Characterisation of Fulvic Acids and Glycyrrhizic Acid by Time‐of‐Flight Secondary Ion Mass Spectrometry     

Wilfried Szymczak  Manfred Wolf  Klaus Wittmaack 《洁净——土壤、空气、水》2001,28(7):350-358

Fulvic acids of different origin, spray deposited on polished silicon after dissolution in high‐purity water without any additives, were analysed by time‐of‐flight secondary ion mass spectrometry (TOF‐SIMS) in combination with oblique 24...36 keV SF₅⁺ ion bombardment. The observed, highly reproducible mass spectra cover more than five orders of magnitude in dynamic range, without background subtraction. Apart from lines due to atomic ions and low‐mass ion fragments, the mass spectra exhibit broad maxima between m/z 200...350, mainly due to a beat‐like superposition of lines at every single mass number, up to at least m/z 400. In the negative ion spectra the beats have a spacing of m/z 14, corresponding to a CH₂‐unit. The high‐mass tails of the spectra extend well beyond m/z 5000, with similar slopes in the positive and the negative ion mass spectra. The negative spectra appear to be less affected by fragmentation products than the positive spectra. Fulvic acids (FAs) of different origin show distinctly different spectra, with mean masses ranging between m/z ≈ 450 and 580 (for a low‐mass cut‐off m/z 150). To further verify the ability of TOF‐SIMS to detect molecules and clusters with masses significantly above the maxima of the FA spectra, samples of glycyrrhizic acid (GA, as GA ammonium salt with molecular weight 840) were also analysed. Parent ions as well as multimers (GA)_n were observed as positive and negative ions, up to n = 4 (m/z 3320). The results are compared with spectra recently obtained by other mass spectrometric techniques.  相似文献   

Sorption and Chemical Reactions of PAHs with Dissolved Humic Substances and Related Model Polymers     

Frank‐Dieter Kopinke  Anett Georgi  Katrin Mackenzie 《洁净——土壤、空气、水》2001,28(7):385-399

Sorption coefficients measured for PAHs on dissolved humic substances by SPME and FQT were found to be inevitably different and method‐dependent – SPME provides activity‐based and FQT concentration‐based sorption coefficients. Poly(acrylic acid) esters as well‐defined model polymers were used in sorption experiments, leading to the conclusion that short aliphatic chains are more effective in binding PAHs than aromatic moieties. FQT was inappropriate to measure sorption coefficients for the interaction of pyrene with poly(acrylic acid) esters but the experiments revealed a characteristic shift in the fluorescence spectrum. Using pyrene as a probe for the molecular environment in the sorbed state, the observed spectral shift indicated a highly hydrophobic microenvironment. The empirical relationships between lg K_DOC and lg K_OW were generalized on the basis of a modified Flory‐Huggins concept. Introducing only one sorbent‐specific parameter, the solubility parameter δ_DOM, the calculation of sorption coefficients became possible for a wide range of HOCs using fundamental data readily available from the literature. Long‐term experiments showed that reactive PAHs (such as acenaphthylene and 9‐methylanthracene) are able to react with HAs under strictly abiotic and anoxic conditions, whereas less reactive PAHs (such as naphthalene and dihydroanthracene) do not form bound residues. The HA reveals two functions in the interaction, behaving as a reaction partner and as a protecting ligand.  相似文献   

Time-resolved Fluorescence Measurements of Aquatic Natural Organic Matter (NOM)     

M. U. Kumke  G. Abbt-Braun  F. H. Frimmel 《洁净——土壤、空气、水》1998,26(2):73-81

The fluorescence decay of aquatic natural organic matter (NOM) samples was investigated using the time-correlated single photon counting technique (TCSPC). Two different approaches for the data analysis are presented: the discrete component approach (DCA) and the exponential series method (ESM). The parameter set obtained in the DCA is discussed in terms of characterization for NOM of different origins. However, the obtained parameter set can only be interpreted as operationally defined. Using the ESM for a fluorescence decay time distribution analysis no a priori assumption about the number of fluorescing components was introduced into the data analysis. The interpretation of fluorescence decay time data for samples before and after ozonation is in good agreement with results of other analytical methods.  相似文献   

