Phosphorus fractions and phosphate sorption characteristics in relation to the sediment compositions of shallow lakes in the middle and lower reaches of Yangtze River region, China

Phosphorus is recognized as the most critical nutrient limiting lake productivity. The trophic status and development of lake systems are also influenced by the phosphorus content and fractions and phosphate sorption characteristics of the lake sediments. The phosphorus fractions and phosphate sorption characteristics of sediments in shallow lakes from the middle and lower reaches of Yangtze River region in China were investigated. The results show that the phosphorus contents in the sediments ranged from 217.8 to 1640 mg kg(-1); inorganic phosphorus (IP) was the major fraction of total phosphorus (TP); phosphorus bound to Al, Fe, Mn oxides, and hydroxides (Fe/Al-P), and calcium bound phosphorus (Ca-P) were the main fractions of IP. Phosphate sorption on the sediments mainly occurred within 2 h and then reached equilibrium in 10 h. The phosphate sorption rate was closely related to the concentration of fine particles. The phosphate sorption capacity ranged from 128.21 to 833.33 mg kg(-1), showing a significant correlation with the contents of Fe, Fe+Al, total organic carbon (TOC), cationic exchange capacity, total nitrogen, TP, Ca, IP, and the ratio of P/(Al+Fe), and it was higher in the sediments of eutrophic lakes than in mesotrophic lakes. Phosphate was mainly sorbed onto Fe and Al particles. The phosphate sorption efficiency ranged from 26.74 to 312.50 L kg(-1), and had a strong positive correlation with Fe content. For the eutrophic lake sediments, there were no significant relationships between the phosphate sorption efficiency and the selected physical and chemical parameters. But for the mesotrophic lake sediments, the phosphate sorption efficiency was found to be positively related to the contents of Al and Fe+Al.     

Isotopic evidence for condensed aromatics from non-pyrogenic sources in soils--implications for current methods for quantifying soil black carbon

Black carbon (BC) is a complex continuum of partly charred organic matter predominantly consisting of condensed aromatic and graphitic moieties and it has high potential for long-term carbon sequestration in soils and sediments. There has been common agreement that BC is exclusively formed by incomplete combustion of organic matter, while non-pyrogenic sources are negligible. In this study, we investigated the stable carbon isotope signature of benzenepolycarboxylic acids (BPCAs) as molecular markers for BC to test if there is also a significant contribution of non-pyrogenic carbon to this fraction in soils. BPCAs were formed by hot nitric acid oxidation of different soils and analyzed by three different procedures: (i) elemental analysis - isotope ratio mass spectrometry (EA-IRMS) of bulk BPCAs and gas chromatography - combustion - isotope ratio mass spectrometry (GC-C-IRMS) of (ii) BPCA trimethylsilyl (TMS) derivatives, and (iii) BPCA methyl derivatives. Best accuracy and precision of isotope measurements were obtained by EA-IRMS of bulk BPCAs although this method has a risk of contamination by non-BC-derived compounds. The accuracy and precision of GC-C-IRMS measurements were superior for methyl derivatives (+/-0.1 per thousand and 0.5 per thousand, respectively) to those for TMS derivatives (+3.5 per thousand and 2.2 per thousand, respectively).Comparison of BPCA delta(13)C values of soil samples prior to and after laboratory and field incubations with both positive and negative (13)C labels at natural and artificial abundances revealed that up to 25% of the isolated BC fraction in soils had been produced in situ, without fire or charring. Commonly applied methods to quantify BC exclusively formed by pyrogenic processes may thus be biased by a significant non-pyrogenic fraction. Further research is encouraged to better define isolated BC fractions and/or understand mechanisms for non-pyrogenic BC production in soils.     

