Isotopes

同位素
  • 文章类型: Journal Article
    河流是Zn生物地球化学循环的重要途径。这项研究报告了中国西南部澜沧江流域悬浮颗粒物(SPM)的Zn浓度和δ66Zn组成,探讨自然过程和人类活动对Zn循环的影响。SPM样品的平均Zn含量(162mgkg-1)远高于上地壳(67.0mgkg-1),但它接近珠江的价值(187mgkg-1)。Zn在SPM中的富集因子(EF)值为1.08~6.88,平均值为2.15,未表现出显著的人为污染特征。SPM中的δ66Zn值范围为-0.67‰至+0.63‰,平均+0.13‰。在SPM中,δ66Zn值与Ca/Mg比值呈正相关,而与Zn含量的相关性很小。这表明人源对SPM的影响有限,SPM中的Zn同位素组成更有可能继承自风化岩石材料,并受到河水中自然分馏过程的影响。该结果有助于了解Zn的地球化学循环过程及其在水中的环境效应。
    River is an important pathway for the biogeochemical cycle of Zn. This study reports Zn concentration and δ66Zn composition for suspended particulate matter (SPM) from Lancang River basin in Southwest China, and explore the impact of natural processes and human activities on Zn cycle. The SPM samples have a much higher average Zn content (162 mg kg-1) than that of the upper crust (67.0 mg kg-1), but it is close to the value of the Pearl River (187 mg kg-1). The enrichment factor (EF) values of Zn in SPM range from 1.08 to 6.88, with an average of 2.15, which does not show significant pollution characteristics. The δ66Zn values in SPM range from -0.67‰ to +0.63‰, with an average of +0.13‰. The δ66Zn values showed positive correlation with Ca/Mg ratios while showed little correlation with Zn contents in SPM. It indicated that anthropogenic sources have limited influence on SPM, and the Zn isotope composition in SPM is more likely to be inherited from the weathered rocks materials and influenced by natural fractionation processes in river water. This result contributes to understanding of the geochemical cycling process of Zn and its environmental effects in water.
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  • 文章类型: Journal Article
    分析复杂基质中的低水平有机污染物对于监测全球食品安全至关重要。然而,平衡样品通量与复杂的实验设计和/或样品清理以最好地减少基体效应是一个持续的挑战。存在多种策略来减轻这些影响,基于内标的方法,如同位素稀释质谱(IDMS)是最有利的。这里,通过液相色谱-质谱(LC-MS)研究了多种内部校准策略,以定量小麦样品中的曲霉毒素A(OTA)。基于内标的定量方法,如单一(ID1MS),double(ID2MS),和五重(ID5MS)同位素稀释质谱,以及外部标准校准,进行了探索和比较。面粉中OTA的认证参考材料(CRM),MYCO-1用于评估每种方法的准确性。外部校准产生的结果比MYCO-1的认证值低18-38%,这主要是由于基质抑制作用。同时,与ID1MS相比,通过外部校准定量时,小麦样品获得的OTA质量分数始终较低,ID2MS,ID5MS所有同位素稀释方法产生的结果均在MYCO-1的预期范围内(3.17-4.93µg/kg),验证其准确性。然而,与ID2MS和ID5MS相比,从ID1MS获得的结果观察到OTA质量分数平均降低6%。经过审查,这些差异归因于同位素标记的内标[13C6]-OTA用于ID1MS的同位素富集偏差,OTAL-1CRM。说明了每种同位素方法的优点和局限性。
    Analysis of low-level organic contaminants in complex matrices is essential for monitoring global food safety. However, balancing sample throughput with complex experimental designs and/or sample clean-up to best reduce matrix effects is a constant challenge. Multiple strategies exist to mitigate these effects, with internal standard-based methods such as isotope dilution mass spectrometry (IDMS) being the most advantageous. Here, multiple internal calibration strategies were investigated for the quantification of ochratoxin A (OTA) in wheat samples by liquid chromatography-mass spectrometry (LC-MS). Internal standard-based quantitation methods such as single (ID1MS), double (ID2MS), and quintuple (ID5MS) isotope dilution mass spectrometry, as well as external standard calibration, were explored and compared. A certified reference material (CRM) of OTA in flour, MYCO-1, was used to evaluate the accuracy of each method. External calibration generated results 18-38% lower than the certified value for MYCO-1, largely due to matrix suppression effects. Concurrently, consistently lower OTA mass fractions were obtained for the wheat samples upon quantitation by external calibration as opposed to ID1MS, ID2MS, and ID5MS. All isotope dilution methods produced results that fell within the expected range for MYCO-1 (3.17-4.93 µg/kg), validating their accuracy. However, an average 6% decrease in the OTA mass fraction was observed from results obtained by ID1MS compared to those by ID2MS and ID5MS. Upon scrutiny, these differences were attributed to an isotopic enrichment bias in the isotopically labelled internal standard [13C6]-OTA that was used for ID1MS, the OTAL-1 CRM. The advantages and limitations of each isotopic method are illustrated.
