离子选择电极测定岩盐样品中的氯和碘

利用离子选择电极测定岩盐样品中的氯和碘离子的含量,测定氯离子时以KNO_3和柠檬酸三钠为离子强度调节剂,测定碘离子时以硝酸钾、柠檬酸和柠檬酸三钠为离子强度调节剂,Na_2SO_3为还原保护剂,再双盐桥饱和甘汞电极外盐桥填充均为0.1mo L/L的KNO_3溶液。结果表明碘和氯离子线性良好,氯离子检测下限为0.0116μg/g,有良好的样品回收率(98.1%～102.2%);碘离子检测下限为0.0030μg/g,有良好的样品回收率(97.6%～102.5%)。该方法操作过程简单、分析速度快,造价成本低,灵敏度高,同时改善了实验室用ICP-MS测定碘元素背景干扰严重和硝酸汞滴定法测定低含量氯元素难以准确检测的问题,在实际应用中得到有效的验证。     

HPLC-ICP-MS法研究内蒙古锡盟和新疆塔城高碘地区地下水的总碘及碘形态特征

长期饮用高碘水将对人体造成危害,地下水总碘及碘形态分析对于高碘地区碘环境地球化学研究具有重要价值。本文采用高效液相色谱-电感耦合等离子体质谱联用技术对内蒙古锡盟与新疆塔城高碘地区地下水总碘及碘形态进行测定。研究表明:锡盟地区地下水中碘以I-形态为主,总碘量维持在200μg/L,个别点位达到600μg/L甚至1700μg/L,呈环状分布,从东北至西南呈现"低-高-低"的分布规律;塔城地区地下水中的碘以IO-3形态为主,总碘量不足100μg/L,个别点位接近200μg/L,呈层状分布,自东向西逐渐升高。分析认为,氧化性的条件利于不同碘形态之间的转化;溶解氧过高或过低都不利于碘的储存;碘会随着可溶性盐的流失而流失;沿河流的流向,下游地势较低,总碘得到积累。本研究结果对于锡盟和塔城地区科学预防甲状腺肿、制定法律法规具有指导作用。     

电感耦合等离子体质谱法同时测定地质样品中痕量碘溴硒砷的研究：Ⅱ.土壤及沉积物标准物质分析

样品用碳酸钠和氧化锌混合熔剂半熔，热水提取，然后用强酸性阳离子交换树脂将阴离子形式存在的分析元素与溶液中大量钠、锌等阳离子分离，采用电感耦合等离子体质谱法直接同时测定溶液中的碘、溴、硒、砷。用0.07mol/L的氨水溶液清洗进样系统，有效减少了碘等元素的记忆效应和清洗时间。方法检出限（10σ，DF=100）溴、碘分别为0.15和0.028μg/g，砷、硒分别为0.04和0.004μg/g。用土壤和沉积物等地质标准物质分析验证了方法的准确度和精密度，绝大多数分析结果在标准值的允许误差范围之内。样品10次测定的RSD为0.8%～2.8%。     

华北平原原生富碘地下水系统中碘的迁移富集规律:以石家庄-衡水-沧州剖面为例

高碘地下水是继高砷、高氟地下水之后的又一全球性饮水安全问题,但对地下水系统中碘的赋存形态及迁移富集机理研究尚显不足.为了解华北平原地下水系统中碘的空间分布特征及迁移富集规律,选取石家庄-衡水-沧州典型水文地质剖面,完成地下水样品采集,分析其水化学组成、总碘含量及碘形态组成特征,同时运用phreeqc完成水文地质剖面地球化学反向模拟及相关矿物饱和指数计算,定性定量表征水流场内所发生的水文地球化学过程,进而深入探讨上述过程对地下水系统碘迁移富集的影响.结果表明,区域内地下水中碘含量变化范围为3.35~1 106.00 μg/L,其中,41.86%样品碘含量超过《水源性高碘地区和地方性高碘甲状腺肿病区的规定（GB/T19380-2003）》所界定的150 μg/L国家标准;空间上,高碘地下水主要分布于渤海湾区;地下水中碘的主要赋存形态为碘离子及碘酸根离子,其分布受氧化还原环境控制,碘酸根离子主要出现于氧化环境中;沿地下水流向,地下水环境朝利于液相碘迁移富集的方向演变;渤海湾区,海水入侵影响下形成的偏碱性、（弱）还原环境,利于碘从沉积物中迁移释放至地下水中;碘在不同铁矿物相上的搭载能力及氧化还原环境演化导致的铁矿物相转化,是造成华北平原地下水系统中碘迁移富集的主要水文地球化学过程.      

