Isotopic ((13)C) analysis of dissolved organic carbon in stream water using an elemental analyzer coupled to a stable isotope ratio mass spectrometer

A technique for measurement of the stable isotope composition of dissolved organic carbon (DOC) in stream water, using an elemental analyzer (EA) coupled to an isotope ratio mass spectrometer (IRMS), is described. Stream water samples were concentrated by rotary evaporation, acidified to remove dissolved inorganic carbon (DIC), and dried in silver cups prior to analysis. Precision was evaluated with standards (alanine and humic acid), and with stream water samples with varying (13)C enrichment. Standards and samples were also prepared in sealed quartz tubes for high-temperature combustion (HTC) and analyzed by dual inlet for comparison. The delta(13)C values of natural abundance standards and samples measured by the two techniques differed by 相似文献   

A new organic carbon detector for size exclusion chromatography

A novel organic carbon detector (OCD) for size exclusion chromatography (SEC), and its application to the characterisation of aquatic natural organic matter (NOM) in natural and treated potable water samples, is described. The instrument uses a conventional UV-persulfate oxidation technique to convert organic carbon to CO(2). The novelty of the technique is detection of the evolved CO(2) using a sensitive Fourier transform infrared (FTIR) spectroscopy 'lightpipe' detector originally designed for detection of analytes after gas chromatographic separation. With the exception of the lightpipe, the OCD system was constructed using simple, inexpensive, readily available components. The system was designed to minimise deadvolume, allowing for use of smaller sample sizes and smaller columns, substantially shortening analysis time, while maintaining chromatographic integrity through the OCD system. Downscaling resulted in some loss of separation but it was shown that this was caused by the lower separation efficiency of the smaller capacity column, rather than from sample dispersion within the OCD system.     

Size-exclusion chromatography with organic carbon detection using a mass spectrometer

A novel organic carbon detector for size-exclusion chromatography (SEC) is described. The instrument uses the conventional UV-persulfate oxidation method to convert organic carbon to CO(2), which is then detected using a mass spectrometer. This system, using the mass spectrometer, had lower limits of detection (LOD) and limits of quantification (LOQ) than a previously described system using a Fourier transform infrared (FTIR) spectroscopy 'lightpipe' detector (i.e. when quantification was based on calibration using phthalate standards). When used to analyse natural organic matter (NOM) in water, it also had a superior signal-to-noise ratio to the previously described system. The use of a mass spectrometer to detect organic carbon (as CO(2)) enables the possibility of further characterisation of NOM by measuring the stable carbon isotope ratios of the various molecular size fractions of organic carbon, as obtained by SEC.     

Issues of the Study of Detritus in Aquatic Systems

In this paper, we present the analysis of the ecological roles of detritus and suspended particulate matter in aquatic ecosystems. New data that have been obtained for freshwater ecosystems of the central part of Russian Federation (Moscow Region, e.g., Mozhaiskoe Reservoir) have been included in the analysis. These new data include the results of studies of samples of water and detritus from the aquatic ecosystems. The review analysis addresses both freshwater and marine ecosystems. The multifunctional important role of detritus in aquatic ecosystems has been shown and exemplified using data for aquatic bodies of different trophic level, from oligotrophic to eutrophic.     

The application of electrospray ionization coupled to ultrahigh resolution mass spectrometry for the molecular characterization of natural organic matter

Mass spectrometry has recently played a key role in the understanding of natural organic matter (NOM) by providing molecular-level details about its composition. NOM, a complex assemblage of organic molecules present in natural waters and soils/sediments, has the ability to bind and transport anthropogenic materials. An improved understanding of its composition is crucial in order to understand how pollutants interact with NOM and how NOM cycles through global carbon cycles. In the past, low-resolution (>3000) mass analyzers have offered some insights into the structure of NOM, but emerging ultrahigh resolution (>200,000) techniques such as electrospray ionization (ESI) coupled to Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) have significantly advanced our knowledge of NOM chemistry. Here, a review of the recent literature on the advancements of NOM characterization and the applications of mass spectrometry to this central task is presented. Various methods for the analysis and display of the extremely complex mass spectra, such as the van Krevelen diagram and Kendrick mass defect analysis, are discussed. We also review tandem mass spectrometry techniques employed to gain structural information about NOM components. Finally, we show how ESI-FT-ICR-MS has been applied to examine specific issues that are important to the NOM scientific community, such as NOM reactivity, transport and fate, degradation, and existence of components, which are indicators of NOM origin. In general, ultrahigh resolution provided by FT-ICR-MS is essential for the complete separation of the thousands of peaks present in the complex NOM mixture and will clearly lead to additional future advancements in the areas of aquatic, soil, and analytical chemistry.     