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  • 文章类型: Case Reports
    来自Nonomuraeacoxensis的萜烯合酶被鉴定为()-1-表铜醇合酶。该酶在系统发育上与链霉菌中普遍存在的具有相同功能的已知酶无关。进行同位素标记实验以明确分配NMR数据并研究萜烯环化过程中的氢迁移。()-1-epi-cubenol和植物衍生化合物(-)-cubenol和(-)-1-epi-cubenol的环氧化证实了从棕色藻类Dictyopterisdivaricata中分离出的天然产物的结构,并允许得出其绝对构型。报道了来自()-和(-)-1-表-铜苯酚的环氧化物的晶体结构以及酸催化转化为异构酮的过程。
    A terpene synthase from Nonomuraea coxensis was identified as (+)-1-epi-cubenol synthase. The enzyme is phylogenetically unrelated to the known enzyme of the same function that is widespread in streptomycetes. Isotopic labelling experiments were performed to unambiguously assign the NMR data and to investigate hydrogen migrations during terpene cyclisations. Epoxidations of (+)-1-epi-cubenol and of the plant derived compounds (-)-cubenol and (-)-1-epi-cubenol confirmed the structure of a natural product isolated from the brown alga Dictyopteris divaricata and allowed to conclude on its absolute configuration. The crystal structures of the epoxides from (+)- and (-)-1-epi-cubenol and the acid catalysed conversion into an isomeric ketone are reported.
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  • 文章类型: Journal Article
    煤炭开采活动中释放的汞可能危害土壤生态系统,并对人类健康构成威胁。了解煤炭开采土壤中汞的积累特征,对于有效控制汞排放和制定汞污染防治措施具有重要意义。为了确定土壤中汞的潜在来源,本研究确定了煤矿周围地区原煤和不同表层土壤类型的汞浓度和同位素组成特征。结果表明,煤中汞主要以无机汞的形式存在,汞在掺入煤中之前经历了Hg2+光还原。此外,不同表土类型的汞同位素组成差异显著,与煤炭开采土壤相比,农田土壤的δ202Hg值表现出较大的负偏移。三元混合模型进一步揭示了两个地区之间潜在汞来源的实质性差异,随着煤炭开采土壤受到人为活动的极大干扰,以及原煤中汞的相对贡献,煤矸石,背景土壤占煤炭开采土壤的比例为33.42%,34.4%,和32.19%,分别。然而,来自原煤的汞,煤矸石和背景土壤贡献了17.04%,21.46%,农田土壤中汞的61.51%,表明农田土壤中汞的积累主要来自背景土壤。我们的研究表明,采矿活动大量积累的固体废物(脉石)引起的土壤二次污染对生态安全构成了重大挑战。这些发现为控制矿区土壤汞提供了新的见解,并进一步强调了对污染场地采取严格保护措施的紧迫性。
    The Hg released from coal mining activities can endanger soil ecosystems and pose a risk to human health. Understanding the accumulation characteristics of mercury (Hg) in coal mining soil is important for effectively controlling Hg emissions and developing measures for the prevention and control of Hg contamination. To identify the potential sources of Hg in soils, the Hg concentration and isotopic composition characteristics of raw coal and different topsoil types from the areas surrounding a coal mine were determined in this study. The results showed that Hg in coal mainly exists mainly in the form of inorganic Hg, and Hg has experienced Hg2+ photoreduction prior to incorporating into coal. In addition, the composition of Hg isotopes differed significantly among different topsoil types, and the δ202Hg value of the farmland soil exhibited large negative excursions compared to the coal mining soil. The ternary mixed model further revealed the presence of substantial differences in potential Hg sources among the two regions, with the coal mining soil being greatly disturbed by anthropogenic activity, and the relative contributions of Hg from raw coal, coal gangue, and background soil to coal mining soil being 33.42%, 34.4%, and 32.19%, respectively. However, Hg from raw coal, coal gangue and background soil contributed 17.04%, 21.46%, and 61.51% of the Hg in the farmland soil, indicating that the accumulation of Hg in farmland soil was derived primarily from the background soil. Our study demonstrated that secondary pollution in soil caused by immense accumulation of solid waste (gangue) by mining activities offers a significant challenge to ecological security. These findings provide new insights into controlling soil Hg in mining areas and further highlight the urgency of strict protective measures for contaminated sites.
