Measuring dissolved organic carbon δ13C in freshwaters using total organic carbon cavity ring-down spectroscopy (TOC-CRDS)

This article reports the first application of coupled total organic carbon cavity ring-down spectroscopy (TOC-CRDS) for the analysis of the ??¹³C signature of dissolved organic carbon (DOC) in freshwater samples. DOC represents a major, dynamic component of the global carbon cycle. The export of DOC from soils into rivers and groundwaters may be highly climate sensitive, and much of this export may occur in ephemeral fluxes. Thus, a robust, simple and inexpensive method for the continuous determination of DOC concentration and quality is urgently needed. We detail recent advances made in the analysis of the ??¹³C signature of DOC using a TOC-CRDS system optimised for the analysis of DOC with natural abundances greater than 2.5?mg?L^?1 with no sample pre-concentration required and sample volumes of 40?mL. Precision between replicated samples was comparable to conventional analysis by gas-source isotope ratio mass spectrometry, yielding ??¹³C values with standard deviations of?±?0.5??? for DOC concentrations higher than 1.5?mg?L^?1. The utility of this technique for the analysis of DOC in samples with a broad range of compositions and concentrations (2.5?C25?mg?L^?1 DOC) is demonstrated. Since DOC ??¹³C can be measured continuously, ca. 45?min per measurement, this method enables the online monitoring of DOC in river water, water intakes and treated waters, allowing changes in DOC fluxes to be monitored in real time.     

Solid phase extraction and preconcentration of cobalt in mineral waters with PAR-loaded Amberlite XAD-7 and flame atomic absorption spectrometry

A simple, sensitive, accurate, and selective method for determination of ultratrace levels of Co is modified. The method is based on preconcentration of Co on the PAR-loaded Amberlite XAD-7 at pH 2.0 ± 0.2 for contact time as low as 45 min. The adsorbed cobalt was eluted with concentrated nitric acid and measured by flame atomic absorption spectrometry. Recoveries up to 90% were achieved. The optimized preconcentration method was applied to cobalt determination in natural mineral waters. The detection limit was found to be 0.1 ng mL⁻¹. The relative standard deviation was found to be 13% for 600 mL of 2.0 ng mL⁻¹, for 10 replicate preconcentration procedures. Cobalt concentrations in the studied water samples were found to be in the ranges of 0.5–3.5 ng mL⁻¹.     

A novel ligand for cloud point extraction to determine gold content in ore samples

Gold is a valuable metal occurring usually at very low concentrations in complex natural samples. Gold analysis thus needs preconcentration methods. Classical liquid–liquid extraction involves hazardous organic solvents. Alternatively, cloud point extraction involves non-toxic and nonvolatile surfactants. Here, we analyzed ore samples. The complex of Au(III) with sulphapyridylazo resorcin was extracted by the cloud point method. Concentrations were measured by flame atomic absorption spectrometry. We tested the effects of pH, reagent concentration, Triton X-100 surfactant concentration, equilibration temperature and time. Results show that the best detection limit of the method was 0.48 µg L^?1 for Au with a preconcentration factor of 31 times. Calibration is linear in range of 6.4–2,000 µg L^?1, and relative standard deviations are lower than 5 %. Quantum chemical computations reveal the plausible structure of the gold–ligand complex. This report represents the first determination of gold using sulphapyridylazo resorcin as a ligand.     

Voltammetric determination of the herbicide Bifenox in drinking and river water using a silver solid amalgam electrode

A new method for the determination of submicromolar and nanomolar concentrations of herbicide Bifenox using differential pulse voltammetry at a mercury meniscus modified silver solid amalgam electrode is described. This new type of working electrode is non-toxic, environmentally friendly, and compatible with principles of green analytical chemistry, and its surface can be easily electrochemically renewed in the case of passivation. The newly developed direct differential pulse voltammetric determination of Bifenox gives limit of determination 6.7·10^?7 and 6.9·10^?7?M in drinking and river water, respectively. Both the selectivity and the sensitivity can be further increased by preliminary separation and preconcentration using solid phase extraction. This combination enables to reach limit of determination 0.9?×?10^?9 and 1.5?×?10^?9?M for drinking and river water, respectively. Because of lower running and investment costs, this electroanalytical method can be used for large scale monitoring of possible water contamination with tested herbicide.     