Analysis of aquatic‐phase natural organic matter by optimized LDI‐MS method

The composition and physiochemical properties of aquatic‐phase natural organic matter (NOM) are most important problems for both environmental studies and water industry. Laser desorption/ionization (LDI) mass spectrometry facilitated successful examinations of NOM, as humic and fulvic acids in NOM are readily ionized by the nitrogen laser. In this study, hydrophobic NOMs (HPO NOMs) from river, reservoir and waste water were characterized by this technique. The effect of analytical variables like concentration, solvent composition and laser energy was investigated. The exact masses of small molecular NOM moieties in the range of 200–1200 m/z were determined in reflectron mode. In addition, spectra of post‐source‐decay experiments in this range showed that some compounds from different natural NOMs had the same fragmental ions. In the large mass range of 1200–15 000 Da, macromolecules and their aggregates were found in HPO NOMs from natural waters. Highly humic HPO exhibited mass peaks larger than 8000 Da. On the other hand, the waste water and reservoir water mainly had relatively smaller molecules of about 2000 Da. The LDI‐MS measurements indicated that highly humic river waters were able to form large aggregates and membrane foulants, while the HPO NOMs from waste water and reservoir water were unlikely to form large aggregates. Copyright © 2014 John Wiley & Sons, Ltd.     

光化学降解溶解有机物及其对生物过程的影响

溶解有机物对控制海洋和淡水水生系统的化学、生物和物理特性有重要的影响.光化学降解溶解有机物改变了生态体系的溶解有机碳、有机物的分子量及光学特性,并且产生复杂的反应性氧化合物、二氧化碳、一氧化碳、小分子量的有机酸、氨基酸、二硫化碳等,对生物过程有重要的影响.本文简要综述了光化学降解溶解有机物的过程机理及其对生物过程的影响.     

A flow injection analyser conductometric coupled system for the field analysis of free dissolved CO<Subscript>2</Subscript> and total dissolved inorganic carbon in natural waters

A flow injection analyser coupled with a gas diffusion membrane and a conductometric microdetector was adapted for the field analysis of natural concentrations of free dissolved CO₂ and dissolved inorganic carbon in natural waters and used in a number of field campaigns for marine water monitoring. The dissolved gaseous CO₂ presents naturally, or that generated by acidification of the sample, is separated by diffusion using a hydrophobic semipermeable gas porous membrane, and the permeating gas is incorporated into a stream of deionised water and measured by means of an electrical conductometric microdetector. In order to make the system suitable and easy to use for in-field measurements aboard oceanographic ships, the single components of the analyser were compacted into a robust and easy to use system. The calibration of the system is carried out by using standard solutions of potassium bicarbonate at two concentration ranges. Calibration and sample measurements are carried out inside a temperature-constant chamber at 25 °C and in an inert atmosphere (N₂). The detection and quantification limits of the method, evaluated as 3 and 10 times the standard deviation of a series of measurements of the matrix solution were 2.9 and 9.6 μmol/kg of CO₂, respectively. Data quality for dissolved inorganic carbon was checked with replicate measurements of a certified reference material (A. Dickson, Scripps Institution of Oceanography, University of California, San Diego), both accuracy and repeatability were −3.3% and 10%, respectively. Optimization, performance qualification of the system and its application in various natural water samples are reported and discussed. In the future, the calibration step will be operated automatically in order to improve the analytical performance and the applicability will be increased in the course of experimental surveys carried out both in marine and freshwater ecosystems. Considering the present stage of development of the method, it can only be applied for studying of the carbon cycle in oxic environments.     