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  • 文章类型: Journal Article
    塞拉利昂两个主要垃圾场的地下水盐度增加一直是利益攸关方的主要关切。因此,这项研究采用地球化学和稳定水同位素分析来研究控制地下水盐度的因素。还使用贝叶斯同位素混合模型评估了地下水的比例来源。地球化学分析表明,Granvillebrook垃圾场的地下水化学受水-岩相互作用和蒸发控制,而Kingtom的地下水化学则受水-岩相互作用和降水控制。相对于全球大气水线的氘(δ2H)与氧气(δ18O)组成的双图证实了研究区域的地下水是气象来源的。电导率与δ18O的线性图表明,矿化是影响研究区域地下水盐度的主要因素。R(SIMMR)中的稳定同位素混合模型表明,研究区域中96.5%的地下水通过降水补给,而只有3.5%来自地表水。SIMMR模型还描述了Granvillebrook垃圾场的地下水已被渗滤液(33.0%)和生活废水(15.2%)桥接,而对于Kingtom垃圾场,13%和21.5%被渗滤液和生活废水污染。与以前的其他研究相反,这项研究证实了使用贝叶斯同位素混合模型量化影响地下水盐度的因素的可行性。
    The increase in groundwater salinity of the two major dumpsites in Sierra Leone has been a major concern for stakeholders. Therefore, this study employed geochemical and stable water isotope analyses to investigate the factors controlling groundwater salinity. The proportional sources of the groundwaters were also evaluated using the Bayesian isotope mixing model. The geochemical analysis showed that the groundwater chemistry in the Granvillebrook dumpsite is controlled by water-rock interaction and evaporation while that of the Kingtom is dominated by water-rock interaction and precipitation. The biplot of deuterium (δ2H) versus oxygen (δ18O) composition relative to the global meteoric water line confirms that the groundwaters of the study areas are of meteoric origin. The linear plot of electrical conductivity versus δ18O depicts that mineralization is the major factor impacting the groundwater salinity in the study areas. The stable isotope mixing model in R (SIMMR) suggests that 96.5% of the groundwaters in the study areas are recharged by precipitation while only 3.5% originated from surface water. The SIMMR model also depicts that groundwaters in the Granvillebrook dumpsite have been bridged by leachate (33.0%) and domestic wastewater (15.2%) while for the Kingtom dumpsite, 13% and 21.5% are contaminated by leachate and domestic wastewaters. Contrary to other previous studies, this research confirms the feasibility of using the Bayesian isotope mixing model to quantify the factors influencing groundwater salinity.
