A novel tool for stable nitrogen isotope analysis in aqueous samples.

RATIONALE: Bulk stable isotope analysis (BSIA) of dissolved matter (e.g. dissolved organic carbon, total nitrogen bound (TNb ), etc.) is of particular importance since this pool is a prime conduit in the cycling of N and C. Studying the two elemental pools is of importance, as transformation and transport processes of N and C are inextricably linked in all biologically mediated systems. No system able to analyze natural abundance stable carbon and nitrogen isotope composition in aqueous samples (without offline sample preparation) and simultaneously has been reported so far. Extension of the high-temperature combustion (HTC) system, to be capable of measuring TNb stable nitrogen isotope composition, is described in this study. METHODS: To extend the TOC analyzer to be capable of measuring TNb , modifications from the HTC high-performance liquid chromatography/isotope ratio mass spectrometry (HPLC/IRMS) interface were implemented and expanded. A reduction reactor for conversion of NOx into N2 was implemented into the new developed system. The extension addresses mainly the development of the focusing unit for nitrogen and a degassing device for online separation of TNb from molecular nitrogen (N2 ) prior to injection. RESULTS: The proof of principle of the system was demonstrated with different compound solutions. In this initial testing, the δ15 NAIR-N2 values of the tested compounds were determined with precision and trueness of typically ≤0.5‰. Good results (u ≤ 0.5‰) could be achieved down to a TNb concentration of 40 mgN/L and acceptable results (u ≤ 1.0‰) down to 5 mgN/L. In addition, the development resulted in the first system reported to be suitable for simultaneous and direct δ13 C and δ15 N BSIA of aqueous samples. CONCLUSIONS: The development resulted in the first system shown to be suitable for both δ13 C and δ15 N direct BSIA in aqueous samples. This system could open up new possibilities in SIA-based research fields. Copyright © 2016 John Wiley & Sons, Ltd.

Influence of green waste compost on azimsulfuron dissipation and soil functions under oxic and anoxic conditions.

Concerns have been raised over the sustainability of intensive rice cultivation, where the use of chemical fertilizers and pesticides has been associated with numerous environmental problems. The objective of this study was to test the effect of the herbicide azimsulfuron on important soil functions as affected by amendment with a byproduct of the olive oil industry. Soil was collected from a Mediterranean rice field. Part of it was amended with alperujo compost (AC). Amended and unamended soils were incubated for 43days in presence or not of azimsulfuron, under anoxic-flooded (AF) and oxic-unflooded (OU) conditions. We monitored the dissipation of the herbicide azimsulfuron, C mineralization, soil microbial biomass (SMB) and dissolved organic carbon (DOC) content and its nature. Under AF conditions, the application of compost produced an increase in the dissipation of the herbicide (up to 12.4%). It was related with the higher DOC content, 4 times higher than under OU conditions. Though increases in carbon turnover (under AF and OU conditions) and reduction of SMBC after herbicide application (only under AF conditions) were observed, the differences were not statistically significant. The application of this organic amendment is presented as an efficient management strategy to increase C turnover in agricultural soils and reduce some of the negative effects derived from the application of azimsulfuron under flooded conditions.

Determination of n-alkanes in C. annuum (bell pepper) fruit and seed using GC-MS: comparison of extraction methods and application to samples of different geographical origin.

An efficient extraction and analysis method was developed for the isolation and quantification of n-alkanes from bell peppers of different geographical locations. Five extraction techniques, i.e., accelerated solvent extraction (ASE), ball mill extraction, ultrasonication, rinsing, and shaking, were quantitatively compared using gas chromatography coupled to mass spectrometry (GC-MS). Rinsing of the surface wax layer of freeze-dried bell peppers with chloroform proved to be a relatively quick and easy method to efficiently extract the main n-alkanes C27, C29, C31, and C33. A combined cleanup and fractionation approach on Teflon-coated silica SPE columns resulted in clean chromatograms and gave reproducible results (recoveries 90-95 %). The GC-MS method was reproducible (R(2) = 0.994-0.997, peak area standard deviation = 2-5%) and sensitive (LODs, S/N = 3, 0.05-0.15 ng/µL). The total main n-alkane concentrations were in the range of 5-50 µg/g dry weight. Seed extractions resulted in much lower total amounts of extracted n-alkanes compared to flesh and surface extractions, demonstrating the need for further improvement of pre-concentration and cleanup. The method was applied to 131 pepper samples from four different countries, and by using the relative n-alkane concentration ratios, Dutch peppers could be discriminated from those of the other countries, with the exception of peppers from the same cultivar. Graphical Abstract Procedure for pepper origin determination.