Online coupling of ultraviolet titanium dioxide film reactor with poly(methyl methacrylate) solid phase extraction–inductively coupled plasma mass spectrometry for speciation of trace heavy metals in freshwater

To rapidly discriminate dissolved labile and stable organic-complexed metal ions, a fully automated approach comprising a photocatalyst-assisted digestion reactor (PADR), a non-functionalized poly(methyl methacrylate) (PMMA) solid-phase extraction (SPE) column, and inductively coupled plasma-mass spectrometry (ICP-MS) instrumentation was developed. To separate labile dissolved metals from other concomitant metal complexes, a non-functionalized PMMA bead was used as the SPE adsorbent because of its selective interaction with labile metal ions. The PMMA SPE–ICP-MS hyphenated system was optimized, and its analytical reliability was confirmed by using it to analyze the certified reference material—NIST 1643e (artificial saline water). Detection limits (σ = 3, n = 7) for all analyte ions (Ni, Cu, Zn, Cd, and Pb), which ranged from 0.005 to 0.186 μg L^{− 1}, could be reached; therefore, this technique appeared uniquely suited to determining levels of trace elements in most natural freshwater samples. To determine the total quantity of dissolved metals, a new digestion reactor (PADR) was developed for online conversion of metal–organic complexes to their labile forms. Compared to conventional photolysis methods, the digestion time improved considerably and the digestion efficiency for organic substances was excellent (> 90%) in the PADR format, with a very short resident time of 10 min. After construction of the PADR–PMMA SPE–ICP-MS hyphenated system, the speciation potential of our developed method was evaluated by analyzing three intentionally contaminated water samples. Results indicated that our developed hyphenated system is effective for online determination of total, labile, and metal–humic complexes in freshwater samples and that is capable of providing representative metal speciation patterns for different aquatic systems.     

Preparation of a novel magnetic resin for effective removal of both natural organic matter and organic micropollutants

A novel,bifunctional,hypercrosslinked.magnetic resin W2 was prepared using divinylbenzene(DVB) and glycidyl methacrylate(GMA) as comonomers in three steps(i.e.,suspension polymerization, amination and post-crosslinking reactions).To evaluate the adsorption of natural organic matter(NOM) and organic micropollutants(OMPs) on the obtained resin W2,two magnetic resins Wl(the precursor of W2 before post-crosslinking) and WO(the precursor of Wl before amination) were chosen for comparison.The results indicated that W2 would be a promising material for the removal of both NOM and OMPs from aquatic environments.     

Determination of organic carbon in water with a silver-catalyzed peroxydisulfate wet chemical oxidation method

The application of Ag(I) catalysis of S₂O₈^2? to the oxidation of organic carbon to CO₂ for determination of dissolved organic carbon in aqueous samples is described. The resulting method combines to a significant degree the speed of high-temperature combustion methods and the sensitivity of wet chemical oxidation. For some samples, a higher oxidation efficiency has been observed than with an uncatalyzed wet chemical oxidation method.     

New methods for the direct determination of dissolved inorganic, organic and total carbon in natural waters by Reagent-Free Ion Chromatography and inductively coupled plasma atomic emission spectrometry

New methods have been developed and applied successfully for the determination of dissolved inorganic, organic and total carbon in water samples. The new methods utilize two instrumental setups, Reagent-Free™ Ion Chromatography (RF™-IC) and inductively coupled plasma atomic emission spectrometry (ICP-AES). Dissolved inorganic carbon (DIC) was measured in untreated samples along with Cl⁻, F⁻ and SO₄²⁻ using RF™-IC and by in-line mixing with 0.1 M HNO₃ to enhance CO₂ removal in the nebulizer, followed by ICP-AES analysis. Total dissolved carbon (TDC) was measured by in-line mixing with 0.1 M NaOH following ICP-AES analysis. Dissolved organic carbon (DOC) was obtained as the difference between DIC and TDC. Only non-volatile organic carbon could be detected by the present method. The workable limits of detection obtained in the present study were 0.5 mM (RF™-IC) and 0.1 mM (ICP-AES) for dissolved inorganic and organic carbon, respectively. The power of the new methods lies in routine analysis of DIC and DOC in samples of natural waters of variable composition and salinity using analytical techniques and facilities available in most laboratories doing water sample analysis. The techniques are sensitive and precise, can be automated using gas-tight sample vials and auto-samplers, and are independent of most elemental interferences with the exception of chloride overload by saline samples when using RF™-IC. The new methods were successfully applied for analysis of DIC and DOC in selected samples of natural and synthetic waters.     