华北平原与大同盆地原生高碘地下水赋存主控因素的异同

原生高碘地下水在我国有广泛分布,为查明不同区域地下水碘赋存机理的异同,通过选取我国大同盆地以及华北平原为代表性区域,完成区域地下水样品系统性采集及水化学、碘形态测试工作,对区域地下水水环境及其演化特征完成详细刻画.结果表明:大同盆地地下水总碘含量为2.86~1 286 μg/L,华北平原地下水总碘含量为2.40~1 106 μg/L,分别约有50.0%及49.5%地下水碘含量超过（GB19380- 2016）《水源性高碘地区和高碘病区的划定》中界定的100 μg/L国家标准.地下水水环境特征表明,在大同盆地,第四纪河湖相沉积所形成的,富含有机质、偏碱性、还原性、Na-HCO₃型水环境,利于赋存于固相介质上的碘以碘离子的形式进入地下水中,沿地下水流向,富集于盆地中心排泄区;在华北平原,由第四纪6次海侵形成的冲湖积、海积松散沉积物中富含Na、Cl、I等元素,其偏碱性、还原性、Na-Cl型水环境及低水力坡度的平缓地形利于赋存在固相介质上的碘以碘离子的形式进入地下水,沿地下水流向富集于沿海排泄区.控制两个地区高碘地下水形成的相同因素是偏碱性及偏还原的地下水环境,且该环境下碘的主要赋存形态均为碘离子,但大同盆地高碘地下水形成主要受富有机质环境影响,而华北平原高碘地下水形成的主要受富碘的海相沉积控制.      

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。     

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%。     

南海北部孔隙水碘与天然气水合物成藏关系研究

天然气水合物是一种重要的新型能源。然而,深海水合物具有埋藏深、作业难度大等特点,水合物难以被高效准确地识别,这已成为制约南海水合物地质调查的瓶颈之一。针对这一问题,本文结合近年来国际上新兴的碘及碘同位素方法,对南海北部台西南盆地两个站位的柱状沉积物(HD-86V和HD-109)开展了水合物成藏识别的研究。该沉积物孔隙水中碘离子含量分别介于8.3~132.0μmol/L和7.4~118.1μmol/L之间,远高于正常海水值(0.44μmol/L)。结合区域水合物勘查结果及甲烷含量特征,发现孔隙水碘离子含量与甲烷含量表现为显著的正相关关系。对比琼东南盆地及神狐工区等区域数据,均表明沉积物孔隙水碘离子含量在南海水合物成藏示踪方面具有良好的应用前景和推广价值。     

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。     

高效阴离子交换色谱-紫外检测器联用测定海水中碘

建立了在碱性体系中采用高效阴离子交换色谱和紫外检测器联用测定海水中碘离子的分析方法。以63mmol／L NaOH为淋洗液，利用IonPac AS16型强亲水性阴离子交换分离柱．碘离子在8．3min洗脱，经抑制器后进入紫外检测器在波长226nm处检测。方法的检出限为0．05μg／L（进样量500μL，3倍信噪比），标准曲线的线性范围为1～2000μg／L（r=0．9995）。20μg／L碘离子标准溶液9次连续进样的相对标准偏差为1．85％。方法已成功地应用于海水中碘离子的测定，1μg／L碘离子的加标回收率为98％～105％。     

ION EXCHANGE-FLOW INJECTION SPECTROPHOTOMETRIC SIMULTANEOUS DETERMINATION OF TRACES OF BROMIDE AND IODIDE IN SOME CHINESE STANDARD SAMPLES

An ion exchange flow injection method is presented for the simultaneous determination of bromide and iodide based on the catalytic reaction during the oxidation of Pyrocatechol Violet by hydrogen peroxide in strongly acid solution. Bromide and iodide in sample solutions are concentrated when they flow through the ion exchange column; they are removed and separated with sodium nitrate eluant flowing through the column, and are monitored spectrophotometrically at 555 nm. All possible anionic interferences were studied. The procedure has been applied successfully to the determination of bromide and iodide in some Chinese standard reference samples. The limits of detection are 0.2 ppm and 0.4 ppm of bromide and iodide respectively in soils and stream sediments.     

Preliminary Evidence for Iodate Reduction in Bottom Waters of the Gulf of Mexico During an Hypoxic Event

The distributions of iodate and total inorganic iodine concentrations in the waters on the Texas?CLouisiana shelf in April, June, and August 2004 are described. Iodine?Csalinity graphs show three-end-member mixing involving onshore and offshore surface waters and deep offshore water. The April survey showed simple mixing on the surface, but in the later surveys, iodate concentrations were often much lower than predicted by the mixing curve while those for total inorganic iodine were higher. This demonstrated both iodate reduction in the water and iodide addition, although individual samples did not show equivalent speciation changes. Hydrographically, the system consists of the estuaries of the Mississippi and Atchafalaya rivers as they spill onto the shelf. The waters are stratified seasonally by a robust halocline, leading to hypoxia in the bottom waters from the combined effect of restricted downward diffusion of oxygen and the sinking of the luxuriant growth of phytoplankton induced by riverine nutrient supply. The distributions of iodate and total inorganic iodine are, therefore, interpreted in terms of water?Csediment interaction as the shelf shoals to the north.     