A novel high-temperature combustion based system for stable isotope analysis of dissolved organic carbon in aqueous samples. I: development and validation.

RATIONALE: Traditionally, dissolved organic carbon (DOC) stable isotope analysis (SIA) is performed using either offline sample preparation followed by elemental analyzer/isotope ratio mass spectrometry (EA/IRMS) or a wet chemical oxidation (WCO)-based device coupled to an isotope ratio mass spectrometer. The first method is time-consuming and laborious. The second involves the risks of underestimation of DOC concentration and isotopic fractionation due to incomplete oxidation. The development of an analytical method for accurate and sensitive DOC SIA is described in this study. METHODS: A high-temperature combustion (HTC) system improves upon traditional methods. A novel total organic carbon (TOC) system, specially designed for SIA, was coupled to an isotope ratio mass spectrometer. An integrated purge and trap technique (peak focusing), flexible injection volume (0.05-3 mL), favorable carrier gas flow, modified ash crucible, new design of combustion tube and optimized drying system were used to achieve the necessary performance. RESULTS: The system can reliably measure concentrations up to 1000 mgC/L. Compounds resistant to oxidation, such as barbituric acid, melamine and humic acid, were analyzed with recovery rates of 100 ± 1% proving complete oxidation. In this initial testing, the δ(13) C values of these compounds were determined with precision and trueness of ≤ 0.2‰ even with 3.5% salinity. Further tests with samples with low DOC concentrations resulted in LOQSIA method values of 0.5 mgC/L and 0.2 mgC/L for LOQSIA instr , considering an accuracy of ± 0.5‰ as acceptable. CONCLUSIONS: The novel HTC system coupled to an isotope ratio mass spectrometer resulted in significantly improved sensitivity. The system is suitable for salt-containing liquids and compounds that are resistant to oxidation, and it offers a large concentration range. A second paper (which follows this one in this issue) will present a more comprehensive assessment of the analytical performance with a broad set of solutions and real samples. This highly efficient TOC stable isotopic analyzer will probably open up new possibilities in biogeochemical carbon cycle research.

A novel high-temperature combustion based system for stable isotope analysis of dissolved organic carbon in aqueous samples. II: optimization and assessment of analytical performance.

RATIONALE: Dissolved organic carbon (DOC) plays an important role in carbon cycling, making precise and routine measurement of δ(13)C values and DOC concentration highly desirable. A new promising system has been developed for this purpose. However, broad-scale application of this new technique requires an in-depth assessment of analytical performance, and this is described here. METHODS: A high-temperature combustion Total Organic Carbon analyzer was interfaced with continuous flow isotope ratio mass spectrometry (TOC/IRMS) for the simultaneous analysis of the bulk DOC concentration and δ(13)C signature. The analytical performance (precision, memory effects, linearity, volume/concentration effects, accuracy) was thoroughly evaluated, including realistic and challenging conditions such as low DOC concentrations and natural DOC. RESULTS: High precision (standard deviation, SD predominantly ≤ 0.15 ‰) and accuracy (R(2) = 0.9997) were achieved for the δ(13)C analysis of a broad diversity of DOC solutions. Simultaneously, good results were obtained for the measurement of DOC concentration. Assessment of natural abundance and slightly (13)C-enriched DOC, a wide range of concentrations (~0.2-150 mgC/L) and injection volumes (0.05-3 mL), demonstrated minor/negligible memory effects, good linearity and flexible usage. Finally, TOC/IRMS was successfully applied to determine low DOC concentrations (<2 mgC/L) and DOC from diverse terrestrial, freshwater and marine environments (SD ≤ 0.23 ‰). CONCLUSIONS: TOC/IRMS enables fast and reliable measurement of DOC concentrations and δ(13)C values in aqueous samples, without pre-concentration and freeze-drying. Further investigations should focus on complex, saline matrices and very low DOC concentrations, to achieve a potential lower limit of 0.2 mgC/L. Thus, TOC/IRMS will give DOC research in terrestrial and aquatic environments a huge impulse with high-resolution, routine δ(13)C analysis.

Salinity increases mobility of heavy metals in soils.

