首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 971 毫秒
1.
Arsenic speciation was determined by anion-exchange chromatography-inductively coupled plasma-mass spectrometry (AEC-ICP-MS) in groundwater samples collected from an aquifer impacted by methylated As pesticides. Besides the four expected arsenic species AsO3(3-), As4(3-), (CH3)AsO3(2-) and (CH3)2AsO2-, up to nine other arsenic species were encountered, which constituted a major fraction of the total arsenic concentration in most samples. We then synthesized the thio-derivatives of (CH3)AsO3(2-) and (CH3)2AsO2-, and characterized the formed products by electrospray-tandem mass spectrometry (ES-MS-MS). The presence of (CH3)AsO2S2-, (CH3)AsOS2(2-), (CH3)2AsOS- and (CH3)2AsS2-, was confirmed in the groundwater by retention time matching plus ES-MS-MS in collected AEC fraction, and the presence of the trivalent methylated arsenic species (CH3)AsO2(2-) was suggested based on retention time matching only. These arsenic species have not been observed in ambient waters before, and are likely to occur in many environments containing methylated arsenic species and reduced sulfur compounds. They can persist in some of these particular samples for periods of up to six months without preservation, but tend to convert into the corresponding pentavalent oxy-species. Acidification with HCI shifted speciation equilibria rapidly, and is thus unsuitable for stabilizing samples containing these novel arsenic species; cryofreezing or no sample preservation avoided this artifact.  相似文献   

2.
Mono-, di-, tri-, and tetrathioarsenate, as well as methylated arsenic oxy- and thioanions, were determined besides arsenite and arsenate in geothermal waters of Yellowstone National Park using anion-exchange chromatography inductively coupled plasma mass spectrometry. Retention time match with synthetic standards, measured S:As ratios, and molecular electrospray mass spectra support the identification. Acidification was unsuitable for arsenic species preservation in sulfidic waters, with HCI addition causing loss of total dissolved arsenic, presumably by precipitation of arsenic-sulfides. Flash-freezing is preferred for the preservation of arsenic species for several weeks. After thawing, samples must be analyzed immediately. Thioarsenates occurred over a pH range of 2.1 to 9.3 in the geothermal waters. They clearly predominated under alkaline conditions (up to 83% of total arsenic), but monothioarsenate also was detected in acidic waters (up to 34%). Kinetic studies along a drainage channel showed the importance of thioarsenates for the fate of arsenic discharged from the sulfidic hot spring. The observed arsenic speciation changes suggest three separate reactions: the transformation of trithioarsenate to arsenite (major initial reaction), the stepwise ligand exchange from tri- via di- and monothioarsenate to arsenate (minor reaction), and the oxidation of arsenite to arsenate, which only becomes quantitatively important after thioarsenates have disappeared.  相似文献   

3.
In this study we evaluate the potential of anaerobic granular sludge as an inoculum for the bioremediation of selenium-contaminated waters using species-specific analytical methods. Solid species formed by microbial reduction were investigated using X-ray absorption near-edge structure (XANES) spectroscopy at the selenium K-edge. Furthermore, dissolved selenium species were specifically determined by ion chromatography (IC) and solid-phase microextraction gas chromatography-mass spectrometry (SPME-GC-MS). Least-squares linear combination of the XANES spectra for samples incubated with the highest selenate/selenite concentrations (10(-3) M) show the predominance of elemental selenium and a Se(-I) selenide, such as ferroselite, the thermodynamically most stable iron selenide. In contrast, elemental selenium and Se(-II) selenides are the main species detected at the lower selenate/selenite concentrations. In each repeated fed batch incubation, most aqueous selenite anions were converted into solid selenium species, regardless of the type of electron donor used (acetate or H(2)/CO(2)) and the selenium concentration applied. On the other hand, at higher concentrations of selenate (10(-4) and 10(-3) M), significant amounts of the oxyanion remained unconverted after consecutive incubations. SPME-GC-MS demonstrated selenium alkylation with both electron donors investigated, as dimethyl selenide (DMSe) and dimethyl diselenide (DMDSe). Selenite was even more alkylated in the presence of H(2)/CO(2) (maximum 2156 μg of Se/L of DMSe + DMDSe) as compared to acetate (maximum 50 μg of Se/L). In contrast, selenate was less alkylated using both electron donors (maximum 166 and 3 μg of Se/L, respectively). The high alkylation potential for selenite limits its bioremediation in selenium laden waters involving H(2)/CO(2) as the electron donor despite the fact that nontoxic elemental selenium and thermodynamically stable metal selenide species are formed.  相似文献   

