离子交换树脂分解磷矿测定氟、氯、碘

磷矿中氟、氯、碘的定量分析,通常采用分别取样,碱熔测定,手续比较麻烦。有人早已报导离子交换树脂可在水溶液中分解难溶块,文献介绍可以分解磷灰石,并用于测定氟。其后,则未见有实际应用的报导,我们在此基础上,详细地试验了用国产732型阳离子交换树脂分解磷矿的条件。试验证明,在分解样品后所得的溶液中,由于阳离子被分离除去,可以直接分取溶液采用一般方法测定氟、氯和碘。手续简便,效果较好。     

艾斯卡试剂熔矿、动态树脂交换——等离子体质谱法测定土壤样品中的痕量碘

研究了电感耦合等离子体质谱法（ICP—MS）测定土壤样品中微量碘的可行性,对测定碘的条件作了部分改进及进一步优化。样品经艾斯卡试剂分解,热水提取,阳离子交换树脂动态分离溶液中大量的钠、铁、锌等阳离子,干过滤部分溶液,采用电感耦合等离体子质谱法（ICP—MS）直接测定溶液中的碘。本方法用国家标准物质进行验证,测定结果和标准值吻合。并用该法顺利完成了陕西省宝鸡地区多目标区域地球化学调查样品中碘的测定。     

黄铁矿单矿物分析

黄铁矿常规分析多采用单独取样,针对某些元素采用有关分析方法。因而手续较繁琐,需要样品量也大。为了简化分析流程,减少样品用量,经试验拟定了黄铁矿单矿物系统分析流程。其特点是在一分称样中通过阳离子交换树脂分离,使阴阳离子分成两部分。在含阴离子溶液中可测定硫、砷、硒、磷等元素;在含阳离子溶液中可测定铁、铜、     

溴、碘的半熔法-电感耦合等离子质谱(ICP-MS)测定

样品用碳酸钠和氧化锌混合熔剂半熔,用80℃～100℃水提取,用强酸型阳离子树脂分离溶液中的大量钠等阳离子,采用电感耦合等离子质谱直接测定溶液中的溴和碘。测定下限溴为0．15μg／g,碘为0．028μg／g。     

黄铁矿单矿物分析

黄铁矿常规分析多采用单独取样,针对某些元素采用有关分析方法。因而手续较繁琐,需要样品量也大。为了简化分析流程,减少样品用量,经试验拟定了黄铁矿单矿物系统分析流程。其特点是在一分称样中通过阳离子交换树脂分离,使阴阳离子分成两部分。在含阴离子溶液中可测定硫、砷、硒、磷等元素;在含阳离子溶液中可测定铁、铜、锌、镉、钴、镍、锰、锢、钙、镁等元素。解决了黄铁矿单矿物主要项目的测定。 试剂及装置     

离子色谱法和动力学法测定地质样品中的氟、氯、溴、硫和碘

在本文中试验了氟、氯、溴、碘和硫的热水解的条件以及用离子色谱—电导法测定F~-、 Cl~-、Br~-和SO_4~(2-)和用催化比色法测定碘的条件。用本方法测定了14个国内外的沉积物和岩石标准样品。测定的结果与报导值吻合。对I~-的测定下限为0.1微克/克,F~-和Cl~-为30微克/克,Br~-和SO_4~(2-)为50微克/克。     

岩石土壤中微量氯、碘的离子电极的连续测定

用于地球化学探矿的氯碘分析方法已有一些报道,但至令尚感缺乏一个较理想的方法。有的方法灵敏度不够,有的又麻烦或分析条件要求太高,不适合大批样品分析。笔者在前人工作的基础上试验了碳酸钠—氧化锌半熔分解样品,用抗坏血酸还原高价碘,离子电极连续测定碘氯的方法。样品测定下限达到碘0.25ppm,氯50ppm。精度能满足要求,方法简便,成本低。初试地质效果良好。     

火焰原子吸收法间接测定磷矿中氯

火焰原子吸收法间接测定磷矿中氯达刘生１云南个旧市化肥厂中心化验室个旧６６１４１１目前磷矿中Ｃｌ－含量的测定多采用浊度法、氯离子选择电极法及离子色谱法。本文采用火焰原子吸收法来间接测定磷矿中Ｃｌ－，即在试样溶液中加入定量的Ａｇ＋，试样中Ｃｌ－与Ａｇ＋生...     

