Seasonal variations in the speciation of dissolved iodine in the Chesapeake Bay

The speciation of dissolved iodine and the distributions of the iodine species in the deep Chesapeake Bay underwent seasonal variations in response to changes in the prevailing redox condition. In the deep water, the ratios of iodate to iodide and iodate to inorganic iodine decreased progressively from the Winter through the Summer as the deep water became more poorly oxygenated before they rebounded in the Fall when the deep water became re-oxygenated again. The composition of the surface water followed the same trend. However, in this case, the higher biological activities in the Spring and the Summer could also have enhanced the biologically mediated reduction of iodate to iodide by phytoplankton and contributed to the lower ratios found during those seasons. Superimposed on this redox cycle was a cycle of input and removal of dissolved iodine probably as a result of the interactions between the water column and the underlying sediments. Iodine was added to the Bay during the Summer when the deep water was more reducing and removed from the Bay in the Fall when the deep water became re-oxygenated. A third cycle was the inter-conversion between inorganic iodine and ‘dissolved organic iodine’, or ‘‘DOI’’. The conversion of inorganic iodine to ‘DOI’ was more prevalent in the Spring. As a result of these biogeochemical reactions in the Bay, during exchanges between the Bay and the North Atlantic, iodate-rich and ‘DOI’-poor water was imported into the Bay while iodide- and ‘DOI’-rich water was exported to the Atlantic. The export of iodide from these geochemically reactive systems along the land margins contributes to the enrichment of iodide in the surface open oceans.     

碘－钒盐催化下合成的四溴邻苯二甲酸酐

报道一种新的有效催化剂－碘－钒盐和在一定条件下合成四溴邻苯二甲酸酐的方法。探讨催化剂的组成配比、用量、温度及废酸循环使用等因素对合成方法的影响。该催化剂的催化效果和常用的碘、碘－铁催化剂相同，适用于四溴邻苯二甲酸酐的合成。     

黔西南地甲病重病区与环境地球化学关系研究

贵州是我国碘缺乏病严重地区之一，特别是黔西南地区。本根据含碘量的调查，编制了贵州露头地层、地表土壤和地表水中含碘量分布图，并与地甲病患病率分布图进行对比研究。研究表明，地甲病患病率与露头地层中碘含量关系不明显，地表土壤中碘含量与地甲病患病率有一定关系，而地表水中碘含量与地甲病患病率关系较为密切，地表水中含碘量高的地区，地甲病患病率就低，反之则地甲病患病率高。     

便携式Li-K分析仪的研制及其在锂辉石中锂的分析应用

我国锂钾主要矿产资源大多分布在西部偏远地区,其勘查找矿或综合利用迫切需要现场快速分析技术的支持。本文介绍了自行开发的便携式Li-K分析仪的主要性能及其在锂辉石中锂的分析应用。Li-K分析仪是一种基于大气压的液体阴极辉光放电光谱仪,以待测液体为放电阴极,实现了样品中Li、K等元素的原子化和激发。该仪器以光纤传导CCD光谱仪作为检测器,其波长范围为345~1015 nm,分辨率3 nm;以Li 670.78 nm和K 769.90 nm分析谱线,在仪器最佳工作条件下测定Li、K的精密度(RSD,n=14)均低于2%,检出限为0.03μg/m L,检测范围0.1~10μg/m L。研究表明,不同酸度和酸的类型对谱线强度影响较大,且存在显著的样品基体效应,标准曲线法分析锂辉石中Li的结果偏差高达267%;而标准加入法可克服基体效应的影响,获得与ICP-OES一致性较好的分析结果,为现场开展固体样品中Li的测定奠定了基础。     

Iodine budget in surface waters from Atacama: Natural and anthropogenic iodine sources revealed by halogen geochemistry and iodine-129 isotopes

Iodine enrichment in the Atacama Desert of northern Chile is widespread and varies significantly between reservoirs, including nitrate-rich “caliche” soils, supergene Cu deposits and marine sedimentary rocks. Recent studies have suggested that groundwater has played a key role in the remobilization, transport and deposition of iodine in Atacama over scales of millions-of-years. However, and considering that natural waters are also anomalously enriched in iodine in the region, the relative source contributions of iodine in the waters and its extent of mixing remain unconstrained. In this study we provide new halogen data and isotopic ratios of iodine (¹²⁹I/I) in shallow seawater, rivers, salt lakes, cold and thermal spring water, rainwater and groundwater that help to constrain the relative influence of meteoric, marine and crustal sources in the Atacama waters. Iodine concentrations in surface and ground waters range between 0.35 μM and 26 μM in the Tarapacá region and between 0.25 μM and 48 μM in the Antofagasta region, and show strong enrichment when compared with seawater concentrations (I = ∼0.4 μM). In contrast, no bromine enrichment is detected (1.3–45.7 μM for Tarapacá and 1.7–87.4 μM for Antofagasta) relative to seawater (Br = ∼600 μM). These data, coupled to the high I/Cl and low Br/Cl ratios are indicative of an organic-rich sedimentary source (related with an “initial” fluid) that interacted with meteoric water to produce a mixed fluid, and preclude an exclusively seawater origin for iodine in Atacama natural waters. Iodine isotopic ratios (¹²⁹I/I) are consistent with halogen chemistry and confirm that most of the iodine present in natural waters derives from a deep initial fluid source (i.e., groundwater which has interacted with Jurassic marine basement), with variable influence of at least one atmospheric or meteoric source. Samples with the lowest isotopic ratios (¹²⁹I/I from ∼215 to ∼1000 × 10⁻¹⁵) strongly suggest mixing between the groundwater and iodine storage in organic-rich rocks (with variable influence of volcanic fluids) and pre-anthropogenic meteoric water, while samples with higher values (∼2000–93,700 × 10⁻¹⁵) indicate the input of anthropogenic meteoric fluid. Taking into account the geological, hydrologic and climatic features of the Atacama region, we propose that the mean contribution of anthropogenic ¹²⁹I is associated with ¹²⁹I releases during nuclear weapon tests carried out in the central Pacific Ocean until the mid 1990's (¹²⁹I/I = ∼12,000 × 10⁻¹⁵). This source reflects rapid redistribution of this radioisotope on a global scale. Our results support the notion of a long-lived continental iodine cycle in the hyperarid margin of western South America, which is driven by local hydrological and climate conditions, and confirm that groundwater was a key agent for iodine remobilization and formation of the extensive iodine-rich soils of Atacama.     