4.
A simple method based on cloud point extraction (CPE) separation and inductively coupled plasma mass spectrometry (ICP-MS) detection was proposed for the determination of species of aqueous-exchangeable selenium and unaqueous-exchangeable selenium. When the system temperature is higher than the cloud point extraction temperature (CPT) of the surfactant of p-octyl polyethyleneglycolphenyl ether (Triton X-100), the complex of selenium(IV)–diethyl-dithiocarbamate (DDTC) (total selenium and aqueous-exchangeable selenium) could be extracted into the surfactant-rich phase, an in situ separation of selenium(IV) could be realized. Unaqueous-exchangeable selenium concentration was obtained by respectively subtracting aqueous-exchangeable selenium from the total selenium. The chemical variables affecting the CPE were optimized. Under the optimized conditions, the limit of detection (LOD) and the relative standard deviations (RSD) was 0.10 ng/mL and 3.2% (c?=?10.0 ng/mL, n?=?11), respectively, for Se(IV). The proposed method was applied to the speciation of aqueous-exchangeable and unaqueous-exchangeable selenium in tea samples with satisfactory results.  相似文献   

5.
转基因大豆对硒的富集作用和形态分布研究   总被引:1,自引:1,他引:0  
目的研究转基因大豆对硒的富集作用以及富集前后转基因大豆中硒的形态分布和形态转化。方法 采用电感耦合等离子体质谱分析转基因大豆富集前后硒的总量,采用蛋白酶提取,高效液相色谱-电感耦合等离子体质谱(high performance liquid chromatography-inductively coupled plasma-mass spectrometry,HPLC-ICP-MS)联用技术分析转基因大豆中的硒酸盐(selenate,Se VI)、亚硒酸盐(selenite,Se IV)、硒代蛋氨酸(selenomethionine,Se Met)和硒代胱氨酸(selenocystine,Se Cys)等几种硒化合物。盆栽种植试验研究转基因大豆对硒的富集作用。通过对照试验,考察大豆植株不同部位总硒含量变化和形态分布的转化情况。结果转基因大豆对硒有较好的富集作用,吸收的亚硒酸盐在大豆植株中部分转化成了硒代蛋氨酸和硒代胱氨酸。结论 了解了转基因大豆的形态分布和转化情况,可以更好地评估转基因大豆的食用安全风险并进行生物利用开发。  相似文献   

6.
目的 对云南省不同地区种植辣木中总硒和硒形态进行研究, 分析辣木各器官中总硒和硒形态以及与其他硒含量较高的农产品的差别。方法 采用Tris-HCl缓冲溶液加热超声提取辣木不同器官的固体粉末样品, 上清液经湿法消解处理, 利用电感耦合等离子体质谱(inductively coupled plasma mass spectrometry, ICP-MS)测定得到无机硒和总硒含量, 差减法计算有机硒含量。结果 辣木各器官中总硒和硒形态含量均较高, 高于绝大多数农产品, 而农产品中除少数几种农产品(巴西菇、竹荪、白寇)中总硒和硒形态含量较高外, 其他含量均较低; 辣木不同器官中总硒和硒形态含量不同, 含量高低顺序为叶>根>枝、干、果荚壳>皮。结论 辣木等农产品对硒及其形态的吸收能力不同, 硒不同形态在辣木等农产品不同器官中的积累能力不同, 尤其是辣木叶、辣木根对硒的富积能力较强。  相似文献   