阳离子静态交换—离子色谱法同时测定地质试样中微量氯、溴及硫

地质样品中不但成分复杂,而且氯、溴及硫的含量相差悬殊,难于在一次取样中同时测定。所见报道的有热解氧化吸收法用于测定金属或岩石样品中氟、硫及氯;另一种是熔融后动态离子交换法,用于测定废水沉积物中氟、氯、磷及硫离子。上述两种分离及前处理方法,其回收率约为82—84％左右。而熔融法的优点是分解完全,不过当取样量多时,溶液中携带下来的大量硅给以后测定带来麻烦,不宜用于地质样品     

电感耦合等离子体质谱法同时测定地质样品中锗碘

样品用NaOH全熔,热水提取,分取部分溶液通过强酸性阳离子交换树脂,分离溶液中大量的钠离子后,采用电感耦合等离子体质谱法同时测定锗和碘。方法的检出限Ge、I分别为0.043μg/g和0.22μg/g,经土壤国家一级标准物质分析验证,结果与标准值相符,12次测定的RSD均小于10%。     

DETERMINATION OF FLUORINE, CHLORINE, BROMINE AND IODINE IN SEVEN GEOCHEMICAL REFERENCE SAMPLES

The concentrations of fluorine, chlorine, bromine and iodine of seven geochemical reference samples have been determined. Analytical techniques were neutron activation analysis for chlorine, bromine and iodine and ion-selective potentiometry for fluorine. After irradiation of the samples, these halogens were separated from the matrix elements by pyrohydrolysis in presence of vanadium (V) oxide. This extraction allows to measure the four halogens in the same sample.     

塔里木盆地南缘绿洲带地下水砷氟碘分布及共富集成因

由于地表水资源稀缺,地下水是塔里木盆地南缘绿洲带重要用水水源,因此,系统查明该区地下水砷氟碘的分布及成因至关重要。基于塔里木盆地南缘绿洲带233组地下水水样检测结果,分析不同含水层中高砷、高氟和高碘地下水的空间分布及水化学特征,结合研究区地质、水文地质条件和地下水赋存环境进一步揭示影响地下水砷氟碘的来源、迁移与富集的水文地球化学过程。结果表明:地下水砷、氟、碘浓度变化范围分别为1.091.2 μg/L、0.0128.31 mg/L、10.02 637.0 μg/L。地下水高砷、高氟和高碘水样分别占总水样的7.3%、47.2%和11.6%,砷氟碘共富集占比为3.0%。砷氟碘共富集地下水主要分布于研究区中部的民丰县,水化学类型主要为Cl·SO₄-Na型。自补给区至过渡区再至蒸发区,地下水氟、碘浓度明显增大,砷浓度在过渡区和蒸发区均较大;砷氟碘共富集地下水取样点主要分布于36.060.0 m深度的浅层承压含水层中。浅层地下水受蒸发作用和矿物溶解沉淀作用的影响,随砷氟碘富集项的增多而增大。第四纪成因类型中风积物对氟浓度的影响较大,洪积-湖积物对砷和碘浓度的影响较大。细粒岩性、平缓的地形、地下水浅埋条件、偏碱性的地下水环境、微生物降解作用下有机质介导的矿物溶解是利于砷氟碘共富集的主要机制。     

Iodine (and Other Halogens) in Twenty Six Geological Reference Materials by ICP-MS and Ion Chromatography

Analytical results for iodine in twenty six geological reference materials (RM) are presented. Bromine, fluorine and chlorine were also determined in some samples. Pyrohydrolysis in a heated quartz tube under a wet oxygen flow was used for the separation of the halogens from the matrix and the evolved gas was absorbed in a trap solution. The halogens were measured by ICP-MS and ion chromatography (IC). All four halogens can be collected in the trap solution from one combustion procedure. The analysed samples range in type from igneous rocks to terrestrial and marine sediments. Precision, detection limits, and accuracy are also presented.     

大同盆地地下水高砷、氟、碘分布规律与成因分析及质量区划

为了对大同盆地地下水中砷、氟、碘等的分布和成因进行分析,开展地下水质量区划,依据地下水污染调查取得的最新系列测试数据,结合以往水文地质和水文地球化学研究成果,编制大同盆地浅层和中深层地下水砷含量、氟含量、碘含量等水化学特征分布图,以直观反映大同盆地地下水高砷、高氟、高碘区的空间分布规律; 通过分析pH值、硫酸根含量、硝酸根含量、铁含量、锰含量与砷的关系,探讨高砷水的形成原因; 根据pH值、钙离子、重碳酸氢根离子与氟的关系,分析氟超标原因; 指出高碘区与高氟区分布的相似性和成因的相似性。研究结果表明,盆地周边高砷、高氟岩层是地下水砷、氟的原生来源,特定的河湖相沉积环境则为砷、碘的富集提供了原生地质条件; 北部地区氟增高与地下水位下降致使黏性土中的氟离子进入含水层有关,中部地区高氟与土壤盐渍化有关; 中部富含淤泥质黏土的湖相地层是碘富集的原生地质因素,冲积洼地地下水径流条件滞缓是碘富集的水动力因素; 干旱气候条件下强烈的蒸发浓缩作用亦是高氟、高碘地下水形成的重要因素。依据砷、氟、碘、硝酸盐、亚硝酸盐、总含盐量(total dissolved salt,TDS)、总硬度、氨氮等单组分含量分布,利用GIS空间分析功能,进行了大同盆地浅层和中深层地下水质量区划,可为当地地下水开发利用提供地学依据。     

Determination of Halogens (F, Cl, Br, I), Sulfur and Water in Seventeen Geological Reference Materials

