Inter‐laboratory Characterisation of Apatite Reference Materials for Chlorine Isotope Analysis

Here we report on a set of six apatite reference materials (chlorapatites MGMH#133648, TUBAF#38 and fluorapatites MGMH#128441A, TUBAF#37, 40, 50) which we have characterised for their chlorine isotope ratios; these RMs span a range of Cl mass fractions within the apatite Ca₁₀(PO₄)₆(F,Cl,OH)₂ solid solution series. Numerous apatite specimens, obtained from mineralogical collections, were initially screened for ³⁷Cl/³⁵Cl homogeneity using SIMS followed by δ³⁷Cl characterisation by gas source mass spectrometry using both dual‐inlet and continuous‐flow modes. We also report major and key trace element compositions as determined by EPMA. The repeatability of our SIMS results was better than ± 0.10‰ (1s) for the five samples with > 0.5 % m/m Cl and ± 0.19‰ (1s) for the low Cl abundance material (0.27% m/m). We also observed a small, but significant crystal orientation effect of 0.38‰ between the mean ³⁷Cl/³⁵Cl ratios measured on three oriented apatite fragments. Furthermore, the results of GS‐IRMS analyses show small but systematic offset of δ³⁷Cl_SMOC values between the three laboratories. Nonetheless, all studied samples have comparable chlorine isotope compositions, with mean 10³δ³⁷Cl_SMOC values between +0.09 and +0.42 and in all cases with 1s ≤ ± 0.25.     

DPD比色法测定电解海水产生的有效氯浓度

论文是用DPD(N,N-二乙基-1,4-苯二胺)比色法测定电解海水中的有效氯浓度,并将测定结果与碘量滴定法测定有效氯浓度相比较。此外,对该方法在海水中的实验条件进行了试验。结果得出,在海水环境下,DPD比色法在常温下,波长为550 nm,pH值6.5左右,显色后10 m in内测定。在海水中用此方法测定有效氯浓度的范围在0~2 m g/L,误差在5%以下。     

化合氯对浮游植物对绿素a和光合作用影响的室内研究

化合氯是温排水中主要的化学物质,它的存在会对电厂邻近水域中生活的浮游植物造成一定的影响,运用均匀设计的实验方法研究温度,化合氯浓度,氯处理时间,及这3个因素之间的交互作用,从中筛选出影响叶绿素a含量与光合作用过程的主要因子,结果表明：影响叶绿素a的主要因子是氯处理时间,氯浓度与处理时间之间的交互作用（置信水平为99％）,影响光合作用的主要是氯处理时间,氯浓度,氯处理时间与氯浓度之间的交互作用,以及温度与氯处理时间的交互作用（置换水平为98％）。     

四川盆地东部垫江凹陷三叠系嘉陵江组岩盐氯同位素特征与成钾指标研究

垫江凹陷位于四川盆地东部,是四川盆地三叠纪时期重要的成盐凹陷之一,但当时古卤水是否达到钾盐沉积阶段,是否具备形成海相钾盐的良好条件,一直存在争议。本文通过对垫江凹陷长平3井、高探1井和ZK001井嘉陵江组岩盐样品进行化学成分分析,以及对长平3井典型岩盐样品进行氯同位素分析来判断古卤水沉积阶段和成钾条件。结果发现垫江凹陷三叠系嘉陵江组岩盐δ37 Cl值均为负值,均小于-0.32‰,最低达到-1.18‰,绝大部分岩盐样品溴氯系数大于0.31,有很大一部分样品溴氯系数超过0.45,进一步表明垫江凹陷在嘉陵江期古卤水浓缩已达到钾石盐析出阶段,与岩盐包裹体成分分析结果一致。综合气候-物源-构造因素,认为垫江凹陷三叠纪嘉陵江期气候条件炎热,物质来源丰富,存在次级凹陷,古构造条件优越,具备良好的成钾潜力。     

常顶瓦斯油吸附法脱除微量氯的实验研究

炼油厂将常压塔顶油和减一线油作为重整原料,但由于氯含量过高(30×10-6)无法利用,传统方法是将其中的有机氯转化为无机氯化氢后脱除,但其对加氢催化剂有毒害,采用常顶瓦斯油吸附法可直接脱除微量氯。     