Atmospheric mercury at mediterranean coastal stations

Mercury in air has been measured at five coastal Mediterranean sites, involving measurements in Spain, France, Italy, Slovenia and Israel. Four two-weeks long measurements campaigns were performed at the five sites. The measurements were carried out during autumn 2003 and winter, spring and summer 2004. Total gaseous mercury/elemental gaseous mercury, particulate mercury and divalent gaseous mercury were measured in parallel at the five sites. The activities constituted a subtask of the EU funded MERCYMS research project, which also included Mediterranean Sea cruises where both mercury in air and water were measured. The result from an evaluation of all the coastal air data is presented. Mercury concentrations from the different sites are compared with similar data obtained in northern Europe and elsewhere. The result shows that the background concentration of mercury in Mediterranean coastal air is lower than earlier anticipated. Background concentrations of TGM, RGM and TPM corresponded to 1.75–1.80 ng m⁻³, 1–13 and 3–23 pg m⁻³, respectively. The measurements also showed that the mercury concentration occasionally can be very high in some areas due to local anthropogenic emissions. It is proposed that diurnal variation in RGM concentrations observed during situation with nocturnal inversion merely is an effect of meteorology rather than due to local photochemistry.     

Mercury distribution in the sediments of Ambarlı Port Area,Sea of Marmara (Turkey)

The purpose of this study is to investigate historical and current mercury (Hg) contamination in the surface and core sediments of the Ambarl? Port area. Textural parameters, total organic carbon (TOC), ²¹⁰Pb and total Hg (THg) contents were measured. Mercury contamination of the sediments was assessed on the basis of the enrichment factor (EF), anthropogenic factor (AF), index of geoaccumulation (Igeo) and corresponding sediment quality guidelines. Most surface sediment samples were also non-toxic with mercury concentrations below the effects range-low (ERL) value, but mercury levels at five stations were between ERL and effects range-median (ERM) values, where occasional adverse effects concerning risk analysis are expected. The EF and Igeo analysis showed that there was no significant mercury enrichment and contamination in the core sediment before the 1650s, but values increased from then onwards to 2009 (being especially accelerated in line with port activities from 1989), disclosing a serious ecotoxicological risk to sediment-inhabited marine organisms.     

Mercury pollution in the Sonbhadra district of Uttar Pradesh,India, and its health impacts

The Sonbhadra district in the Singrauli area of Uttar Pradesh, India, has many coal mines and thermal power plants and is a critically polluted area. Many residents of this area reported adverse health conditions which may be linked to metal pollution, especially of mercury investigated here.

In May 2012, samples of water (23), soil (7), blood, hair, and nails from persons showing adverse health conditions selected at random were collected and analyzed for total mercury by atomic absorption spectrometry.

Twenty percent drinking water samples contained mercury from 3 to 26 μg L^?1 (3–26 times the permissible limit). Soil samples had 0.5–10.1 mg kg^?1 Hg.

The average concentrations of mercury in human blood, hair, and nails were found to be 34 μg L^?1, 7.4 mg kg^?1, and 0.8 mg kg^?1, respectively. Mercury concentrations in the blood of these persons were 45 and 28 μg L^?1 on average in the case of men and women. This is much higher than the safe level of 5.8 μg L^?1 set by the United States Environmental Protection Agency (USEPA).

It was concluded that all residents of Sonbhadra sampled could be suffering from mercury toxicity as the area is polluted by Hg released from the coal-fired thermal power plants.     

Synthesis of 2,3-dihydroxynaphthalene-functionalized Amberlite XAD-4 resin: Applications for the separation and preconcentration of trace metal ions prior to their determination by inductively coupled plasma atomic emission spectrometry

A simple, sensitive column solid-phase extraction procedure for separation and preconcentration of Cu(II), Ni(II), Co(II), and Cd(II) in spiked and natural water samples using 2,3-dihydroxynaphthalene-functionalized Amberlite XAD-4 (XAD-4-DHN) chelating resin prior to their determination by inductively coupled plasma atomic emission spectrometry was discussed. The optimum experimental parameters such as pH, volume of sample and eluent, flow-rates of uptake and stripping, and sorption capacity of the chelating resin, were evaluated. The effect of the electrolytes and the cations on the preconcentration of metal ions was also investigated. The chelating resin could be reused for more than 20 cycles of sorption–desorption without any significant change (<1.0%). Recoveries obtained from this method range from 96 to 102% with R.S.D of 2.50 (n = 4). The detection limits for Cu(II), Ni(II), Co(II), and Cd(II) were found to be 1.9, 0.9, 1.2 µg, and 1.4 µg L^?1, respectively. The proposed method was applied for the determination of Cu(II), Ni(II), Co(II), and Cd(II) in spiked, tap water, and river water samples.     