7.
In this study, three liquid chromatographic techniques were employed to better understand selenium species distribution in Chives (Allium schoenoprasum) separately grown in three different supplementation media Se(IV), Se(VI), and SeMet. The highest selenium accumulation up to 700 μg Se g−1 was observed in the case of the Se(VI)-enriched samples on the basis of total selenium measurements. Size-exclusion chromatography (SEC-HPLC) was performed for investigation of selenium containing proteins in chives. For speciation of selenium containing amino acids, reversed-phase ion-pairing chromatography (RP-IP-HPLC) and for enantiomeric separations, a crown ether column was used. In all three cases online detection with inductively coupled plasma mass spectrometry was performed for selenium specific detection. Two extractions (perchloric acid–ethanol and enzymatic) were carried out on chive samples. Speciation analysis on the chives grown in three different media revealed that selenium distribution among different forms of amino acids in the sample strongly depends on the type of enrichment employed. Enrichment with Se(VI) leads to accumulation of selenium in inorganic forms, while in case of Se(IV) and SeMet-enriched samples, methyl-selenocysteine and selenocystine were found to be present. Not surprisingly, chiral speciation revealed the presence of the l-enantiomeric forms of selenoamino acids in the sample. The major enantiomer found in the perchloric acid–ethanol extracts was l-MeSeCys, while in the enzymatic extracts l-SeMet was also detected.  相似文献   

8.
《Food chemistry》2004,86(4):617-623
In this work chromatographic separation was coupled with mass spectrometry detection to study the speciation of selenium in selenium enriched onion leaves. The plants of onion (Allium cepa L.) were grown hydroponically for one week in standard medium containing inorganic selenium. The leaves and bulbs were separated from roots, the two types of material (leaves and bulbs) were dried and homogenized. The sodium hydroxide (0.1 mol l−1) extracts were analyzed by size exclusion chromatography (with spectrophotometric and mass spectrometric detection) showing the incorporation of selenium to the high molecular weight fraction, which was more pronounced in the leaves relative to the bulbs. This incorporation was better with Se(IV) enrichment (33% in leaves and 26% in bulbs) than with Se(VI) (3% and 5%, respectively). After extraction of the low molecular weight compounds (chloroform–methanol–water or 0.4 M perchloric acid–ethanol) and elimination of inorganic selenium (Dowex 1X8), selenium speciation was carried out by ion-pairing high performance chromatography [5 mmol l−1 citric acid, 5 mmol l−1 hexanesulfonic acid, pH 4.5: methanol (95:5)]. The primary organic selenium species found in leaves extracts was Se-methylselenocysteine, which has been reported as one of the most active chemopreventive selenium species as found in cell and animal experiments. The percentage contribution of selenium in this species was 4.0% and 1.9%, respectively, of the total selenium in leaves enriched with Se(IV) and Se(VI). It may be possible to use selenium enriched leaves as a dietary source of Se-methylselenocysteine. The important advantage of this source is the simple and fast enrichment process.  相似文献   

9.
Fish consumption today is widely recognized as highly beneficial since it constitutes a good source of several essential nutrients, such as selenium and polyunsaturated fatty acids (n-3 PUFA). However, fish can also contain contaminants such as mercury, which make the consumer, especially pregnant women, confused about the risk–benefit balance associated with fish consumption. This is particularly true for tropical fish species for which little information is available. We have previously reported that some Bermudian neonates had elevated mercury in their umbilical blood compared with international guidelines. The objective of this study was to give precise and balanced information on the content of mercury, selenium and PUFA in the most consumed fish species in Bermuda. In 2003 and 2006, a total of 307 fish were collected from 43 fish species and 351 samples were analysed (305 flesh samples, 44 liver samples, one roe and one fat sample) by inductively coupled plasma-mass spectrometry (ICP-MS) (metals) and high-resolution gas chromatography (HRGC) (fatty acids). Results show that mercury varies among species from 0.03 to 3.3 µg g?1 and that it is possible for at-risk groups such as pregnant women to make informed choices concerning fish consumption, e.g. maximizing fish species rich in nutrients and low in mercury.  相似文献   

10.
A method is described that allows precise determination of 234U/238U activity ratios (UAR) in most natural waters using commonly available inductively coupled plasma/mass spectrometry (ICP/MS) instrumentation and accessories. The precision achieved by this technique (+/- 0.5% RSD, 1 sigma) is intermediate between thermal ionization mass spectrometry (+/- 0.25% RSD, 1 sigma) and alpha particle spectrometry (+/- 5% RSD, 1 sigma). It is precise and rapid enough to allow analysis of a large number of samples in a short period of time at low cost using standard, commercially available quadrupole instrumentation with ultrasonic nebulizer and desolvator accessories. UARs have been analyzed successfully in fresh to moderately saline waters with U concentrations of from less than 1 microg/L to nearly 100 microg/L. An example of the uses of these data is shown for a study of surface-water mixing in the North Platte River in western Nebraska. This rapid and easy technique should encourage the wider use of uranium isotopes in surface-water and groundwater investigations, both for qualitative (e.g. identifying sources of water) and quantitative (e.g. determining end-member mixing ratios purposes.  相似文献   