Fluorine, chlorine, bromine, iodine and sulfur were determined in seventeen geological reference materials after extraction by pyrohydrolysis. Fluorine, Cl and S (as sulfate ions) were determined in the extraction solution by ion chromatography with detection limits of around 0.2 mg l⁻¹. Bromine and I were measured by ICP-MS with detection limits of 1 μg l⁻¹ for Br and 0.1 μg l⁻¹ for I. For rock samples, using normal extraction conditions (500 mg of sample and 100 ml of final solution) detection limits were 40 mg kg⁻¹ for F and Cl, 15 mg kg⁻¹ for S, 0.2 mg kg⁻¹ for Br and 0.02 mg kg⁻¹ for I. These detection limits may be improved by increasing the amount of sample and hence the concentration of the final solution. Water was also determined using an extraction technique based on H₂O degassing, reduction on zinc at 1000 °C and H₂ manometry. Our results for fluorine, chlorine, sulfur and water are in good agreement with literature data. Very few reference materials have recommended values for bromine and especially for iodine. Among the analysed samples, three are new reference materials: BHVO-2, BCR-2 and AGV-2.     

环境氟与人体健康——致世界卫生组织的一封公开信

总结了环境中的氟与人体健康的关系。呼吁人们不可忽视微量元素氟对人体的生理功能，摄入不足轻则臻龋齿，重则导臻大骨节病的发生；在全面认识氟的基础上，发现了卤素和人体健康有氟主骨，氯主心，溴主神和碘主智的重要关系。同时提出“元素丰欠皆致病”和“多祛少补乃原则”的地方病发病机制和治疗原则；地方病的防治提倡食疗和饮疗，最后建议地方病以摄入的元素多少来命名，因为它既能反映致病原因，又明确了治疗方法，医患皆知。     

On the behaviour of fluorine and chlorine during magmatic differentiation

The behaviour of fluorine and chlorine during differentiation is considered in the light of halogen data for granites and separated biotites from the Dartmoor granite pluton of S.W. England, hornblende-bearing ultrabasic and basic rocks from a layered intrusion at Rhiw, N. Wales, and recent literature data on halogens in apatites from the Shonkin Sag laccolith and the Skaergaard intrusion.The data indicate that whereas fluorine concentrations are highest in the late stage differentiates, chlorine concentration is highest in the earlier differentiates. It is suggested that this behaviour of the two halogens is due to their relative affinities for silicate melts. Chlorine having a low solubility in silicate melts and a strong affinity for associated aqueous phases will tend to be concentrated in early formed hydrous minerals, leaving fluorine with its strong affinity for the melt to be enriched in the late-formed hydrous minerals.     

煤中氯赋存形态的试验研究

采用艾氏卡熔样—硫氰酸钾滴定法,对我国41个煤中氯的含量进行测定,并研究了煤中氯含量与挥发分、固定碳、灰分以及碱金属的关系。结果表明,我国煤中氯含量普遍较低,一般为0.1%~0.2%;煤中氯含量与煤的煤化程度有明显关系,煤的变质程度越高,煤中氯的含量越少。煤中氯含量与煤中水分和氟的含量无关。随着煤中碱金属含量的增加,煤中氯含量呈下降趋势,煤中氯与碱金属(Na,K,Ca,Mg)等存在负相关性。煤中氯主要以有机形式存在。      

Ion Chromatographic Determination of Fluorine and Chlorine in Silicate Rocks Following Alkaline Fusion

A simple and accurate method to determine fluorine and chlorine contents in small amounts (∼ 30 mg) in rock has been developed using ion chromatography after extraction by alkaline fusion. Powdered sample was mixed with sodium carbonate and zinc oxide at a mass ratio of 1:3:1, and was fused in an electric furnace at 900 °C for 30-40 minutes. An aqueous solution obtained by dissolving the fused silicate rock was diluted to the appropriate concentration of sodium carbonate (< ∼ 24 mmol l^-1) to minimise the tailing effect on F^- during ion chromatography caused by the large amount of carbonate species originating from the flux. Fluorine and chlorine contents were then determined by a standard additions method. Based on the relative standard deviation of the backgrounds, detection limits of both fluorine and chlorine were ∼ 4 μg g^-1, when 30 mg test portions were fused and diluted by a factor of 1200. We also report new fluorine and chlorine contents in nine GSJ (Geological Survey of Japan) reference materials, including peridotite (JP-1), granite (JG-1a), basalts (JB-1b, 2 and 3), andesites (JA-1 and 2) and rhyolites (JR-1 and 2). Fluorine and chlorine contents in the reference materials in this study were consistent with previously reported values. Reproducibilities were < 10 % for samples with F and Cl concentrations of > 20 μg g-1 and < 20 % with F and Cl < 20 μg g^-1.     

The compositions of coexisting pyroxenes and garnet in the system CaO-MgO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> at 900°–1,100°C and high pressures

Literature data on chlorine and fluorine in apatite and biotite of different rocks correspond reasonably well with thermodynamic expectations, indicating that concentrations are related to primary or major crystallisation events. Petrographically similar leucogabbros in the Riwaka and Milford Sound areas, widely separated on opposite sides of the Alpine Fault, are characterised by similar fluorine and similar, unusually high, chlorine concentrations in their minerals and appear genetically equivalent.