太湖、洞庭湖野生青虾肌肉中有机氯农药的气相色谱-质谱法测定   总被引：4，自引：0，他引：4  

史双昕  卢婉云  邵丁丁  周丽  张烃  黄业茹 《湖泊科学》2009,21(5):631-636

使用气相色谱质谱技术测定了青虾肌肉组织中的8种有机氯农药.包括六氯苯、氯丹、滴滴涕(ΣDDTs)、艾氏剂、狄氏剂、异狄氏剂、七氯和灭蚁灵,对太湖和洞庭湖15个点位29组野士青虾样品的测定结果显示,青虾肌肉组织内残留的有机氯农药主要是六氯苯和滴滴涕,六氯苯含量为nd-13.2μg/kg(湿重),滴滴涕含量为0.790-5.82μg/kg(湿重),洞庭湖青虾肌肉中有机氯农药的含量略高于太湖青虾,两湖青虾肌肉残留有机氯农药在枯水期时的含量多数大于丰水期时的含量.  相似文献   

Untersuchungen zum Abbau von Pharmaka in kommunalen Kläranlagen mit HPLC-Electrospray-Massenspektrometrie     

E. Mhle  C. Kempter  A. Kern  J. W. Metzger 《洁净——土壤、空气、水》1999,27(6):430-436

Examination of the Degradation of Drugs in Municipal Sewage Plants Using Liquid Chromatography-Electrospray Mass Spectrometry Numerous drugs can be identified in the secondary effluent of municipal sewage plants. In order to obtain information about the degree of elimination (adsorption, aerobic degradation) of these compounds, a batch reactor containing different drugs in environmentally relevant concentrations and a suspension of activated sludge was coupled to a HPLC-MS-MS system. During a testing period of three days concentration-time-curves were recorded. For most of the examined drugs (acetamidoantipyrine, crotamiton, diclofenac, primidone, propyphenazone) solely a strong decrease of the initial concentration within the first 15 minutes was observed, which was interpreted primarily as adsorption to the activated sludge. For acetaminophenol and pentoxifyllin an additional slower decrease in concentration within several hours was observed. This slower elimination was interpreted to be caused mainly by primary degradation. It could be shown that dihydrocodeine is oxidized to hydrocodone in the batch reactor. The conjugate acetaminophen glucuronide was cleaved.  相似文献   

Occurrence and Distribution of Organic Contaminants in the Aquatic System in Berlin. Part III: Determination of Synthetic Musks in Berlin Surface Water Applying Solid-phase Microextraction (SPME) and Gas Chromatography-Mass Spectrometry (GC-MS)     

Th. Heberer  S. Gramer  H.-J. Stan 《洁净——土壤、空气、水》1999,27(3):150-156

Polycyclic musks and nitro musks were found as environmental pollutants in screening analyses of 30 representative surface water samples collected from rivers, lakes, and canals in Berlin. These synthetic musks, which are used as fragrances in cosmetics, detergents, and other products, are discharged by the municipal sewage treatment plants into Berlinπs surface waters. In particular, the polycyclic musks 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-(g)-2-benzopyrane (HHCB; Galaxolide®, Abbalide®) and 7-acetyl-1,1,3,4,4,6-hexamethyltetraline (AHTN; Tonalide®, Fixolide®) were found in the receiving surface waters at considerable concentrations up to the μg/L-level. In the Wuhle, a small brook almost totally consisting of sewage effluents, maximum concentrations were 12.5 μg/L for HHCB and 6.8 μg/L for AHTN. Additionally, the polycyclic musk 4-acetyl-1,1-dimethyl-6-tert-butylindane (ADBI; Celestolide®, Crysolide®) and 1-tert-butyl-3,5-dimethyl-2,6-dinitro-4-acetylbenzene (musk ketone) were detected at low concentrations in most of the samples. Two other nitro musks, namely 1,1,3,3,5-pentamethyl-4,6-dinitroindene (musk moskene) and 1-tert-butyl-3,5-dimethyl-2,4,6-trinitrobenzene (musk xylene), were only detected in a single surface water sample. Solid-phase microextraction (SPME) with detection by gas chromatography-mass spectrometry (GC-MS) has proven to be a rapid and reliable tool for the screening of synthetic musks in surface and sewage water samples. Internal calibration with a suitable internal standard enables reproducible quantitation of the analytes down to the low ng/L-level.  相似文献   

Occurrence and Distribution of Organic Contaminants in the Aquatic System in Berlin.Part II: Substituted Phenols in Berlin Surface Water     