Speciation Analysis for Iodine in Groundwater Using High Performance Liquid Chromatography-Inductively Coupled Plasma-Mass Spectrometry (HPLC-ICP-MS)

Methods based on high performance liquid chromatography coupled with inductively coupled plasma-mass spectrometry (HPLC-ICP-MS) for iodine speciation analysis are described. Experiments were performed relating to iodine species, preservative medium and time. The concentration and pH of the buffer are also discussed in relation to separation efficiency. The developed methods allowed the fast and sensitive determination of iodine species with detection limits of 0.025 μg l⁻¹ (as 1) for both iodide and iodate with < 5% relative standard deviation (RSD) for 50 nmol l⁻¹. Attempts were made to quantify total organo-iodine by size-exclusion chromatography (SEC). By way of example, a number of groundwater samples were analysed by these methods, revealing that iodide is the main iodine species in the sampled waters, but that high concentrations of organo-iodine compounds were observed in some samples as well. In summary, the total concentration and the dominant species of iodine in aquatic freshwater environments is easily and accurately measured using this new method.     

The marine chemistry of iodine in anoxic basins

The distribution of dissolved iodate and iodide has been determined in two anoxic basins, the Black Sea and the Cariaco Trench; and the oxic Venezuela Basin which serves as a comparison for normal oceanic conditions. In normal oceanic waters, iodate is the predominant species; its concentration is lowest at the surface (ca. 0.3 μM) and increases with depth to ca. 0.5 μM. In contrast, the iodide concentration shows maximum values in surface waters and rapidly decreases to <0.01 μM below the euphotic zone. In anoxic basins, the reduced pE reverses this trend. The concentration of iodide increases rapidly in the oxygen-sulfide mixing zone from 0.02 to 0.46 μM, and 0.01 to 0.43 μM, in the Cariaco Trench and the Black Sea, respectively. The iodate concentration, meanwhile, decreases to zero.The total iodine to salinity ratio is lower in the surface waters with a range of 7.3–12.1 nmoles/g suggesting a possible depletion by organisms. In the anoxic basins, a maximum in this ratio is observed just above the oxygen-sulfide boundary (15–17 nmoles/g) and is indicative of particle dissolution in a strong pycnocline. In the anoxic zone of the Cariaco Trench, the ratio is constant at 12.3 nmoles/g, whereas in the Black Sea, it increases with depth from 10.0 to 19.3 nmoles/g, suggesting a possible flux of iodide from the bottom sediments.By considering the distribution of iodate and iodide in oxic and anoxic basins, the lower limit of the pE of the oxic ocean is estimated to be 10.7, given our present analytical capability. Thermodynamic considerations further suggest that the iodide-iodate couple is a poor indicator for the pE of the oceans with a limited usable range of 10.0–10.7.     

The determination of cassiterite tin in soils and sediments by an atomic absorption-volatile hydride method

Cassiterite tin is determined after sample decomposition with ammonium iodide. The sublimate, collected in a separate condenser, is dissolved in tartaric acid solution and the tin is reduced to tin hydride in a continuous flow system by means of sodium tetrahydroborate. Atomisation is effected in a shielded hydrogen-argon diffusion flame to provide a high sensitivity determination. Interferences are negligible and the precision (12% R.S.D.) and detection limit (0.2 μ/g^-1) obtained, as well as the throughput (60 samples per hour), are suitable for geochemical exploration.     

Fluoride contamination in Gharbar Village of Dhanbad District,Jharkhand, India: source identification and management

This paper reports occurrence of high fluoride concentration in groundwater of Gharbar Village, Dhanbad District, Jharkhand, India. The concentration of fluoride varied from 0.3 to 14.9 mg/L in 27 groundwater samples. The correlation studies demonstrate that fluoride has strong positive correlation with pH and sodium and negative correlation with calcium. It indicates dominance of ion exchange activity and rock water interaction. Thermodynamic consideration shows that all the samples were oversaturated with calcite and most of the samples were under saturated with fluorite. The results indicate that occurrence of high concentration of fluoride is leading by geochemical composition of rocks, alkaline environmental condition, weathering of rocks and ion exchange processes.     