Negative thermal ionization mass spectrometry of selenium part 4. Selenium trace determination in sediments and related samples

Summary Selenium traces have been determined in different sediments (estuarine, river, lake), sandy soil and sewage sludge with isotope dilution mass spectrometry (IDMS). Negative selenium atomic ions are formed in a double-filament thermal ion source. The use of a silica gel technique for ionization improves the mass spectrometric sensitivity by a factor of 40 compared with the technique previously applied. An enriched⁸²Se spike is used for the isotope dilution process. The samples are decomposed with a mixture of conc. HNO₃ and conc. HE After decomposition selenium is separated by the formation of SeH₂ in a hydride generation system which is normally applied for atomic absorption spectrometry. The IDMS results for three standard reference sediments agree well with the certified values. In the case of three other standard reference materials, which are not certified for selenium up to now, the IDMS analyses were able to improve the selenium data given for information or as indicative values. The precision of the IDMS method in the concentration range of 0.2–3.5 g/g lies between 0.8 % and 4.1 %. The detection limit is 6 ng/g. A comparison with several other methods shows that IDMS is one of the very few analytical methods which produces accurate selenium results even at concentration levels of 0.2 g/g and less in sediments and related samples of environmental interest.

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Negative Thermionen-Massenspektrometrie von Selen Teil 4. Selenspurenbestimmung in Sedimenten und vergleichbaren Proben

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Dedicated to Prof. Dr. G. Tblg on the occasion of his 60th birthday     

Heavy metals in lake water: a review on occurrence and analytical determination

Many lakes especially in Asia are source of livelihood for the surrounding communities. With increased urbanisation and industrialisation, however, these lakes are threatened with emerging environmental contaminants, including heavy metals. Some heavy metals are harmful to human health and the environment. This review aims to describe the different sampling, sample preparation and pretreatment, and instrumental methods of analysis for heavy metals in lake water. Filtration and acid digestion are common sample treatment methods used prior to analytical determination. Atomic absorption spectroscopy and inductively-coupled plasma – mass spectrometry (ICP-MS) are typical analytical techniques but nowadays ICP-MS is frequently used. This review also describes the sources and extent of heavy metals contamination in different lakes. Although some lakes still have natural levels of heavy metals in the water, many have elevated concentrations due to anthropogenic sources, such as vehicular, household, agricultural, industrial and mining activities.     

The geochemistry of uranium in pore waters from lake sediments

The concentration of pore water uranium in six sediments from oligotrophic, mesotrophic, acidotrophic and dystrophic lakes was measured by inductively coupled plasma-mass spectrometry. Profiles of pore water U can be divided into two groups such as low (17±7 ng/l) and high concentration (69±30 ng/l). These values were 1–2 orders of magnitude higher than that of lake waters (6±4 ng/l) due to the release of U from the sediments by decomposition of organic materials. Variations in pore water U concentrations seem to relate to the differences in pore water pH, the association forms, and their contents of U in the lake sediments.     

Proteomics based on selecting and quantifying cysteine containing peptides by covalent chromatography

This paper describes a procedure in which cysteine containing peptides from tryptic digests of complex protein mixtures were selected by covalent chromatography based on thiol-disulfide exchange. identified by mass spectrometry, and quantified by differential isotope labeling. Following disruption of disulfide bridges with 2,2'-dipyridyl disulfide, all proteins were digested with trypsin and acylated with succinic anhydride. Cysteine containing peptides were then selected from the acylated digest by disulfide interchange with sulfhydryl groups on a thiopropyl Sepharose gel. Captured cysteine containing peptides were released from the gel with 25 mM dithiothreitol (pH 7.5) containing 1 mM (ethylenedinitrilo)tetraacetic acid disodium salt and alkylated with iodoacetic acid subsequent to fractionation by reversed-phase liquid chromatography (RPLC). Fractions collected from the RPLC column were analyzed by matrix-assisted laser desorption ionization mass spectrometry. Based on isotope ratios of peptides from experimental and control samples labeled with succinic and deuterated succinic anhydride, respectively, it was possible to determine the relative concentration of each peptide species between the two samples. Peptides obtained from proteins that were up-regulated in the experimental sample were easily identified by an increase of the relative amount of the deuterated peptide. The results of these studies indicate that by selecting cysteine containing peptides, the complexity of protein digest could be reduced and database searches greatly simplified. When coupled with the isotope labeling strategy for quantification it was possible to determine proteins that were up-regulated in plasmid bearing Escherichia coli when expression of plasmid proteins was induced. Up-regulation of several proteins of E. coli origin was also noted.     