Preliminary study on health risk from mercury exposure to residents of Wujiazhan town on the Di’er Songhua river, Northeast China

Mercury concentrations in hair are typically used as a biomarker to assess exposure to mercury. A total of 108 hair samples were collected from residents (age range 5–73 years) of Wujiazhan town, northeast China, to determine total mercury concentrations. Hair mercury concentrations ranged from 0.16 to 199 mg kg^–1 with an average value of 3.41 mg kg⁻¹. The relationships between mercury concentration and gender and between hair mercury concentration and age were not significant. Overall, 16.7% of all samples were above the RfD value published by the United States Environmental Protection agency. The results indicate that there may be some been health risk from mercury exposure to the residents in the study area.     

Online solid phase preconcentration using EGDMA–MAA copolymer for lead determination by FAAS

A Ethylene glycol dimethacrylate (EGDMA) methacrylic acid (MAA) resin was used for preconcentration of lead at trace levels in water samples. For this purpose, a flow-injection, solid phase extraction method was developed for the determination of lead by flame atomic absorption spectrometry. Lead ions were sorbed on a EGDMA–MAA column at pH 4, followed by an elution step using 288 µL of 4.0 M nitric acid solution and determination by flame atomic absorption spectrometry. Optimum conditions for quantitative sorption involving the pH, sample volume, loading and elution flow rates, eluent type, and volume were investigated. A 868-fold enrichment factor could be reached. The detection limit for the water samples, estimated from the noise on the signal obtained for 250 mL of 10 µg L^?1 loaded at 4.9 mL min^?1 was 1.04 µg L^?1. The method was applied for lead determination in river water samples collected in Edirne, Turkey. Recoveries of spiked solutions (10 µg L^?1) to river water samples were quantitative. Finally, the method was validated by the analysis of certified reference material SRM 2704 (Buffalo River Sediment).     

Distribution of mercury in the sediments of some freshwater bodies in Ethiopia

Sediment samples were collected from Tinishu Akaki River (TAR), Lake Awassa, and Lake Ziway, Ethiopia for determination of mercury. The air-dried samples were analyzed for mercury with a differential atomic absorption spectrometer after thermal evaporation of bound mercury converting it to its atomic form. Certified reference materials (CRMs) of sediments and soils were used to validate the method. The recovery of mercury from CRMs and sediments was in the range of 95–100%. The limit of detection for the determination of mercury was 50?ng?kg^?1. The concentration of total mercury in the sediments varied from 3.9 to 110?µg?kg^?1 for TAR, 14 to 67?µg?kg^?1 for Lake Awassa, and 17 to 110?µg?kg^?1 for Lake Ziway. It was found that the total mercury concentrations in all samples were below the United States Environmental Protection Agency guideline of 200?µg?kg^?1.     

Determination of cobalt by air-assisted liquid–liquid microextraction

Abstract

A rapid and selective technique for extraction, preconcentration and determination of trace amounts of cobalt in water and pharmaceutical samples by air-assisted liquid–liquid microextraction combined with flame atomic absorption spectrometry is proposed. 1-Nitroso-2-naphthol is used as a complexing agent and 1-octanol as an extraction solvent. Parameters relevant for analytical effectivity, i.e. pH of sample solution, concentration of complexing agent, volume of extraction solvent, and number of extraction cycles are optimized using a Box–Behnken design. At optimum conditions, a dynamic linear range of 5–600?µg L^?1 is obtained, with a limit of detection of 1.2?µg L^?1. The method is used for determination of Co(II) in environmental water and pharmaceutical samples.     

A simple ligandless microextraction method based on ionic liquid for the determination of trace cadmium in water and biological samples

A simple and efficient ionic liquid-based ligandless microextraction method has been developed for preconcentration of cadmium ions (Cd²⁺) as a step prior to its determination by flame atomic absorption spectrometry (FAAS) with a micro-sample introduction system. In this approach, the ionic liquid (IL) 1-butyl-3-methylimidazolium hexafluorophosphate [C₄mim][PF₆] and ethanol were used as extractant and dispersive solvents to preconcentrate the Cd²⁺ in different waters, acid digested scalp hair, and nail samples. Some analytical parameters influencing the extraction efficiency of Cd²⁺ and its subsequent determination, including pH, IL volume, dispersant solvent volume, sample volume, temperature, incubation time, and matrix effect, were optimized. Under optimal conditions, the limit of detection (LOD), limit of quantification (LOQ), and enhancement factor (EF) were 0.4 μg L^?1, 1.3 μg L^?1, and 50, respectively. The relative standard deviation (RSD) of 100 μgL^?1 Cd²⁺ was 4.3% (n = 6). The validity of the proposed method was checked by determining Cd²⁺ in certified reference material (TM-25.3 fortified water) and standard addition; the results showed sufficient recovery (>98%) of Cd²⁺ within the certified value. The method was applied for preconcentration and determination of cadmium in waters and biological samples.     