11.
目的 随着人们膳食营养健康意识的不断提高,富硒辣木作为一种多功能植物具有很高的附加值和巨大的发展潜力。方法 为了研究硒在辣木-土壤中的富集转运,以盆栽辣木为试验材料,以电感耦合等离子体质谱仪为检测手段,以基施和喷施为外源硒添加方式,研究了硒在辣木中的富集效果以及土壤、辣木中硒含量的相关性。结果 结果表明,辣木是较好的硒富集植物,喷施添加比基施添加对硒的富集作用明显,喷施处理后,辣木杆、根及土壤中硒含量比未添加分别增加了约10倍、6倍、1倍,基施处理后,辣木杆、根及土壤中硒含量比未添加分别增加了约2倍、2倍、3倍,与基施相比,喷施后硒的生物可利用性更高;硒添加后,在土壤-辣木系统中迁移转运,与从地下部分到地上部分的转运效率相比,从地上部分到地下部分的转运效率更高,且硒主要在杆中积累;随着添加量的增加,硒会逐渐迁移转运至根部和土壤中,并在土壤中积累;无论哪种添加方式,硒的富集效果均是:杆>根>土壤。结论 本试验的研究为生产中通过施硒肥的外源调控措施来改善植物中硒含量,为更合理的开发利用富硒产品提供了技术支撑。  相似文献   

12.
The retention and speciation of selenium in flour and bread was determined following experimental applications of selenium fertilisers to a high-yielding UK wheat crop. Flour and bread were produced using standard commercial practices. Total selenium was measured using inductively coupled plasma-mass spectrometry (ICP-MS) and the profile of selenium species in the flour and bread were determined using high performance liquid chromatography (HPLC) ICP-MS. The selenium concentration of flour ranged from 30 ng/g in white flour and 35 ng/g in wholemeal flour from untreated plots up to >1800 ng/g in white and >2200 ng/g in wholemeal flour processed from grain treated with selenium (as selenate) at the highest application rate of 100 g/ha. The relationship between the amount of selenium applied to the crop and the amount of selenium in flour and bread was approximately linear, indicating minimal loss of Se during grain processing and bread production. On average, application of selenium at 10 g/ha increased total selenium in white and wholemeal bread by 155 and 185 ng/g, respectively, equivalent to 6.4 and 7.1 μg selenium per average slice of white and wholemeal bread, respectively. Selenomethionine accounted for 65–87% of total extractable selenium species in Se-enriched flour and bread; selenocysteine, Se-methylselenocysteine selenite and selenate were also detected. Controlled agronomic biofortification of wheat crops for flour and bread production could provide an appropriate strategy to increase the intake of bioavailable selenium.  相似文献   

13.
硒是人体必不可少的微量元素, 不同形态的硒对人体的功能不同, 其中有机硒在抗氧化、抗癌、抗病毒、提高免疫力等方面对人体有重要作用。人体获取硒的途径主要通过膳食摄取, 如食用天然富硒食品、人工合成有机硒产品及有机硒强化剂等。市场上的富硒食品质量参差不齐, 为合理地评价食品中硒的摄入形态和水平, 对食品中硒的形态及含量的检测是近年来研究的一个重点。本文对食品中有机硒检测分离、形态分析以及含量测定等进行了综述, 并对以液相萃取法和酶解法为主的分离方法, 以气相色谱-电感耦合等离子体质谱法(gas chromatography-inductively coupled plasma spectrometry, GC-ICP-MS)、高效液相色谱-电感耦合等离子体质谱法(high performance liquid chromatography-inductively coupled plasma spectrometry, HPLC-ICP-MS)、高效液相色谱-串联三重四级杆质谱法(high performance liquid chromatography-tandem mass spectrometry, HPLC-MS/MS)以及电泳-电感耦合等离子体质谱法(capillary electrophoresis-inductively coupled plasma spectrometry, CE-ICP-MS)为主的检测方法等研究进展进行了总结, 以期对食品中有机硒的检测提供相应的理论依据, 促进食品中有机硒检测标准的发展。  相似文献   