Pretreatment technique for siderite removal for organic carbon isotope and C:N ratio analysis in geological samples

A method for the removal of siderite from geological samples to determine organic carbon isotope compositions using elemental analysis isotope ratio mass spectrometry is presented which includes calculations for % organic carbon in samples that contain diagenetic carbonate. The proposed method employs in situ acidification of geological samples with 6 N HCl and silver capsule sample holders and was tested on modern peach leaf samples (NIST 1547) and ancient lacustrine samples from Valles Caldera, New Mexico. The in situ acidification technique eliminates potential errors associated with the removal of soluble organic material using standard acid decanting techniques and allows for removal of the less soluble siderite, which is not efficiently removed using vapor acidification techniques.     

Bulk and compound-specific isotopic characterisation of illicit heroin and cling film

Comparative analysis involves various but complementary methods and can be used for forensic intelligence purposes to group seizures of heroin into batches. Much forensic analysis now combines expertise in the traditional area of drugs investigation with a detailed understanding of supply, packaging, distribution, and drugs intelligence. It was the intention of this research to determine whether illicit heroin seizures and packaging material can be grouped according to isotopic compositions, and to explore factors that affect the isotopic compositions. In order to achieve these aims, 14 samples of seized heroin, thirteen provided by Avon and Somerset Constabulary (UK), were analysed by elemental analysis/isotope ratio mass spectrometry (EA/IRMS) and gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS) for carbon and hydrogen isotopes. These tests elucidated that a combination of the delta13C, delta15N, delta18O and delta2H results from EA/IRMS is able to distinguish between most samples of bulk heroin. We speculate that the delta13C values of the alkaloids, obtained by GC/C/IRMS, give indications of different geographical or temporal origins of some of the heroin samples. GC/C/IRMS of the cutting agent, caffeine, provides a means to link dilution events. Fifteen retail cling film samples and seven cling film samples from heroin seizures were analysed by EA/IRMS. A multivariate comparison of the carbon, hydrogen and oxygen isotope ratios was able to distinguish between most of the samples. This technique enabled the cling films from the heroin to be grouped according to seizure. Three solvents were tested on two samples of cling film of known composition. Methanol and chloroform were both found to extract material from PVC and from non-PVC cling films. Water-treated PVC was indistinguishable from the untreated PVC and thus water was found to be the most suitable solvent when washing cling film prior to IRMS analysis.     

Measurement of isotope ratios in solids by glow discharge mass spectrometry

A commercial thermion mass spectrometer has been modified for glow discharge mass spectrometry. GDMS isotope ratio measurements on osmium, uranium, and boron containing samples are compared with TIMS measurements.     

Carbon isotope ratio measurements of glyphosate and AMPA by liquid chromatography coupled to isotope ratio mass spectrometry

The interest in compound-specific isotope analysis for product authenticity control and source differentiation in environmental sciences has grown rapidly during the last decade. However, the isotopic analysis of very polar analytes is a challenging task due to the lack of suitable chromatographic separation techniques which can be used coupled to isotope ratio mass spectrometry. In this work, we present the first method to measure carbon isotope compositions of the widely applied herbicide glyphosate and its metabolite aminomethylphosphonic acid (AMPA) by liquid chromatography coupled to isotope ratio mass spectrometry. We demonstrate that this analysis can be carried out either in cation exchange or in reversed-phase separation modes. The reversed-phase separation yields a better performance in terms of resolution compared with the cation exchange method. The measurement of commercial glyphosate herbicide samples show its principal applicability and reveals a wide range of δ¹³C values between ?24 and ?34 ‰ for different manufacturers. The absolute minimum amounts required to perform a precise and accurate determination of carbon isotope compositions of glyphosate and AMPA were in the sub-microgram range. The method proposed is sensitive enough to further perform the experiments that are necessary to better understand the carbon isotope fractionation associated to the natural degradation of glyphosate into AMPA. Furthermore, it can be used for contaminant source allocation and product authenticity as well.     

