of proteins from 0.2 to 0.5 g g^?1 cell dry weight. However, if the immobilized cells were incubated with mixtures of cadmium and nickel, the specific polysaccharide content decreased to less than 0.2 g g^?1 cell dry weight, resulting in a detachment of the biofilms.     

Nitrate content and potential microbial signature of rock glacier outflow,Colorado Front Range

Here we characterize the nutrient content in the outflow of the Green Lake 5 rock glacier, located in the Green Lakes Valley of the Colorado Front Range. Dissolved organic carbon (DOC) was present in all samples with a mean concentration of 0·85 mg L^?1 . A one‐way analysis of variance test shows no statistical difference in DOC amounts among surface waters (p = 0·42). Average nitrate concentrations were 69 µmoles L^?1 in the outflow of the rock glacier, compared to 7 µmoles L^?1 in snow and 25 µmoles L^?1 in rain. Nitrate concentrations from the rock glacier generally increased with time, with maximum concentrations of 135 µmoles L^?1 in October, among the highest nitrate concentrations reported for high‐elevation surface waters. These high nitrate concentrations appear to be characteristic of rock glacier outflow in the Rocky Mountains, as a paired‐difference t‐test shows that nitrate concentrations from the outflow of 7 additional rock glaciers were significantly greater compared to their reference streams (p = 0·003). End‐member mixing analysis suggest that snow was the dominant source of nitrate in June, ‘soil’ solution was the dominant nitrate source in July, and base flow was the dominant source in September. Fluoresence index values and PARAFAC analyses of dissolved organic matter (DOM) are also consistent with a switch from terrestrial DOM in the summer time period to an increasing aquatic‐like microbial source during the autumn months. Copyright © 2006 John Wiley & Sons, Ltd.     

Comparison of Pb(Ⅱ) and Cd(Ⅱ) micro-interfacial adsorption on fine sediment in the Pearl River Basin,China

The complex micro-interfacial interaction theories of heavy metal ions such as Pb(Ⅱ)and Cd(Ⅱ)adsorption on fine sediment in aqueous solution were not systematically investigated.The aim of this work was to reflect the micro-interfacial adsorption characteristics.Sediment samples were collected from an estuary.The Isothermal and kinetics adsorption experiment were done to acquire the data.Isothermal,kinetics,film diffusion and intraparticle diffusion models were adopted to fit the adsorption experimental data.The results indicated that the Langmuir,Freundlich and Temkin models were suitable for analyzing the isothermal experimental data.The maximum adsorption capacities of Pb(Ⅱ)and Cd(Ⅱ)on the sediment were 1.1377 and 0.9821 mg·g-1,respectively.The qm and KL of the Langmuir model,Kf and nF of the Freundlich model,and b and A of the Temkin model all exhibited a power function relationship with the initial adsorbate concentration.The pseudo-second-order model provided a better fit for the experimental kinetics data compared with the fit of the pseudo-first-order and Elovich models.The pseudo-second-order parameters k2 and qe of Pb(Ⅱ)and qe of Cd(Ⅱ)both had a power function relationship with adsorption time,additionally,the k2 of Cd(Ⅱ)had an exponential function relationship with adsorption time.The liquid-film diffusion parameters kfd of Pb(Ⅱ)and Cd(Ⅱ)were 0.0569 and 0.1806 min
1,respectively.The intraparticle diffusion parameter kid values of Pb(Ⅱ)and Cd(Ⅱ)were 0.0055 mg$g
1$min1/2 and 0.0049 mg$g
1$min1/2,respectively.The physical significance of the model parameters showed that Pb(Ⅱ)adsorption on sediment was stronger than Cd(Ⅱ).The results of this study provided a theoretical reference for the micro-interfacial mechanism of heavy metal ion adsorption on sediment.     

Determination of Trace Levels of Nickel and Manganese in Soil,Vegetable, and Water

A simple and reliable method for rapid and selective extraction and determination of trace levels of Ni²⁺ and Mn²⁺ was developed by ionic liquid (IL) based dispersive liquid–liquid microextraction coupled to flame atomic absorption spectrometry (FAAS) detection. The proposed method was successfully applied to the preconcentration and determination of nickel and manganese in soil, vegetable, and water samples. After preconcentration, the settled IL‐phase was dissolved in 100 µL of ethanol and aspirated into the FAAS using a home‐made microsample introduction system. Injection of 50 µL of each analyte into an air–acetylene flame provided very sensitive spike‐like and reproducible signals. Effective parameters such as pH, amount of IL, volume of the disperser solvent, concentration of the chelating agent, and effect of salt concentration were inspected by a (2^5‐1) fractional factorial design to identify the most important parameters and their interactions. Under optimum conditions, preconcentration of 10 mL sample solution permitted the detection of 0.93 µg L^?1 Ni²⁺ and 0.52 µg L^?1 Mn²⁺ with enrichment factors 77.2 and 82.6 for Ni²⁺ and Mn²⁺, respectively. The accuracy of the procedure was evaluated by analysis of a certified reference material (CRM TMDW‐500, drinking water).     

