碘酸钡置换碘-四氯化碳萃取光度法测定矿物气液包裹体中微量SO_4~(2-)

本文根据碘酸钡与矿物气液包裹体中ＳＯ２－４交换反应析出的碘酸根与碘化镉反应析出碘,采用碘－四氯化碳萃取光度法间接测定ＳＯ２－４,取得了较为满意的结果。     

Iodine Chemistry and its Role in Halogen Activation and Ozone Loss in the Marine Boundary Layer: A Model Study

A detailed set of reactions treating the gas and aqueous phase chemistry of the most important iodine species in the marine boundary layer (MBL) has been added to a box model which describes Br and Cl chemistry in the MBL. While Br and Cl originate from seasalt, the I compounds are largely derived photochemically from several biogenic alkyl iodides, in particular CH2I2, CH2ClI, C2H5I, C3H7I, or CH3I which are released from the sea. Their photodissociation produces some inorganic iodine gases which can rapidly react in the gas and aqueous phase with other halogen compounds. Scavenging of the iodine species HI, HOI, INO2, and IONO2 by aerosol particles is not a permanent sink as assumed in previous modeling studies. Aqueous-phase chemical reactions can produce the compounds IBr, ICl, and I2, which will be released back into the gas phase due to their low solubility. Our study, although highly theoretical, suggests that almost all particulate iodine is in the chemical form of IO-3. Other aqueous-phase species are only temporary reservoirs and can be re-activated to yield gas phase iodine. Assuming release rates of the organic iodine compounds which yield atmospheric concentrations similar to some measurements, we calculate significant concentrations of reactive halogen gases. The addition of iodine chemistry to our reaction scheme has the effect of accelerating photochemical Br and Cl release from the seasalt. This causes an enhancement in ozone destruction rates in the MBL over that arising from the well established reactions O(1D) + H2O 2OH, HO2 + O3 OH + 2O2, and OH + O3 HO2 + O2. The given reaction scheme accounts for the formation of particulate iodine which is preferably accumulated in the smaller sulfate aerosol particles.     

The UV-Visible Absorption Cross-Sections and Atmospheric Photolysis Rate of HOI

The UV-visible absorption cross-sections of HOI have been recorded over the wavelength range 278-494 nm and at 298 K following generation of HOI in the gas phase using laser flash photolysis. The gas phase reaction of OH with I₂ was used to produce HOI, and the absorption spectrum of HOI was calibrated relative to the consumption of I₂. The HOI spectrum recorded exhibits 2 broad absorption maxima of = 3.99 × 10^-19 cm² and = 2.85 × 10^-19 cm², centred at 338.4 nm and 404.8 nm respectively. The spectrum is adequately described by a parameterisation consisting of two semi-logarithmic Gaussian distribution functions. The HOI spectrum is more intense than that recorded in previous work of Jenkin, but is in good agreement with more recent work by Bauer et al. The parameterised HOI absorption spectrum recorded in this work was used in a radiative model to calculate the atmospheric photolysis rate (J-value) of HOI. These results indicate that, under most sunlit conditions, HOI has a lifetime with respect to solar photolysis of the order of minutes. Experiments attempting to generate HOI by the reaction of O atoms with C₂H₅I led to complex absorption spectra containing a negative contribution to the absorption from the photolytic removal of an unidentified species. In addition, evidence was found for adsorption and desorption of an iodine-containing species in the reaction vessel. This behaviour is rationalised in terms of the disproportionation of HOI to I₂O, and an uncalibrated spectrum tentatively attributed to I₂O has been recorded.     

Photochemical aspects of tropospheric iodine behaviour

The I-atom sensitised decomposition of ozone in air at 1 atm pressure and ambient temperature has been investigated. Iodine atoms were produced by photolysis of I₂ using visible light or of CH₃I using ultraviolet light. In both cases, the quantum yield for O₃ decomposition was 1.25 (±0.11) per I atom. An important role is proposed for the self-reaction of IO radicals leading to higher oxides of iodine, IO+IO(+M)I₂O₂(+M)higher oxides, which predominated over the bimolecular reaction leading to regeneration of I atoms, IO+IO2I+O₂, with k _2a/k _2b4. Simple computer modelling calculations indicate that reaction (2a) may be important in determining the fate of photolabile iodine species in the atmosphere. The consequences for the behaviour of radioiodine releases are also discussed.     

环境地球化学中的碘与我国的碘缺乏病

本文概述了我国的确缺乏病研究及防治现状，该病流行分布与环境地球化学中碘的关系密切。     

地下水和土壤中不同形态碘的分离测定

实验选用717强碱型阴离子树脂吸附溶液中的碘离子和碘酸根,用30g/L氯化钠溶液和2.0mol/L硝酸钠溶液先后从树脂上洗脱碘酸根和碘离子,达到不同形态碘分离的目的。洗脱液用碘-淀粉比色法测定碘的含量。方法已用于我国高碘地区地下水和土壤样品中不同形态碘的分析。     