The discovery of hidden arsenic species in coastal waters

The analysis of ultraviolet (UV)-irradiated and untreated seawater samples has shown that the dissolved arsenic content of marine waters cannot be completely determined by hydride generation–atomic absorption spectrophotometry without sample pretreatment. Irradiation of water samples obtained during a survey of arsenic species in coastal waters during the summer of 1988 gave large increases in the measured speciation. Average increases in the measured speciation. Average increases in total arsenic, monomethylarsenic and dimethylarsenic were 0.29 μg As dm^?3 (25%), 0.03 μg As dm^?3 (47%) and 0.12 μg As dm^?3 (79%), respectively. Overall, an average 25% increase in the concentration of dissolved arsenic was observed following irradiation. This additional arsenic may be derived from compounds related to algal arsenosugars or to their breakdown products. These do not readily yield volatile hydrides when treated with borohydride and are not therefore detected by the normal hydride generation technique. This has important repercussions as for many years this procedure, and other analytical procedures which are equally unlikely to respond to such compounds, have been accepted as giving a true representation of the dissolved arsenic speciation in estuarine and coastal waters. A gross underestimate may therefore have been made of biological involvement in arsenic cycling in the aquatic environment.     

Conversion efficiency of the high-temperature combustion technique for dissolved organic carbon and total dissolved nitrogen analysis

The measurements of dissolved organic carbon (DOC) and total dissolved nitrogen (TDN) in seawater are key in global change and coastal eutrophication studies. Nowadays, the high-temperature combustion (HTC) technique is a widely used method for DOC and TDN analysis. However, uncertainties exist about the operation of the catalyst in the conversion process of DOC and TDN in the HTC method. In this study, five different ‘catalyst’ materials were tested for their blanks, calibration slopes, and conversion efficiency of DOC and TDN using the Shimadzu TOC 5000A total organic carbon analyser coupled to a Sievers NCD 255 nitrogen chemiluminescence detector. The materials included four metallic catalysts (Shimadzu and Johnson 0.5% Pt–alumina, 13% Cu(II)O–alumina, 0.5% Pd–alumina) and quartz beads. The results indicated that DOC blank signals for the HTC approach using metallic catalysts with an alumina support are higher compared with quartz beads, as a result of the amphoteric nature of the alumina. However, the slopes of the standard calibration graphs were lowest for DOC and TDN determinations on the quartz beads. The DOC recoveries for the metallic catalysts were close to 100% for all compounds tested, with the exception of ammonium pyrrolidine dithiocarbamate. Using quartz beads, poor recoveries were obtained for a range of organic compounds, including the commonly used calibration compounds potassium hydrogen phthalate and glycine. The TDN recoveries for all compounds were typically >90%, with the exception of NaNO₂. Furthermore, analysis using the CuO–alumina and Pd–alumina catalysts and quartz beads showed low recoveries for NH₄Cl. This study showed that catalyst performance should be verified on a regular basis using model compounds and blank checks made during every run, and that the Shimadzu 0.5% Pt–alumina material was an efficient catalyst for DOC and TDN analyses using the coupled total organic carbon–nitrogen chemiluminescence detector (TOC-NCD) analyser.     

Determination of molecular formulas of natural organic matter molecules by (ultra-) high-resolution mass spectrometry: Status and needs

Electrospray ionization (ESI) combined with ultra-high-resolution mass spectrometry on a Fourier transform ion cyclotron resonance mass spectrometer has been shown to be a very powerful tool for the analysis of fulvic and humic acids and of natural organic matter (NOM) at the molecular level. With this technique thousands of ions can be separated from each other and their m/z ratio determined with sufficient accuracy to allow molecular formula calculation. Organic biogeochemistry, water chemistry, and atmospheric chemistry greatly benefit from this technique. Methodical aspects concerning the application of Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) to NOM isolated from surface water, groundwater, marine waters, and soils as well as from secondary organic aerosol in the atmospheric are reviewed. Enrichment of NOM and its chromatographic separation as well as possible influences of the ionization process on the appearance of the mass spectra are discussed. These steps of the analytical process require more systematic investigations. A basic drawback, however, is the lack of well defined single reference compounds of NOM or fulvic acids. Approaches of molecular formula calculation from the mass spectrometric data are reviewed and available graphical presentation methods are summarized. Finally, unsolved issues that limit the quality of data generated by FTICR-MS analysis of NOM are elaborated. It is concluded that further development in NOM enrichment and chromatographic separation is required and that tools for data analysis, data comparison and data visualization ought to be improved to make full use of FTICR-MS in NOM analysis.     