Assessment of arsenic and heavy metal pollution and ecological risk in inshore sediments of the Yellow River estuary,China

In order to investigate the pollution levels, sources and ecological risks of arsenic (As) and heavy metals (Cr, Ni, Cu, Zn, Pb and Cd) in inshore sediments of the Yellow River estuary, the surface sediment in areas of inshore coastal waters were sampled in October 2014 as the flow-sediment regulation project (FSRP) was implemented for 13 years. Results showed that the concentrations of As and heavy metals in inshore sediments of the Yellow River estuary were in the order of Zn?>?Cr?>?Cu?>?Ni?>?Pb?>?As?>?Cd. Higher levels of As, Cr, Ni, Cu, Zn and Pb generally occurred in fine-grained sediments of the Yellow River estuary and the southeast region, which was consistent with the spatial distribution of clay. In contrast, higher concentrations of Cd were generally observed in northwest area of the Yellow River estuary and near the Qingshuigou estuary, which showed similarly spatial distribution with that of sand. The sediment quality guidelines (SQG_S) and geoaccumulation indices (I_geo) indicated that the inshore sediments were polluted by Cu, Cd, As, Pb and Zn, and, among them, Cd pollution was more serious. Ecological risk indices (E _r ⁱ ) demonstrated low risks for Cr, Ni, Cu, Zn, Pb and As, and high potential toxicity by Cd. The integrated ecological risk index implied that 6.8% of stations presented moderate risk, 4.5% of stations exhibited disastrous risk, and 88.7% of stations demonstrated considerable risk. Principal component analysis indicated that Ni, Cu, Zn, Pb and As might originate from common pollution sources, while Cr and Cd might share another similar sources. With the continuous implementation of FSRP, As and heavy metal levels in inshore sediments of the Yellow River estuary could be classified as stage I (2002–2010) and stage II (2010–2014). In the stage I, As, Cr, Ni, Cu, Zn and Pb levels fluctuated but decreased significantly, whereas Cd concentrations showed little variation. In the stage II, As and heavy metal levels significantly increased although some little fluctuations occurred. The continuous accumulation of As and heavy metals (especially for Cd) in inshore sediments of the Yellow River estuary would occur again as the FSRP was implemented for 9 years (since 2010). The ecotoxicological risk of Cd, As, Ni and Cu in inshore sediments might be more serious since the accumulation of the four elements would be continuously occurred in future years. Next step, there will be long-term potential consequences for marine organism if effective measures are not taken to control the loadings of metal pollutants into estuary.     

Heavy metal concentrations during storm events in a rehabilitated industrialized catchment

Water quality data collected on a fortnightly or monthly basis are inadequate for assessment and modelling of many water quality problems as storm event samples are underrepresented or missed. This paper examines the stormflow dynamics of heavy metals (Pb, Cu, Cd and Zn) in the Nant‐y‐Fendrod stream, South Wales, which has been affected by 250 years of metal smelting, followed by 35 years of landscape rehabilitation measures. For storm events of contrasting (very dry and very wet) antecedent conditions in May 2000 and February 2001, respectively, temporal changes in streamwater heavy metal concentrations above and below an in‐line flood detention lake are analysed. At the upstream site, peaks in total metal concentration were recorded on the rising limb for Pb (0·150 mg l^?1) and Cu (0·038 mg l^?1) but on the falling limb for Zn (1·660 mg l^?1) and Cd (0·006 mg l^?1) in the summer 2000 storm event, yielding clockwise and anticlockwise hysteretic loops respectively. In contrast, metal concentrations, although high throughout the winter storm event, were diluted somewhat during the storm peak itself. The Pb and Cu appear to be supplied by quickflow processes and transported in close association with fine sediment, whereas Zn and Cd are delivered to the channel and lake by slower subsurface seepage in dissolved form. In the winter 2001 event, antecedent soil moisture and shallow groundwater levels were anomalously high and seepage sources of dissolved metals dominated. Downstream of the lake, Pb and Cu levels and suspended sediment were high in the summer storm, but low in the winter storm, suggesting retention with deposition of fine sediment in the lake during the latter. In the winter storm, Zn and Cd levels were higher downstream than upstream of the lake, perhaps because of additional seepage inputs from the surrounding slopes, which failed to have an impact during summer. An understanding of the complex interplay of antecedent soil moisture and the dynamics of subsurface seepage pathways in relation to the three‐dimensional distribution of sources is important in modelling heavy metal fluxes and levels in contaminated urban catchments. Copyright © 2003 John Wiley & Sons, Ltd.     