14.
目的 分析样品基体给检测结果造成的增敏效应影响,建立一种能消除待测样品中基体的干扰,从而准确测定痕量硒的电感耦合等离子体质谱的检测方法。方法 样品经硝酸消解后, 采用标准加入法,标准溶液加入的体积不大于待测液体积2%的前提下,在氦气模式下以元素特定质量数定性,以待测元素质谱信号与内标元素质谱信号的强度比与待测元素的浓度成正比进行定量分析。结果 样品基底对硒有增敏效果采用标准加入法能很好消除样品基底干扰,检测5种标准物质的硒含量均在标示值范围内。工作曲线相关系数达到0.998,精密度试验的相对标准偏差为3.2%。结论 该方法相对外标法能更准确对痕量硒进行定量,适合测定基底复杂存在干扰的样品,对相同或相近的样品可以共用相同工作曲线测定硒含量。  相似文献   

15.
Analytical methods for determining perfluorochemicals (PFCs) and fluorotelomer alcohols (FTOHs) in plants using liquid chromatography/tandem mass spectrometry (LC/MS/MS) and gas chromatography/mass spectrometry (GC/MS) were developed, and applied to quantify a suite of analytes in plants from biosolid-amended fields. Dichloromethane-methanol and ethylacetate were chosen as extracting solutions for PFCs and FTOHs, respectively. Nine perfluorocarboxylic acids (PFCAs), three perfluorosulfonic acids (PFSAs), and ten FTOHs were monitored. Most PFCAs and perfluorooctanesulfonate (PFOS) were quantifiable in plants grown in contaminated soils, whereas PFCs went undetected in plants from two background fields. Perfluorooctanoic acid (PFOA) was a major homologue (~10-200 ng/g dry wt), followed by perfluorodecanoic acid (~3-170 ng/g). [PFOS] in plants (1-20 ng/g) generally was less than or equal to most [PFCAs]. The site-specific grass/soil accumulation factor (GSAF = [PFC](Grass)/[PFC](Soil)) was calculated to assess transfer potentials from soils. Perfluorohexanoic acid had the highest GSAF (= 3.8), but the GSAF decreased considerably with increasing PFCA chain length. Log-transformed GSAF was significantly correlated with the PFCA carbon-length (p < 0.05). Of the measured alcohols, 8:2nFTOH was the dominant species (≤1.5 ng/g), but generally was present at ≥10× lower concentrations than PFOA.  相似文献   

16.
目的优化电感耦合等离子体质谱法(inductively coupled plasma mass spectrometer, ICP-MS)测定食品中硒元素含量的条件,并对河北省食品中硒元素含量情况进行调查分析。方法选取8种不同基质的国家标准物质作为检测样品对实验条件进行优化,同时选择80Se作为检测目标,采用碰撞模式并加入内标和5%异丙醇的优化条件下对样品中硒元素含量进行检测。通过对比结果,分析河北省膳食样品中硒元素含量,对居民通过膳食补充硒元素给予指导。结果通过采用碰撞模式及内标添加法可以有效降低基质干扰,同时加入异丙醇可极大提高硒元素的信号强度;其在5.00~100.00μg/L范围内呈现良好的线性关系(r2=0.999),检出限为0.002mg/kg;坚果及籽类、豆类及豆制品和肉及肉制品含硒较高,坚果及籽类样品中鲍鱼果含量最高为1.472mg/kg,豆类及豆制品中黄豆含量最高为0.123mg/kg,肉及肉制品中鸭肉含量最高为0.169 mg/kg。结论在检测的6类食品中,坚果及籽类、豆类及豆制品和肉及肉制品中硒含量相对较高,缺硒人群可适量增加食用。  相似文献   