Microwave extraction of phthalate esters from marine sediment and soil

Summary As part of an on-going ASEAN⁺⁾-Canada Cooperative Programme on Marine Science, microwave-assisted solvent extraction has been employed for the extraction of six phthalate esters from marine sediment and soil samples. Five of the six esters studied are among the United States Environmental Protection Agency's list of top priority pollutants. The effects of extraction solvent, extraction temperature, duration of extraction and extraction volume on the mean recoveries of the six phthalate esters were quantitatively evaluated by means of an analysis of variance, followed by testing the differences among the level means for each condition with least significant difference method. Microwave-assisted solvent extraction allowed comparable or higher recoveries of the six phthalate esters (70.1–91.0%) in comparison with conventional soxhlet (65.5–89.5%) and sonication (64.6–88.6%). The precision of results by microwave-assisted solvent extraction was improved significantly compared to the conventional techniques. The microwave extraction system has many advantages over the soxhlet and sonication extraction, e.g., no laborious clean-up procedure, lower usage of hazardous organic solvent, and larger sample throughput. The technique has been employed for the analysis of native marine sediment and soil samples in Singapore.     

The application of the MBTH method for carbohydrate determination in freshwaters revisited

There is a lack of reliable and easy-to-use methods for the quantitative determination of carbohydrates in natural waters. Among the existing methods, the 3-methyl-2-benzothiazolinone hydrochloride (MBTH) method has been widely used to determine total dissolved carbohydrates in seawater. Its application to freshwaters has, so far, been less frequent. The objective of this study is to critically examine the application of the MBTH method to the analysis of carbohydrates in freshwater samples in order to understand what the method really measures. Following a comprehensive revision of the literature, the method has first been applied to representative model compounds and then to a variety of freshwaters of contrasting trophic characteristics. By simultaneously determining the total dissolved organic carbon and humic-type compounds in the same samples, it has been possible to show that sometimes a significant part of the organic carbon remains undetected. This seems to indicate that a substantial amount of carbohydrate present in some natural waters is probably not ‘seen’ by the MBTH method.     

Transmission electron microscopy of the natural organic matter of surface waters

Some components of aquatic natural organic matter (NOM) can be analysed effectively by methods of particle analysis employing transmission electron microscopy in conjunction with multi-method analytical approaches in the field, minimum perturbation techniques for sample handling and technology transfer from the biomedical sciences. The NOM components, include fulvic acids, colloidal fibrils and organic polymers of MW > 30 000. The use of a water-compatible embedding resin permits shape and size analyses of colloidal NOM (1–1000 nm) in ultrathin sections which minimize the misleading dehydration artifacts of the past. Experimentally induced perturbations allow one to follow aggregation/coagulation events at 1 nm resolution, while permitting the analyst to relate some components of coagulum structure to chemical entities. This review presents the current status of attempts to optimize a combination of analytical chemistry and transmission electron microscopy for describing NOM and its behaviour in surface waters.     

Synthesis and Study of Nanodispersed Carbon in the Combustion of Acetylene in a Flow Detonation Tube

Nanodispersed carbon was obtained via high-temperature combustion of acetylene–oxygen mixtures in a flow-through tubular chamber in cyclic detonation waves (“pulsed detonation”) at a constant propagation velocity (D_det ≈ 2150 m s^–1). It was found that the position of a plateau in the curve describing how the detonation velocity depends on the content of oxygen in the starting detonation mixture in the range 15–30% coincides with the range of descending branches of the dependences of the specific adsorption surface area and adsorption of dibutyl phthalate by aggregated particles. Various physicochemical methods of analysis (X-ray diffraction analysis, Raman spectroscopy, high-resolution transmission electron microscopy, etc.) were used to comparatively examine the properties of nanodispersed carbon and of the known industrially produced domestic and foreign brands of technical-grade carbon. The conditions were found in which detonation nanocarbon particles are obtained in a certain range of parameters of micro- and macrostructures with improved morphology and basic electrical properties.