The effect of salinity induced by CaCl(2), MgCl(2), NaCl and Na(2)SO(4) on the mobility of Cu, Cd, Pb and Zn was studied. An increase of ionic strength by any salts promoted a higher release of Cd than the others metals. When CaCl(2) and NaCl were applied, Cd and Pb showed the highest degree of mobilization. When MgCl(2) was applied, Cd and Cu were mobilized the most. Finally, an increase of Na(2)SO(4) also promoted the strongest mobilization of Cd and Cu. As the total heavy metal content was higher, the percentage of Pb and Cu released upon salinization decreased, indicating that these metals are strongly bound to soil constituents. An increase of carbonates in the soil promoted a higher release of Pb for all used salts and for Zn when MgCl(2) and NaCl were used. This indicates that Pb and Zn are adsorbed on the surface of carbonate crystals. An increase of fine particles promoted a decrease of percentage of released Cd for all salts, indicating that Cd is strongly retained in the fine fractions. The main mechanism regulating Pb and Cd mobility was competition with Ca(2+) for sorption sites followed for metal chloro-complexation, association between the Cd/Pb-sulfates and competition with Mg(2+). The main mechanism regulating Cu mobility was the formation of Cu-sulfate, followed by competition with cations (Mg > Ca) and chloride. For Zn, competition with Ca(2+) for sorption sites was the most important process for its mobility; followed by Zn-sulfate association and, finally, chloride and competition with Mg with the same effect.

A comparative characterization of dissolved organic matter by means of original aqueous samples and isolated humic substances.

The aim of our study is to test the use of less time-consuming spectroscopic methods applied on original water samples in order to obtain information about DOM composition without any sample preparation. These results were directly compared with results from a conventional isolation and characterization procedure of dissolved humic substances (fulvic acids--FA) isolated from the same water sample. FAs were characterized by UV-, fluorescence-, FTIR spectroscopy and elemental composition. UV absorbance and fluorescence behavior of FAs and original water samples follow the same pattern. A lower UV absorbance and a lower humification index (derived from the synchronous fluorescence spectra) of about 15% is typical for water samples compared to the FAs. We computed linear relationships between properties of the original water sample (UV-, synchronous fluorescence spectra) and the isolated FA (IR absorption, C/N ratio). The application of synchronous fluorescence and UV spectroscopy of aqueous samples has been proved to result in similar information about DOM composition as the characterization of isolated humic substances concerning the content of aromatic structures and the degree of humification.

Seasonal impacts on beta-hexachlorocyclohexane concentration in soil solution.

We analysed monthly the concentration of beta-hexachlorocyclohexane (beta-HCH), a hydrophobic organic contaminant, in aqueous saturation extracts of the topsoil from five differently contaminated sites. beta-HCH concentration in the aqueous soil extract shows a high seasonal variability. Concentrations differ up to 60-fold with peaks up to 2.24 microg l(-1). Higher beta-HCH concentrations were found in summer and autumn and accompanied by peaks in dissolved organic carbon concentration. This indicates the importance of dissolved organic matter for beta-HCH mobilization and the risks for groundwater pollution and plant uptake.

Mobilization of heavy metals and arsenic in polluted wetland soils and its dependence on dissolved organic matter.

The wetland soils of the Mulde river in the industrial district of Bitterfeld-Wolfen (Germany) are highly contaminated with heavy metals and arsenic. We studied the mobility of accumulated heavy metals and arsenic and the influence of dissolved organic matter (DOM) on element mobility. Undisturbed soil cores were taken from five different sites to represent a wide range of heavy-metal contamination, soil properties and dissolved organic carbon (DOC) concentrations. The acid-soluble concentrations (mostly equal to the total content) were up to 1100 mg kg-1 for Zn, 800 mg kg-1 for Cr, 364 mg kg-1 for Cu, 265 mg kg-1 for As and 37 mg kg-1 for Hg, depending on the sampling site. Percolation experiments using small lysimeters with undisturbed topsoil cores illustrated a considerable mobilization of Zn, Cd, Cu, Cr and Hg, depending on soil properties. Up to 80 micrograms l-1 Cd, 8 mg 1-1 Zn, 130 micrograms l-1 Cr, 160 micrograms l-1 Cu and 7 micrograms l-1 Hg were detected in the soil percolates. Arsenic mobilization was low. The concentration of Cr, Hg, Cu and As in the soil percolates was positively correlated with DOM. Besides the element content (mobile or acid-soluble), soil pH and soil characteristics describing the soil potential for heavy-metal adsorption (clay, oxides, cation exchange capacity), the DOC concentration in the soil solution should be known to access the potential mobilization of Hg, Cr, Cu and As. In contrast, Cd and Zn mobilization depends on soil pH and mobile element content, but not on DOM. Additional studies on two soil profiles (down to 1.5 m) confirmed the translocation of heavy metals from the highly contaminated topsoil into deeper soil horizons and into the groundwater and the influence of DOM as revealed with the percolation experiment. Our results also showed that DOM is of minor importance on the mobilization of heavy metals in soils with a low soil pH (< 4.5).