K. Schmidt-Bumler  Th. Heberer  H.-J. Stan 《洁净——土壤、空气、水》1999,27(3):143-149

In a surface water screening, 30 representative surface water samples collected from rivers, canals, and lakes in Berlin were investigated for the presence of 22 substituted phenols. The phenols selected include the 11 phenols considered as “priority pollutants” by the US Environmental Protection Agency (US-EPA). Surface water samples were extracted applying solid-phase extraction with styrenedivinylbenzene adsorbent. The recoveries, determined in spiking experiments, were between 80 % and 103 %. After derivatization with N-(tert-butyldimethylsilyl)-N-methyl-trifluoroacetamide (MTBSTFA) the samples were analyzed by capillary gas chromatography-mass spectrometry (GC-MS). Phenol, cresols, 2-ethylphenol, 2-chlorophenol, 4-chloro-3-methylphenol, pentachlorophenol, 2-nitrophenol, and 4-nitrophenol were detected in the surface water samples at concentrations between 0.02 μg/L and 7.8 μg/L, respectively. The distribution of these residues in the Berlin surface waters showed that the phenolic residues, with the exception of pentachlorophenol and 2-ethylphenol, do not originate primarily from municipal sewage treatment plants discharges. Some of the phenols are formed naturally or occur as ubiquitous anthropogenic contaminants in the aquatic system.  相似文献   

Extent and nature of hydrocarbon occurrence in the groundwater of Kuwait     

Eman Al-Awadi  Michael Quinn  Amitabha Mukhopadhyay  Andre Hauser  Adnan Akber  Adel Al-Haddad  Majed Al-Rashedi 《Environmental Geology》2009,56(5):877-889

A study, aimed at characterizing the nature of anthropogenic and biogenic hydrocarbon contamination in the groundwater of Kuwait, was carried out using fluorescence spectroscopy and other analytical techniques. The results of these analyses have demonstrated that the groundwater in certain areas of northern Kuwait has been significantly impacted by contamination originating from the oil-contaminated surface soils. The study revealed that a water-soluble fraction (WSF) of the crude oil surface contamination appeared to be slowly leaching into the freshwater lenses located in the area. The study also showed that hydrocarbon pollutants were practically absent in the brackish water areas of central and southern Kuwait, except for a few isolated sites. However, nonpetroleum hydrocarbons, with ultraviolet-visible absorption characteristics and fluorescence characteristics typically associated with humic substances, were observed at a few sites in the brackish water fields.  相似文献   

Interaction between Microbes DNA and Atrazine in Black Soil Analyzed by Spectroscopy          下载免费PDF全文

Ying Zhang  Huosheng Guo  Dongfang Meng  Yang Wang  Po‐keung Wong 《洁净——土壤、空气、水》2015,43(6):867-871

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短波红外光谱技术在矽卡岩型矿床中的应用——以鄂东南铜绿山铜铁金矿床为例   总被引：2，自引：2，他引：0  

张世涛  陈华勇  张小波  张维峰  许超  韩金生  陈觅 《矿床地质》2017,36(6):1263-1288

铜绿山铜铁金矿床是长江中下游铜铁多金属成矿带最重要的矽卡岩型矿床之一,矿床的形成与铜绿山石英闪长岩株体密切相关,矿体主要沿北北东向断裂产于石英闪长岩与大理岩/白云质大理岩的接触带,形成钙-镁复合型矽卡岩铜多金属矿化。围岩蚀变由致矿岩体到接触-蚀变矿化中心为:绢云母-绿泥石-钾化带、高岭石-绿泥石-弱矽卡岩化带、皂石-绿泥石-强矽卡岩化带。蚀变矿化期次可分为岩浆-热液期和表生期,其中,岩浆-热液期可分为矽卡岩阶段、退化蚀变阶段、氧化物阶段、硫化物阶段和碳酸盐阶段。绿泥石是钻孔岩芯中出现最多且分布最为广泛的蚀变矿物之一。经短波红外光谱(SWIR)研究发现,从蚀变矿化中心到外围,绿泥石出现由铁绿泥石/铁镁绿泥石逐渐转变为镁绿泥石,且绿泥石Fe-OH特征吸收峰位值(Pos2250)显示出从高值变为低值的趋势。结合其他蚀变矿物的空间分布特征,文章提出绿泥石的高Fe-OH特征吸收峰位值(Pos22502253 nm)与金云母、蛇纹石、绿帘石、皂石和高岭石的大量出现,对指示铜绿山矽卡岩型矿床的矿化中心具有一定的作用。  相似文献