Atmospheric pressure chemical ionisation reversed-phase liquid chromatography/ion trap mass spectrometry of intact bacteriohopanepolyols

Atmospheric pressure chemical ionisation liquid chromatography/multi-stage ion trap mass spectrometry (APCI-LC/MS(n)) has been applied to the study of intact bacteriohopanepolyols. Spectral characterisation of bacteriohopanepolyols of known structure present in bacterial extracts (Zymomonas mobilis and a fermenter containing methanotrophs including Methylococcus capsulatus) has revealed greater structural detail than previous liquid chromatography/mass spectrometry (LC/MS) methods and identified characteristic fragmentations indicative of numerous biohopanoid structures. Analysis of a Recent sedimentary extract from Lake Druzhby (Antarctica) has demonstrated the power of this technique to detect biohopanoids in complex samples including at least partial characterisation of previously unknown composite structures.     

High-throughput characterization of sediment organic matter by pyrolysis–gas chromatography/mass spectrometry and multivariate curve resolution: A promising analytical tool in (paleo)limnology

Molecular-level chemical information about organic matter (OM) in sediments helps to establish the sources of OM and the prevalent degradation/diagenetic processes, both essential for understanding the cycling of carbon (C) and of the elements associated with OM (toxic trace metals and nutrients) in lake ecosystems. Ideally, analytical methods for characterizing OM should allow high sample throughput, consume small amounts of sample and yield relevant chemical information, which are essential for multidisciplinary, high-temporal resolution and/or large spatial scale investigations. We have developed a high-throughput analytical method based on pyrolysis–gas chromatography/mass spectrometry and automated data processing to characterize sedimentary OM in sediments. Our method consumes 200 μg of freeze-dried and ground sediment sample. Pyrolysis was performed at 450 °C, which was found to avoid degradation of specific biomarkers (e.g., lignin compounds, fresh carbohydrates/cellulose) compared to 650 °C, which is in the range of temperatures commonly applied for environmental samples. The optimization was conducted using the top ten sediment samples of an annually resolved sediment record (containing 16–18% and 1.3–1.9% of total carbon and nitrogen, respectively). Several hundred pyrolytic compound peaks were detected of which over 200 were identified, which represent different classes of organic compounds (i.e., n-alkanes, n-alkenes, 2-ketones, carboxylic acids, carbohydrates, proteins, other N compounds, (methoxy)phenols, (poly)aromatics, chlorophyll and steroids/hopanoids). Technical reproducibility measured as relative standard deviation of the identified peaks in triplicate analyses was 5.5 ± 4.3%, with 90% of the RSD values within 10% and 98% within 15%. Finally, a multivariate calibration model was calculated between the pyrolytic degradation compounds and the sediment depth (i.e., sediment age), which is a function of degradation processes and changes in OM source type. This allowed validation of the Py–GC/MS dataset against fundamental processes involved in OM cycling in aquatic ecosystems.     

Development of a definitive method for iodine speciation in aquatic systems

Summary A definitive method of isotope dilution mass spectrometry (IDMS) was developed to determine four different iodine species in aquatic systems (iodide, iodate and two organoiodine compounds: one of the organic species is chromatographically elutable from a column filled with an anion exchanger resin, the other one is not). The iodine species were analysed after the isotope dilution step with an enriched ¹²⁹I spike and after their chromatographic separation. The total iodine concentration was measured after decomposition of organic compounds in the aquatic system by UV irradiation. Different types of natural water samples (river water, water of a pond, moorland lake water) were analysed and important water parameters like pH-value, redox potential, oxygen content and dissolved organic carbon were measured for each of these samples. The total iodine concentration in the different samples differed only slightly in the range of 2–7 g/l. In most of the moorland lake water samples only the two organoiodine species could be detected. In these samples the concentration of iodide and iodate was less than the detection limit of 0.5 g/l and 0.1 g/l, respectively. On the other hand, all four iodine species could be determined in most of the river water samples. Positive correlations were found for the oxygen content of the water samples and the iodate concentration as well as for the redox potential and the anionic organoiodine compound.In memoriam of Dr. I. Linus Barnes who died in January, 1990. Dr. Barnes was senior scientist at the National Institute of Standard and Technology in Gaithersburg, USA. He made numerous outstanding contributions to the field of mass spectrometry and IDMS     