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  • 文章类型: Journal Article
    目标:到目前为止,尚未对比利时的新石器时代遗骸进行87Sr/86Sr迁移率研究,有关该地区Sr同位素变化的信息很少。这项研究旨在探索来自葬礼洞穴“GrottedeLaFaucille”的最终新石器时代人口的流动性,有助于理解比利时生物可利用Sr的同位素组成,使用蛋白质组学分析评估男性流动性的证据,并探索非本地个人的可能来源。
    方法:测定了6名成人和6名青少年牙釉质的87Sr/86Sr同位素比。采用基于液相色谱质谱的蛋白质分析来鉴定男性生物性别的个体。微型哺乳动物牙齿的87Sr/86Sr,蜗牛壳,并对比利时三个地质地区的现代植物进行了测量,以建立生物可利用锶的同位素特征。通过比较人类87Sr/86Sr同位素比与87Sr/86Sr的生物可利用度Sr范围来评估非局部性。
    结果:四个个体产生的87Sr/86Sr同位素比与非本地来源一致。成人和青少年之间没有发现统计学差异。在样本集中检测到三名男性,其中两个显示非局部87Sr/86Sr值。
    结论:这项研究为最终的新石器时代比利时的流动性提供了证据。四个非本地87Sr/86Sr签名与荷兰南林堡的生物可用Sr的87Sr/86Sr相对应,德国西南部的黑森林,和法国的地区,例如巴黎盆地和Vosges的部分地区。结果支持与法国北部联系的统治假设,通过考古学研究发现。
    So far, no 87 Sr/86 Sr mobility studies have been done for Neolithic remains from Belgium and information on the Sr isotopic variability in the region is scarce. This study aims to explore mobility in a Final Neolithic population from the funerary cave \'Grotte de La Faucille\', contribute to the understanding of the isotopic composition of bioavailable Sr in Belgium, assess evidence for male mobility using proteomic analysis, and explore possible places of origin for nonlocal individuals.
    The 87 Sr/86 Sr isotope ratio of dental enamel from six adults and six juveniles was determined. Liquid chromatography mass spectrometry-based protein analysis was employed to identify individuals of male biological sex. 87 Sr/86 Sr of micromammal teeth, snail shells, and modern plants from three geological areas in Belgium were measured to establish isotopic signatures for bioavailable strontium. Nonlocality was assessed by comparing human 87 Sr/86 Sr isotope ratios to the 87 Sr/86 Sr range for bioavailable Sr.
    Four individuals yielded 87 Sr/86 Sr isotope ratios consistent with a nonlocal origin. No statistical differences were found between adults and juveniles. Three males were detected in the sample set, of which two show nonlocal 87 Sr/86 Sr values.
    This study provides evidence for mobility in Final Neolithic Belgium. The four nonlocal 87 Sr/86 Sr signatures correspond with the 87 Sr/86 Sr of bio-available Sr in Dutch South Limburg, the Black Forest in Southwest Germany, and regions of France, such as parts of the Paris Basin and the Vosges. The results support the ruling hypothesis of connections with Northern France, brought to light by archeological research.
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  • 文章类型: Journal Article
    Patagonian aquatic environments have been invaded since the end of the last century by different species of salmonids. Knowing the natal origin and homing/straying rate of the salmonids in colonised environments is essential to understanding the dispersal mechanisms and developing management plans. In the last two decades, Chinook salmon Oncorhynchus tshawytscha showed the greatest natural dispersal capacity in Patagonia. The main goal of this study was to evaluate the environmental strontium isotope ratio (87Sr/86Sr) as a potential natural tag to infer the natal origin and ontogenetic habitat use of salmonids in Patagonia, specifically Chinook salmon. 87Sr/86Sr ratio was determined in water samples from 26 sites distributed in 14 Atlantic and Pacific basins in low and high water seasons. Environmental 87Sr/86Sr showed greater spatial than temporal variation, revealing great potential as a tool to infer the natal origin and life history of several migratory fish species in Patagonia. Otolith core-to-edge 87Sr/86Sr profiles were also analysed in 108 Chinook salmon from six basins. A cluster analysis based on the Unweighted Pair Group method (UPGMA) and Euclidean distances without prior classification grouped the sampled rivers into five main groups with significantly different (p < 0.05) isotopic ratios, sometimes integrated basins with different slopes (Atlantic or Pacific). The cluster analysis based on the natal 87Sr/86Sr period in otolith (∼natal origin) showed clear segregation between the Atlantic and Pacific samples. A mismatch between water and otolith natal 87Sr/86Sr ratio was detected in some Atlantic basins (e.g. De las Vueltas River in Santa Cruz Basin) and Pacific (e.g. Liquiñe Basin) and, which could be explained either by straying behaviours or by large geochemical variability between tributaries, within river systems. Our results showed that 87Sr/86Sr is a useful natural tag to trace the life history of migratory fishes in Patagonia, especially for invasive species such as Chinook salmon.