利用AutoPrep技术抑制型电导离子色谱法检测土壤中碘

利用AutoPrep自动样品前处理技术，对土壤燃烧吸收液进行在线预浓缩，抑制型电导进行检测，建立了一种全新思路的检测土壤样品中碘的方法。选择亲水性非常强的氢氧化物选择性IonPac AS16阴离子交换色谱柱，淋洗液发生装置在线产生KOH进行等梯度淋洗，抑制型电导检测。结果表明，对于土壤燃烧吸收液中碘离子的测定，方法检出限（S／N=3）可达1．2μg/L，线性相关系数为0．9998，方法精密度（RSD，n=7）为1．161％～4．566％，回收率在90．6％～100．8％。采用AutoPrep电导检测和脉冲安培检测离子色谱法测定不同土壤样品中的碘，两种方法的检测结果基本一致。方法在提供了稳定的系统空白的同时，还具备自动化程度高、操作简单、重现性好、灵敏度高、系统稳定、节约时间、成本低廉和对环境友好等多方面特点，适合于大批量土壤普查中碘的分析。     

流动注射-光度法测定地质样品中痕量碘

利用I~-对4,4′-四甲基二氨基二苯甲烷(4,4′-TMB-DPM)与氯胺T反应的催化作用,建立了流动注射-分光光度测定地质样品中痕量碘的方法。采用不等流速合并带法,分析速度快、节省试剂、灵敏度高。与高温水解法释放I~-相结合,使样品处理简单、干扰离子少。对于含I~-10μg/L的水样,其RSD(n=19)为1.1％,检出限为0.3ng/ml。用于水系沉积物、土壤分析时,含碘1.6×10~(-6)的样品RSD(n=10)为6.1％,检出限为0.08×10~(-6)。测量速度50N/h。     

Determination of Bromine and Iodine in Twenty-three Geochemical Reference Materials by ICP-MS

Trace amounts (from nanogram to microgram levels) of bromine and iodine were determined by inductively coupled plasma-mass spectrometry (ICP-MS) in twenty-three geochemical reference materials issued by the GSJ, USGS, IAEA etc. The pyrohydrolysis technique was used to separate bromine and iodine from samples analysed in the form of powder. The accuracy and precision of the experimental values were assessed by the comparative analysis of well established reference materials such as USGS AGV-1, BCR-1 and IGGE GBW07312. The measured values agreed well with reported values within a 10% error range. We also report reliable new data for these elements in these geochemical reference materials.     

IODINE CONTENT OF SARCASSUM IN SOUTHERN CHINA

SeaweedsareAnownas"elementaccUrnulabe",eSPeCiallyforiwhneandbrodrine.AiIgassumwasusedtoPreVntgoiterinancientChina.TheSpeCiesreconledinMQteriaMedica,SampsumthunbergiiandSampsum~lhaun,arewidelydistributedinNorth-ernChina.Chinesescientistsdetendnedtheiwhnecontentsinsomeseaweedsincludinghampsum(Jietal.,lwn).forumresoareesinSOuthernChinaaremoreabundantthanthoseintheNorth.MorethanoosPeCiesaremeOnledinliterathe.Mostspecieslist-edin"CommnSeaWeedsOfChina"(TSeng,l983)aresouthemsPeCies.Iwh…     

Upper Limit of Iodine Oxide in the Lower Stratosphere

It has been suggested that iodine oxides, IOx, could play a significant role in the ozone destruction in the lower stratosphere. To investigate this suggestion, spectra from nine SAOZ uv-visible spectrometer balloon flights were examined for the IO absorption signature between 405 and 450 nm. IO was not detected, either at mid- or high latitude, in the morning or the evening, in summer or winter. An upper limit of 0.2 parts per trillion by volume (pptv) at 20 km and 0.1 pptv at 15 km at the 95% confidence level (2), was derived from the best measurements at 90° SZA at sunset and sunrise. Since a photochemical model shows that 70% of inorganic iodine should be in the form IO at that time, it is concluded that unless iodine chemistry is different from that assumed at the moment, the role of iodine in stratospheric ozone depletion is small.