17.
X-ray absorption fine structure spectroscopy has been used to determine directly the oxidation states and speciation of selenium and arsenic in 10 fly ash samples collected from full-scale utility plants. Such information is needed to assess the health risk posed by these elements in fly ash and to understand their behavior during combustion and in fly ash disposal options, such as sequestration in tailings ponds. Selenium is found predominantly as Se(IV) in selenite (SeO3(2-)) species, whereas arsenic is found predominantly as As(V) in arsenate (AsO4(3-)) species. Two distinct types of selenite and arsenate spectra were observed depending upon whether the fly ash was derived from eastern U.S. bituminous (Fe-rich) coals or from western subbituminous or lignite (Ca-rich) coals. Similar spectral details were observed for both arsenic and selenium in the two different types of fly ash, suggesting that the postcombustion behavior and capture of both of these elements are likely controlled by the same dominant element or phase in each type of fly ash.  相似文献   

18.
《Food chemistry》2001,73(3):357-366
Laboratory experiments were carried out to investigate whether the selenium content of different kinds of cereals grown on Austrian soil could be raised by the application of compound fertilisers containing selenium as selenate. An anion exchange chromatographic system coupled to an HP 4500 inductively coupled plasma mass spectrometer (ICP–MS) was used for the identification and quantification of selenium compounds in cereal samples. The HPLC–ICP–MS system was optimized for the separation of selenite, selenate, selenocystine, and selenomethionine using a Hamilton PRP-X100 column. Separation was obtained, with a 10 mM citrate buffer (pH 5), 2% methanol as mobile phase and a flow rate of 1.5 ml min−1. Four baseline separated chromatographic peaks were obtained within 6 min. The retention behavior of a further five selenium [selenohomocystine (Sehcys), selenocystathionine (Secysta), selenoethionine (Seet), trimethylselenonium iodide (TmSe), and dimethyl(3-amino-3-carboxy-1-propyl)selenonium iodide (DmpSe)] compounds was investigated. Aqueous extraction and enzymatic hydrolysis of the biological materials were also compared with respect to the amount of selenium extracted. In the aqueous extracts only 3–9% of the total concentration of selenium was found. When the cereal samples were exposed to an enzymatic hydrolysis, recovery rates ranging from 80 to 95% were obtained. A major part of the selenate, which had been taken up by the cereals was converted to selenomethionine.  相似文献   

19.
A combination of ion chromatography (IC) and inductively coupled plasma-mass spectrometry (ICP-MS) was used to determine iodine species in Thuringian milk samples. The developed method allows the fast and sensitive determination of iodine species with limits of determination for iodide and iodate <2 µg/L. Iodide was identified as the main iodine species in milk, but in a few samples also traces of iodate and several unidentified, presumably organoiodine compounds were observed as well. In addition, the total iodine concentration in the samples was determined by ICP-MS and gives an idea about the actual iodine state in Thuringian milk.  相似文献   

20.
黄彪  刘文静  方灵  韦航  吴建鸿  傅建炜 《食品工业科技》2020,41(10):254-258,270
目的:建立超高效液相色谱-串联质谱法(UPLC-MS/MS)快速分析茶叶中儿茶素类物质如儿茶素(Catechin,C)、表儿茶素(Epicatechin,EC)、没食子儿茶素(Gallocatechin,GC)、表没食子儿茶素(Epigallocatechin,EGC)、表没食子儿茶素没食子酸酯(Epigallocatechin gallate,EGCG)等,对几种福建乌龙茶和白茶中的儿茶素类物质进行分析。方法:实验使用Waters T3 C18色谱柱(250 mm×4.6 mm,5 μm),以0.1%(V/V)甲酸水溶液和甲醇为流动相对目标物进行梯度洗脱后,电喷雾正离子扫描方式下多反应监测(MRM)模式分析。结果:8 min内即可完成茶叶中8种儿茶素类物质的上机检测;儿茶素类物质的检出限为0.2~1.1 μg/L,线性方程的相关系数(r)为0.9966~0.9994。用建立的方法分析所采集的几种福建茶叶样品,表没食子儿茶素没食子酸酯(EGCG)相对于其它儿茶素类物质在茶叶中的含量最高,约占茶叶中儿茶素总量的60%。乌龙茶中儿茶素总量的含量范围为43.59~45.21 mg/g,白茶儿茶素总量的含量范围为50.52~70.71 mg/g。结论:建立的方法灵敏、准确、快速,研究结果可为福建茶叶产品的开发提供一定的科学依据。  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号