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  • 文章类型: Journal Article
    黄铁矿是一种典型的硫化物矿物,含有各种潜在的有毒金属(类)(PTM)。黄铁矿冶炼和随后的工业利用活动通常会将大量的PTM释放到附近的生态系统中。它们可能富含附近农田的土壤和作物,通过食物链对人类健康造成隐藏但不可逆转的危害。在这里,分布模式,来源分配,铅的潜在健康风险,Zn,Cu,Cd和多个很少监测的PTM(Ag,Bi,Sb,Sr,Th,U,W,和V)在典型工业区十个不同地点的稻田土壤和水稻植物的不同器官中进行了调查,在那里,黄铁矿用于生产硫酸和随后的水泥几十年。结果表明,研究的稻田土壤中的Pb和Zn普遍超过了中国的最大允许水平(MPL),Sb和V的含量接近MPL。此外,水稻更容易生物积累Cd,Cu,和锌比其他研究的元素。危险商(HQ)计算表明,含有这种多种元素的大米可能对居民造成很高的潜在非致癌和致癌健康风险,特别是对于高级集团。Pb同位素示踪法结合PCA(主成分分析)进一步发现,黄铁矿的工业利用对水稻土中高富集PTM的贡献为18.58-55.41%。所有这些发现都表明,稻田土壤系统已受到黄铁矿工业活动的污染,应严格禁止在黄铁矿冶炼和相关工业场所附近种植水稻。
    Pyrite is a typical sulfide mineral which contains various potentially toxic metal(loid)s (PTMs). The pyrite smelting and subsequent industrial utilization activities usually release numerous amounts of PTMs into nearby ecosystem, which may be enriched in the nearby farmland soils and crops, leading to hidden but irreversible harm to human health via the food chain. Herein, the distribution pattern, source apportionment, and potential health risks of Pb, Zn, Cu, Cd and multiple seldom monitored PTMs (Ag, Bi, Sb, Sr, Th, U, W, and V) in the paddy soils and different organs of the rice plants from ten various sites in a typical industrial zone were investigated, where pyrite ores were used for the production of sulfuric acid and subsequent cement over several decades. The results showed that the contents of Cd, Pb and Zn in studied paddy soils generally exceeded the maximum permissible level (MPL) in China, and the contents of Sb and V were approaching the MPL. Moreover, the rice is easier to bioaccumulate Cd, Cu, and Zn than the other studied elements. The hazard quotient (HQ) calculations indicate that the rice containing such multiple elements may cause a high potential non-carcinogenic and carcinogenic health risk for residents, particularly for the senior group. The Pb isotope tracing method combined with PCA (principal component analysis) further uncovered that the pyrite industrial utilization contributed 18.58-55.41 % to the highly enriched PTMs in paddy soils. All these findings indicate that the paddy soil system has been contaminated by the pyrite industrial activities and certain distances or areas should be rigidly forbidden from rice cultivation in the proximity of the pyrite smelting and related industrial sites.