大同盆地地下水中碳硫同位素组成特征及其对碘迁移富集的指示

为深入探究地下水系统中影响碘迁移转化的主控水文生物地球化学过程,对大同盆地典型高碘地下水区完成样品采集,分析地下水样品基础理化性质及碳硫同位素组成特征.结果表明,大同盆地地下水碘含量变化范围为14.40~1 030.00 μg/L,高碘地下水（I>100 μg/L）主要分布在盆地中心排泄区.地下水中溶解性无机碳的δ13C_DIC值变化范围为-12.11‰~-9.79‰,硫酸盐δ34S_SO4值介于4.04‰~16.63‰.δ13C_DIC和DOC之间存在较明显的正相关关系,表明有机质的微生物降解过程是区域地下水无机碳的重要来源之一.同时,δ13C_DIC与δ34S_SO4一定的负相关关系表明硫酸盐是有机质微生物降解过程中潜在电子受体之一,且地下水水环境以偏还原环境为主.高碘地下水表现出低δ13C_DIC、高δ34S_SO4的同位素特征,表明有机质的微生物降解过程是控制地下水中碘迁移释放的主要过程之一,与该过程相伴而生的碘形态转化进一步促使碘以碘离子的形式在偏还原的地下水环境中发生富集.      

Reactivity of iodide in volcanic soils and noncrystalline soil constituents

Reaction of iodide [I⁻(aq)] with a series of volcanic-ash soils was compared with reaction onto noncrystalline materials that constitute much of the inorganic fraction of these soils, Our hypothesis is that these high-surface-area materials account for iodide retention by providing sites for anion exchange. Iodide sorption onto imogolite and ferrihydrite is rapid (<30 min) but not particularly extensive; imogolite has a threefold to fourfold greater affinity for iodide compared to ferrihydrite on a mass basis. In contrast, rates of iodide retention by volcanic-ash soils were slow and did not attain a steady-state after 300 h. The extent of this largely irreversible reaction can be attenuated by sterilization, but it cannot be suppressed. The iodide retained by the soils can only be completely recovered by treatment with boiling 2 M sodium hydroxide. The amount of iodide retention by soils was inversely correlated with pH, but showed no relationship with organic matter concentration, surface area, or imogolite and ferrihydrite concentrations.

The reaction of iodide with the volcanic-ash soils is consistent with a rapid initial uptake by soil mineral surfaces, followed by a slower reaction of soil organic matter with oxidized forms of iodide. Under our experimental conditions, iodide is likely slowly oxidized by dissolved oxygen to molecular iodine. Solutions of molecular iodine [I₂(aq)] react relatively quickly with laboratory-grade humic acid solutions and the rate increases with increasing pH. The slow rate of iodination is consistent with the continual formation and reaction of I₂(aq)] or HOI(aq) by titration with soil organic matter.     

Sulphate reducing bacteria to precipitate mercury after electrokinetic soil remediation

Combined treatment with electroremediation and sulphate reducing bacteria (SRB) was tested in laboratory and pilot scale. The contaminated soil came from a chlor-alkali factory and contained about 100 mg/kg Hg. Iodide/iodine complexing agent was used to mobilize mercury. Mercury iodide complexes were moved to the anode solution using an electric field. The anode solution was then mixed with hydrogen sulphide (H₂S) containing water, causing precipitation of mercury sulphide. The H²S was produced at site by a SRB reactor. Precipitation problems arising from the nature of the anode solution were expected, since this solution is highly acidic, very oxidised and may contain iodide/iodine that strongly complexes mercury and can hinder mercury sulphide precipitation. Mercury concentrations in the anode solution were up to 65.7 mg/L (field) and 15.4 mg/L (lab. scale). Reduction of mercury in the water was >93% at all times. Iodide did not hinder the process: Nonetheless, in the lab system, iodide concentration was high in the anode solution but mercury reduction was> 99.9%. The redox potential was sufficiently low for HgS precipitation during the experiments, except for a short period, when the mercury removal decreased to 94%. Sulphate reducing bacteria are shown as a viable tool for the treatment of mercury contaminated, acidic, oxidative, iodide containing water, such as that produced by electrokinetic remediation. A second SRB step or other water treatment is required to reduce the mercury concentration to environmentally acceptable levels. Redox potential is the most sensitive factor in the system.     

AG MP-1M阴离子分离Cu、Fe、Zn及其在Fe同位素测定上的应用

采用新型阴离子交换树脂AG MP-1M,分别以8.2 mol/L HCl+0.01%HF、4 mol/L HCl、2 mol/L HCI和0.5 mol/L HNO,可以有效分离地质样品中Cu、Co、Fe和Zn,克服了AG MP-1阴离子交换树脂分离Cu时Co随Cu同时淋洗下来,以及在分离Co含量较高的地质样品时Co和Cu需过二次柱分离的弊端.对花岗闪长岩等地质标样的研究结果表明,AG MP-1M阴离子交换树脂能有效分离Cu、Fe和Zn,并且它们的回收率均大于99%.标准样品经过离子交换分离后Fe同位素未发生分馏,可满足多接收器电感耦合等离子体质谱(MC-ICPMS)的同位素测定要求.