A versatile method for stable carbon isotope analysis of carbohydrates by high-performance liquid chromatography/isotope ratio mass spectrometry

We have developed a method to analyze stable carbon isotope ((13)C/(12)C) ratios in a variety of carbohydrates using high-performance liquid chromatography/isotope ratio mass spectrometry (HPLC/IRMS). The chromatography is based on strong anion-exchange columns with low strength NaOH eluents. An eluent concentration of 1 mM resulted in low background signals and good separation of most of the typical plant neutral carbohydrates. We also show that more strongly bound carbohydrates such as acidic carbohydrates can be separated by inclusion of NO(3) (-) as an inorganic pusher ion in the eluent. Analyses of neutral carbohydrate concentrations and their stable carbon isotope ratios are shown for plant materials and marine sediment samples both at natural abundance and for (13)C-enriched samples. The main advantage of HPLC/IRMS analysis over traditional gas chromatography based methods is that no derivatization is needed resulting in simple sample treatment and improved accuracy and reproducibility.     

四极杆电感耦合等离子体质谱法测定沉积物中Pb稳定同位素比率研究

本文采用四极杆电感耦合等离子体质谱法测定了玄武湖和莫愁湖,及其相连的河道表层沉积物中Pb稳定同位素的比率.沉积物中208Pb/206Pb和206Pb/207Pb的比率范围分别为2.0931～2.1239和1.1558～1.1845.玄武湖、莫愁湖、护城河等采样点Pb稳定同位素比率,与文献中长江江苏段沉积物相近.其它河道采样点Pb稳定同位素组成与文献中南京市大气、土壤Pb稳定同位素比率相近.     

Preparation of starch and other carbon fractions from higher plant leaves for stable carbon isotope analysis.

The measurement of the carbon isotope composition of starch and cellulose still relies on chemical isolation of these water-insoluble plant constituents and subsequent elemental analysis by isotope ratio mass spectrometry (EA/IRMS) of the purified fractions, while delta(13)C values of low-molecular-weight organic compounds are now routinely measured by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). Here we report a simple and reliable method for processing milligram quantities of dried plant material for the analysis of the carbon isotope composition of lipids, soluble sugars, starch and cellulose from the same sample. We evaluated three different starch preparation methods, namely (1) enzymatic hydrolysis by alpha-amylase, (2) solubilization by dimethyl sulfoxide (DMSO) followed by precipitation with ethanol, and (3) partial hydrolysis by HCl followed by precipitation of the resulting dextrins by ethanol. Starch recovery for three commercially available native starches (from potato, rice and wheat) varied from 48 to 81% for the techniques based on precipitation, whereas the enzymatic technique exhibited yields between 99 and 105%. In addition, the DMSO and HCl techniques introduced a significant (13)C fractionation of up to 1.9 per thousand, while the carbon isotope composition of native starches analyzed after enzymatic digestion did not show any significant difference from that of untreated samples. The enzymatic starch preparation method was then incorporated into a protocol for determination of delta(13)C signatures of lipids, soluble carbohydrates, starch and crude cellulose. The procedure is based on methanol/chloroform/water extraction of dried and ground leaf material. After recovery of the chloroform phase (lipid fraction), the methanol/water phase was deionized by ion exchange (soluble carbohydrate fraction) and the pellet treated with heat-stable alpha-amylase (starch fraction). The remaining insoluble material was subjected to solvolysis by diglyme (cellulose fraction). The method was shown to be applicable to foliar tissues of a variety of different plant species (spruce, erect brome, maize and soybean).     