Solid phase extraction of trace metals from environmental samples using Amberlite XAD-7 loaded with 2-hydroxy-propiophenone-4-phenyl-3-thiosemicarbazone and determination by inductively coupled plasma–atomic emission spectrometry

A method for the solid phase extraction of trace metals, namely Co, Cu, Pb, Ni and Zn, from environmental and biological samples using column Amberlite XAD-7 loaded with 2-hydroxy-propiophenone-4-phenyl-3-thiosemicarbazone (HPPPTSC) and determination by inductively coupled spectrometry (ICP–AES) has been developed. The reagent has the capacity to form chelate complexes with the metals because of three binding sites in the reagent molecule. The optimum experimental conditions for the quantitative sorption of five metals, pH, effect of flow rate, concentration of eluent, sorption capacity and the effect of diverse ions on the preconcentration of analytes have been investigated. The sorption capacity of the resin has 83, 127, 35, 88 and 85?µmol?g^?1 for Co²⁺, Cu²⁺, Pb²⁺, Ni²⁺ and Zn²⁺, respectively. The preconcentration factors for Co²⁺, Cu²⁺, Pb²⁺, Ni²⁺ and Zn²⁺ were 100, 110, 120, 140 and 150, respectively. The accuracy of the proposed procedure was evaluated by standard reference materials. The achieved results were in good agreement with certified values. The proposed method was applied for the determination of trace metals in river water and plant leaves.     

A gradient of mercury concentrations in Scottish single malt whiskies

Mercury (Hg) concentrations were measured in 26 Scottish single malt whiskies, and all found to be very low (<10 ng L⁻¹), posing no threat to human health through reasonable levels of consumption. However, a significant south-to-north declining gradient in Hg concentrations was observed reflecting that reported for atmospheric deposition. We speculate that this gradient could be due to a combination of contemporary deposition and the legacy of industrial mercury emissions and deposition over the last 200 years affecting concentrations in local waters used in whisky production. As UK atmospheric emissions of mercury have declined by 90 % since the 1970s, we suggest that whisky being produced today should have even lower Hg concentrations when consumed in 10- to 15-years time. This reduction may be compromised by the remobilisation of contaminants stored in catchment soils being transferred to source waters, but is very unlikely to raise the negligible health risk due to Hg from Scottish single malt whisky consumption.

     

Characterization of environmental water samples using strontium and lead stable isotope compositions

A simple procedure using both cation and anion exchange chromatography has been applied in the study of lead and strontium isotope composition in rain and stream water samples from remote catchments in Scotland. Whereas the soil released strontium to stream waters, lead was removed from rain water and the concentrations in stream waters were very low. Highly precise analysis by thermal ionisation mass spectrometry proved necessary in the determination of strontium isotope composition. The ⁸⁷Sr/⁸⁶Sr ratio in rain water was close to that of marine strontium but the ratios in stream waters were constant and highly characteristic for the stream. In the case of the stream at the Sourhope site, the ratio (0.70798 ± 0.00005) was less than that in rain water and probably resulted from the weathering of one specific mineral. The results suggested that the ⁸⁷Sr/⁸⁶Sr ratios could be used as a stable isotope tracer of waters and to provide information on the weathering processes. Two major anthropogenic components of lead were identified in water samples. One had its origin in petrol additives whereas the other was probably of industrial origin. The low ²⁰⁶Pb/²⁰⁷Pb ratios observed in stream waters confirmed the lead as being of anthropogenic origin and the data suggested that there was a movement, albeit very small, of lead from the soil to waters.     