电感耦合等离子体质谱法测定磷矿石中的碘

建立了电感耦合等离子体质谱法测定磷矿石中碘的方法。试样经磷酸、高氯酸分解,用氨水调至弱碱性,直接用电感耦合等离子体质谱法测定,方法检出限为0.33μg/g,加标回收率为95.0%~97.4%,精密度(RSD,n=12)为2.77%~3.17%。经磷矿石国家一级标准物质(GBW 07210和GBW 07211)验证,结果满意。     

Dating of Dissolved Iodine in Pore Waters from the Gas Hydrate Occurrence Offshore Shimokita Peninsula,Japan: 129I Results from the D/V Chikyu Shakedown Cruise

Iodine concentration and radioisotopic composition (¹²⁹I/I) were measured in the pore waters from the gas hydrate occurrence in the forearc basin offshore Shimokita Peninsula, north-eastern Japan, to determine the source formation of I and accompanying hydrocarbons. Iodine concentrations correlate well with the alkalinity and SO₄ patterns, reflecting degradation stages of I-rich buried organic matter, rapidly increasing in the sulfate reduction interval, and becoming constant below 250 meters below the seafloor with an upwelling flux of 1.5 × 10⁻¹¹ µmol cm⁻² year⁻¹. The ¹²⁹I/I ratios of 300 × 10⁻¹⁵–400 × 10⁻¹⁵ in deep pore waters suggest ages for iodine and hydrocarbon sources as old as 40 Ma. These ages correlate well with the coaly source formations of the Eocene age thought to be responsible for the conventional natural gas deposits underlying the gas hydrate stability zone. Similar profiles are observed in ¹²⁹I/I ratios of pore waters in the gas hydrate stability zone from the forearc basin in the eastern Nankai Trough, offshore central Japan, where pore waters are enriched in I and reach ages as old as ∼50 Ma through the sediment column. At the outer ridge site along the trough, on the other hand, relatively younger I are more frequently delivered probably through thrusts/faults associated with subduction. The nature of source formations of I and hydrocarbons in the offshore Shimokita Peninsula has a more terrestrial contribution compared with those in the Nankai Trough, but these formations are also considerably older than the host sediments, suggesting long-term transport of I and hydrocarbons for the accumulation of gas hydrates in both locations.     

封闭酸溶-盐酸羟胺还原ICP-MS法测定土壤沉积物岩石中的痕量碘

碘是活跃元素,价态多,各价态间易相互转化,化学性质不稳定,使用ICP-MS测定土壤、沉积物和岩石样品中的痕量碘,样品前处理和测定结果的稳定性是主要问题。本文采用磷酸-高氯酸高压密闭消解处理样品,提高了样品分解效率,也避免了碘的挥发损失,通过加入0.5mL 20g/L盐酸羟胺溶液将碘还原为I~-,提高了碘的稳定性,再于100℃烘箱中保温至少20min,以稀氨水作介质,降低了ICP-MS测定过程中的记忆效应。方法相对标准偏差(RSD)为4.88%～9.19%,相对误差为-6.90%～8.33%,回收率为92.5%～109.6%,检出限(3s)为0.012μg/g。本方法的测定数据与半熔法一致,解决了当前方法存在的分析流程长、空白高、岩石样品提取不完全、提取装置繁多等问题,可以作为土壤、沉积物、岩石中痕量碘测定方法的一种补充,适合批量样品分析。     

能谱CT成像在恶性肺结节大小与血含量相关性研究中的应用价值

目的:运用宝石能谱CT和GSI浏览器,研究肺癌患者结节大小与血含量的相关性。方法:收集2014年8月至2015年6月在中国医科大学附属第一医院经临床病理证实为肺癌的40例患者,46个结节。按结节大小分为三组:直径≤2cm的16例、>2cm~3cm的15例、>3cm的15例。行能谱CT、GSI模式双期扫描,获得能谱系列成像,在肿瘤最大层面测量不同大小结节之间的平均CT值、平均水密度值和平均碘密度值,分别对上述参数进行独立样本单因素方差分析及相关性分析。结果:在能谱模式双期扫描中随着结节体积增大平均碘密度明显降低,直径为≤2cm、>2cm~3cm、>3cm结节平均碘密度在动脉期分别为(17.45±4.56)、(12.05±4.89)、(10.31±5.76)(100μg/cm3),在静脉期分别为(18.32±3.59)、(14.05±4.13)、(12.82±4.58)(100μg/cm3),直径≤2cm的结节与另外两组差异均有统计学意义(P<0.05)。在能谱模式双期扫描中三组之间的平均CT值和平均水密度没有统计学差异(P>0.05)。平均水密度和平均CT值都受肿块里的气体含量影响,但是平均碘密度不受影响,GGN与实性结节在动脉期平均CT值与平均水密度分别为(-323.83±220.27)、(43.63±15.02)HU,(638.47±227.07)、(1017.27±15.23)(100μg/cm3)。GGN的平均CT值和平均水密度与实性结节相比明显降低,并且有明显统计学差异(P<0.05),两者之间动脉期碘密度分别为(12.86±5.92)、(12.70±4.28)(100μg/cm3)没有明显统计学差异。结论:宝石能谱CT可对肺内结节血含量进行定量分析,随着结节体积增大,平均碘密度逐渐降低。平均水密度与平均CT值明显相关,而平均碘密度与平均CT值无明显相关性,运用平均碘密度表示肿块血含量比CT值更准确。