Boron Determination—A Review of Analytical Methods

This paper reviews published methods of sample preparation, determinand purification, and the determination of boron concentration and isotopic composition in a sample. The most common methods for the determination of B concentration are spectrophotometric and plasma-source spectrometric methods. Although most spectrophotometric methods are based on colorimetric reactions of B with azomethine-H, curcumin, or carmine, other colorimetric and fluorometric methods have also been used to some extent. These methods, in general, suffer from numerous interferences and have low sensitivity and precision. Application of nuclear reaction and atomic emission/absorption spectrometric (AES/AAS) methods has remained limited because these methods have poor sensitivity and suffer from serious memory effects and interferences. Among a large number of published nuclear reaction methods only prompt-γ spectrometry has been of practical use. The prompt-γ method can determine B concentration in intact samples, which makes this method especially useful for some medical applications, including boron neutron capture therapy. However, this is a time-consuming method and not suitable for detection of low levels of B. Inductively coupled plasma optical emission spectrometry (ICP-OES) created a new dimension in B determination because of its simplicity, sensitivity, and multielement capability. However, it suffers interferences and is not adequately sensitive for some nutritional and medical applications involving animal tissues that are naturally low in B. All methods involving the measurement of B isotopic composition require a mass spectrometer. Thermal ionization mass spectrometry (TIMS) and secondary ion mass spectrometry (SIMS) have been used to measure isotopic composition of B; however, these methods are time consuming and require extensive sample preparation and purification. Development of inductively coupled plasma mass spectrometry (ICP-MS) not only overcame most of the drawbacks of earlier methods, but also its capabiltiy of measuring B isotopes made possible (1) B concentration determination by isotope dilution, (2) verification of B concentration by isotope fingerprinting in routine analysis, and (3) determination of total B concentration and B isotope ratio for biological tracer studies in the same run. Therefore, plasma source MS appears to be the method of choice among present-day technologies.     

Minimization of carbon addition during derivatization of monosaccharides for compound-specific delta13C analysis in environmental research

Little is known about the delta13C composition of monosaccharides representing the largest carbon reservoir in the biosphere. The main reason for this might be that monosaccharides have to be derivatized prior to gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS) analyses and that a large isotopic correction is necessary for the carbon that has to be added to the original molecule during derivatization, resulting in large uncertainty of the calculated delta13C values of individual monosaccharides. The amount of added derivatization carbon is twice (alditol acetates) or even three times (trimethylsilyl (TMS) derivatives) as high as the amount of the original monosaccharide carbon. In addition, isotope fractionation occurs during acetylation. Therefore, the objectives of this study were (i) to minimize carbon addition during derivatization for GC/C/IRMS measurements of monosaccharides in soil and sediment samples and (ii) to quantify improvements in accuracy and precision of the final results. Minimization of carbon addition was accomplished by derivatization with methylboronic acid (MBA) and TMS thereafter (MBA method). Monosaccharides derivatized with the MBA method instead of TMS reduced the number of added carbon atoms from 2.2-2.7 to 0.3-0.8 per sugar carbon atom. Although the precision of GC/C/IRMS measurements with both methods is comparable (about 0.3 per thousand), delta13C values of an internal standard indicated that the newly developed MBA method is about 2 per thousand more accurate than the TMS method. delta13C comparison between soil samples that differed only slightly in their bulk carbon isotope signature showed that the MBA method is better in proving these small differences on a significant level. Total precision of the whole MBA method including all analytical and calculation steps is better by a factor of almost three than the TMS method.     

Performance of alpha spectrometry in the analysis of uranium isotopes in environmental and nuclear materials

The accuracy of alpha spectrometry in the determination of uranium isotopes at various concentrations levels and with various isotope ratios was tested in a round robin international intercomparison exercise. Results of isotope activity/mass and isotope mass ratios obtained by alpha spectrometry were accurate in a wide range of uranium masses and in isotopic ratios typical of depleted, natural, and low enriched uranium samples. Determinations by alpha spectrometry compared very satisfactorily in accuracy with those by mass spectrometry. For example, determination of U isotopes in natural uranium by alpha spectrometry agreed with mass spectrometry determinations at within ±1%. However, the ²³⁶U isotope, particularly if present in activities much lower than ²³⁵U, might not be determined accurately due to overlap in the alpha particle energies of these two uranium isotopes.