Occurrence of endocrine disruptor compounds in the estuary of the Iberian Douro River and nearby Porto Coast (NW Portugal)

Previous studies in the Douro River estuary, based on occasional sampling, showed the presence of several estrogenic disrupting chemicals (EDCs). In sequence, we hypothesized that such type of pollution was more likely an enduring issue than an occasional phenomenon, and that it may even affect recreational beaches in each side of the estuarine mouth. Thus to conclude about the continuous influx of EDCs, water samples were taken twice a day, once per a week, from March to May of 2009, at four sites within the estuary and at two sites in the coastline. After solid-phase extraction, the extracts were prepared for GC-MS analysis of 11 reference EDCs. These embraced natural and pharmaceutical estrogens (17β-estradiol, estrone and 17α-ethynylestradiol) and xenoestrogenic industrial pollutants (4-octylphenol, 4-nonylphenol, and their mono and diethoxylates and bisphenol A). Data showed the ubiquitous presence of potentially hazardous amounts of natural estrogens (particularly of estradiol, ca 5.5?ng?L^?1) and persistent organic pollutants such as nonylphenol mono (up to 550?ng?L^?1) and diethoxylate (up to 2000?ng?L^?1). It was concluded that the targeted area is continuously polluted by the assayed EDCs, and as a consequence, conditions exist for endocrine disturbance in the biota by chronic exposure to EDCs.     

Reassessment of the Ocean-To-Atmosphere Flux of Carbon Monoxide

Abstract

Carbon monoxide (CO) in the surface sea waters is produced predominantly by photochemical processes, oxidized by micro-organisms and outgassed to the atmosphere. to assess carbon monoxide flux from the oceans to the atmosphere, the photochemical production and microbial oxidation of carbon monoxide in the oceanic mixed-layer was investigated during several oeanographic cruises and in the laboratory. the photoproduction rate of carbon monoxide was found to be well correlated to the concentration of dissolved organic carbon (DOC) in coastal and open ocean surface waters. Taking a global average carbon monoxide production rate of 10 ± 2 nmole litre^?1 (mg DOC hr)^?1 in the surface open ocean water, and 25 ± 7 nmole litre^?1 (mg DOC hr)^?1 in coastal sea water, at cloud-free summer solar noon, the photochemical production of carbon monoxide in the global oceans is estimated to be at a rate of 1200 ± 200 Tg CO y^?1. the microbial carbon monoxide turnover time in the mixed-layer was observed to range from hours in a coastal estuary to 16 days in the Pacific along 1057deg; W in dark incubations. Natural sunlight can largely inhibit the microbial consumption of carbon monoxide in surface water. On a global scale, microbial consumption is responsible for the loss of less than 10% of photochemical produced carbon monoxide in the surface ocean. Field measurements have shown that the net transport of carbon monoxide from the euphotic zone to the underlying deeper ocean water is limited and that the overall life time in surface sea waters is less than 3-4 hours. When combined, these field measurements with the photoproduction and microbial consumption rates obtained, we estimate the oceanic flux to the atmosphere is about 1000 ± 200 Tg CO y^?1, which represents the largest single source of atmospheric carbon monoxide.     

Determination of mercury and arsenic levels in fish caught in the Beheshtabad River,Chaharmahal and Bakhtiari Province,Iran

Mercury and arsenic pollution has been recognized as a potential environmental and public health problem for over 40 years. The major source of exposure to mercury for humans is the ingestion of fish. This study was conducted with the aim of determining the levels of mercury and arsenic in the muscles of four fish species caught in the Beheshtabad River and comparing the results with the maximum tolerance levels for mercury and arsenic. The samples of 90 fish were used for the determination of both the metals by graphite furnace atomic absorption spectrometry. The results showed that the concentrations ranged from 1.5 to 3.8 µg kg^?1 for mercury and from 35 to 70 µg kg^?1 for arsenic, with means of 2.7 ± 0.5 and 57 ± 12 µg kg^?1, respectively. Both mean levels were lower than the threshold limits acceptable by WHO standards.     

沉积物中汞的甲基化研究进展

汞是环境中存在的一种重要污染物质,其毒性与之化学形态密切相关。环境中的汞主要以无机汞形态存在,然而无机汞可以通过甲基化作用转化为毒性更强的甲基汞,从而给受到暴露的生物及人类带来更高的健康风险。沉积物是汞在水生环境系统中的主要分布相,也是无机汞甲基化过程发生的主要场所。沉积物中汞的甲基化过程受到生物种类、汞的生物可利用性等生物因素及温度、含硫化合物、有机质、氧化还原条件等环境理化性质的影响。本文对汞在沉积物中甲基化过程的作用机制及其影响因素的研究现状及最新进展进行了总结,并对未来更深入的研究进行了展望。