Evaluating sulfur dynamics during storm events for three watersheds in the northeastern USA: a combined hydrological,chemical and isotopic approach

Concerns related to climate change have resulted in an increasing interest in the importance of hydrological events such as droughts in affecting biogeochemical responses of watersheds. The effects of an unusually dry summer in 2002 had a marked impact on the biogeochemistry of three watersheds in the north‐eastern USA. Chemical, isotopic and hydrological responses with particular emphasis on S dynamics were evaluated for Archer Creek (New York), Sleepers River (Vermont) and Cone Pond (New Hampshire) watersheds. From 1 August to 14 September 2002, all three watersheds had very low precipitation (48 to 69 mm) resulting in either very low or no discharge (mean 0·015, 0·15 and 0·000 mm day^?1 for Archer Creek, Sleepers River and Cone Pond, respectively). From 15 September to 31 October 2002, there was a substantial increase in precipitation totals (212, 246 and 198 mm, respectively) with increased discharge. Archer Creek was characterized by a large range of SO₄^2? concentrations (152 to 389 µeq L^?1, mean = 273 µeq L^?1) and also exhibited the greatest range in δ³⁴S values of SO₄^2? (?1·4 to 8·8 ‰ ). Sleepers River's SO₄^2? concentrations ranged from 136 to 243 µeq L^?1 (mean = 167 µeq L^?1) and δ³⁴S values of SO₄^2? ranged from 4·0 to 9·0 ‰ . Cone Pond's SO₄^2? concentrations (126–187 µeq L^?1, mean = 154 µeq L^?1) and δ³⁴S values (2·4 to 4·3 ‰ ) had the smallest ranges of the three watersheds. The range and mean of δ¹⁸O‐SO₄^2? values for Archer Creek and Cone Pond were similar (3·0 to 8·9 ‰ , mean = 4·5 ‰ ; 3·9 to 6·3 ‰ , mean = 4·9 ‰ ; respectively) while δ¹⁸O‐SO₄^2? values for Sleepers River covered a larger range with a lower mean (1·2 to 10·0 ‰ , mean = 2·5). The difference in Sleepers River chemical and isotopic responses was attributed to weathering reactions contributing SO₄^2?. For Archer Creek wetland areas containing previously reduced S compounds that were reoxidized to SO₄^2? probably provided a substantial source of S. Cone Pond had limited internal S sources and less chemical or isotopic response to storms. Differences among the three watersheds in S biogeochemical responses during these storm events were attributed to differences in S mineral weathering contributions, hydrological pathways and landscape features. Further evaluations of differences and similarities in biogeochemical and hydrological responses among watersheds are needed to predict the impacts of climate change. Copyright © 2008 John Wiley & Sons, Ltd.     

Degradation of Bezafibrate with UV/H2O2 in Surface Water and Wastewater Treatment Plant Effluent

Bezafibrate (BZF), a widely used lipid regulator, is a potential threat to ecosystems and human health in water, and the recent research showed that advanced oxidation processes (AOPs) are much more effective for BZF degradation. In this study, we investigated the photochemical decomposition of BZF in surface water and effluent from waste water treatment plants (WWTP) by UV/H₂O₂ process. The results showed that the UV/H₂O₂ process was a promising method to remove BZF at low concentration, generally at µg L^?1 level. When initial concentrations reach 100 µg L^?1 in the deionized water, >99.8% of BZF could be removed in 16 min under UV intensity of 61.4 µm cm^?2, at the H₂O₂ concentration of 0.1 mg L^?1, and neutral pH condition. Moreover, BZF degradation was inhibited in this process when humic acid (HA) and inorganic solution anions were added to the deionized water solutions, including chloride, nitrate, bicarbonate, and sulfate, significantly. In the surface water and effluent of WWTP, however, the removal efficiency of BZF was lower than that in the deionized water because of the interference of complex constituents in the surface water and effluent. Some main intermediates at the m/z range of 100–400 were observed by high performance LC‐MS (HPLC/MS) and a simple pathway of BZF degradation by UV/H₂O₂ was proposed.