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  • 文章类型: Journal Article
    目的:8-异前列腺素F2α是脂质过氧化的生物标志物,也是最常用的氧化应激指标之一。它是肺癌风险的既定生物标志物。它通常通过酶联免疫吸附测定来测量。鉴于其重要性,我们开发了一种稳定的同位素稀释UPLC-串联质谱方法,用于快速测定血液中的8-异前列腺素。
    方法:我们在49例肺癌患者中测试了该方法的辨别能力,胸部X线检查发现55例良性肺结节患者,41例慢性阻塞性肺疾病(COPD)或哮喘患者。
    结果:三组之间的平均8-异前列腺素水平存在显着差异(p=0.027),和事后检查发现,肺癌患者的水平高于良性结节(p=0.032)和COPD/哮喘患者(p=0.014).用于区分肺癌组与良性结节组的接受操作特征曲线下面积(AUC)为0.69。与COPD/哮喘组的区别为0.7。
    结论:基于UPLC-MS/MS的方法是测量8-异前列腺素血浆浓度的有效分析工具。结果表明,探索其作为早期肺癌筛查标志物的实用性。
    8-iso-prostaglandin F2α is a biomarker of lipid peroxidation, and one of the most commonly used measures of oxidative stress. It is an established biomarker of lung cancer risk. It is commonly measured by enzyme-linked immunosorbent assay. Given its importance, we developed a stable isotope dilution UPLC-tandem mass spectrometric method for the rapid determination of 8-isoprostane in blood.
    We tested the discriminatory capability of the method in 49 lung cancer patients, 55 benign lung nodule patients detected by chest X-ray, and 41 patients with chronic obstructive pulmonary disease (COPD) or asthma.
    Significant differences were found in mean 8-isoprostane levels between the three groups (p = 0.027), and post-hoc tests found higher levels in the lung cancer patients than in patients with benign nodules (p = 0.032) and COPD/asthma (p = 0.014). The receiving operating characteristic area under the curve (AUC) was 0.69 for differentiating the lung cancer group from the benign nodule group, and 0.7 for differentiating from the COPD/asthma group.
    The UPLC-MS/MS-based method is an efficient analytical tool for measuring 8-isoprostane plasma concentrations. The results suggest exploring its utility as a marker for early lung cancer screening.
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  • 文章类型: Journal Article
    在意大利,马尼拉蛤给(菲律宾蛤仔,亚当斯和里夫,1850)主要位于波河三角洲的亚得里亚海北部泻湖,贝类养殖提供了重要的社会经济收入。然而,在我们全球化的世界里,海鲜市场受到欺诈活动的威胁,其中出售出处未经认证的农业食品,对消费者健康构成风险。多同位素比率分析通常用于追踪在不同气候和环境条件下不同国家生产的商品的来源。这里,我们调查了这种方法的可靠性,以追踪在三个彼此靠近的亚得里亚海北部泻湖中收获的马尼拉clam的确切来源。我们还核实了在当地超市购买的样品的来源,并附有出处证明。我们进行了碳(C)的元素分析,氮(N),和硫(S)和各自的同位素比(13C/12C;15N/14N;34S/32S)在马尼拉蛤类组织,加上碳同位素分析(13C/12C),氧气(18O/16O),和锶(87Sr/86Sr)在马尼拉蛤壳上。每个同位素参数可用于识别泻湖中发生的水和/或养分供应的海洋和大陆贡献。因此,线性判别分析(LDA)中同位素参数的组合可以鉴定出产生马尼拉clam的泻湖。
    In Italy, the production of manila clams (Ruditapes philippinarum, Adams and Reeve, 1850) is mainly localized in northern Adriatic lagoons in the Po River delta, where shellfish farming provides important socio-economic revenue. However, in our globalized world, the seafood market is threated by fraudulent activities, in which agri-food products whose provenance is not certified are sold, posing a risk to consumer health. Multi-isotope ratio analysis is commonly used to trace the provenance of goods produced in different countries with different climatic and environmental conditions. Here, we investigated the reliability of this approach in terms of tracing the exact provenance of manila clams harvested in three Adriatic northern lagoons that are close to each other. We also verified the origin of samples bought at a local supermarket with a certificate of provenance. We carried out elemental analyses of carbon (C), nitrogen (N), and sulfur (S) and the respective isotopic ratios (13C/12C; 15N/14N; 34S/32S) on manila clam tissues, plus isotopic analyses of carbon (13C/12C), oxygen (18O/16O), and strontium (87Sr/86Sr) on manila clam shells. Each isotopic parameter can be used to identify the marine and continental contributions of water and/or nutrient supplies occurring in the lagoons. Therefore, the combination of isotopic parameters in a linear discriminant analysis (LDA) allowed for the identification of the lagoons in which the manila clams were produced.
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