Experimental Petrology of the 1991-1995 Unzen Dacite, Japan. Part II: Cl/OH Partitioning between Hornblende and Melt and its Implications for the Origin of Oscillatory Zoning of Hornblende Phenocrysts

High-temperature–pressure experiments were carried outto determine the chlorine–hydroxyl exchange partitioncoefficient between hornblende and melt in the 1992 Unzen dacite.Cl in hornblende and melt was analyzed by electron microprobe,whereas OH in hornblende and melt was calculated assuming anionstoichiometry of hornblende and utilizing the dissociation reactionconstant for H₂O + O = 2(OH) in water-saturated melt, respectively.The partition coefficient strongly depends on the Mg/(Mg + Fe)ratio of hornblende, and is expressed as ln K₁ = (Cl/OH)_hb/(Cl/OH)_melt= 2·37 – 4·6[Mg/(Mg + Fe)]_hb at 2–3kbar and 800–850°C. The twofold variation in Cl contentin the oscillatory zoned cores of hornblende phenocrysts inthe 1991–1995 dacite cannot be explained by the dependenceof the Cl/OH partition coefficient on the Mg/(Mg + Fe)_hb ratio,and requires c. 80% variation of the Cl/OH ratio of the coexistingmelt. Available experimental data at 200 MPa on Cl/OH fractionationbetween fluid and melt suggest that c. 1·2–1·8wt % degassing of water from the magma can explain the required80% variation in the Cl/OH ratio of the melt. The negative correlationbetween Al content and Mg/(Mg + Fe) ratio in the oscillatoryzoned cores of the hornblende phenocrysts is consistent withrepeated influx and convective degassing of the fluid phasein the magma chamber. KEY WORDS: chlorine; element partitioning; hornblende; oscillatory zoning; Unzen volcano     

南海北部海区海底沉积物中孔隙水的Cl~-和SO_4~(2-)浓度异常特征及其对天然气水合物的指示意义

报道了中国南海北部海区海底沉积物中孔隙水的Cl-和SO42-质量浓度的变化特征, 圈定了孔隙水中Cl-质量浓度的高值异常区。由于水合物形成过程中的排盐效应, 会使其上覆浅表层沉积物中孔隙水的盐度增高, 因此这些氯离子的高值异常区值得进一步的勘查。对孔隙水中SO42-的质量浓度分析表明, 研究区的一些站位表现出随深度增加SO42-的质量浓度梯度发生明显的变化, 计算的硫酸盐甲烷交接带SMI界面深度均在 10m左右, 与ODP164航次和ODP204航次有天然气水合物的钻孔的SMI界面深度基本吻合, 说明这些站位深部有天然气水合物存在的可能性。     

The Influence of Chlorine on the Determination of Combined Water: An Investigation of a Correction Procedure

Differential thermal analysis, pH determination and ion chromatography were used to investigate the interference of chlorine in the determination of combined water (H₂O⁺) by the Penfield tube gravimetric method. The magnitude of the chlorine interference was quantified and a correction method was proposed to obtain accurate results for H₂O⁺. The method was applied to the determination of H₂O⁺ in deep sea sediments containing chlorine and certified reference materials of oceanic polymetallic nodules.     

库伦滴定法测定岩矿试样中氯

本文提出用电生Ag~ 库伦滴定岩矿样品中痕量氯的方法。经对电解液组成、不同电解电流下的电流效率、干扰元素的分离等进行了实验研究,确定了最佳分析条件。实验结果表明:当测定氯量≥100μg时,回收率达99.5～99.9％,相对标准偏差0.33～0.03％;测定氯量≥10μg,回收率为98.6～98.9％;相对标准偏差2.5～0.58%;方法准确,重现性好,操作简便。用岩石和土壤一级标准物质检验及参加建材一级标准物质协作定值,结果满意。     

SO4^2—、NO3^—对氯同位素测定的干扰及其消除

在石墨存在下用正热电离质谱法测定 Cs2 Cl+正离子是氯同位素测定的最佳方法 ,但实验过程中发现 ,SO42 - 和 NO3- 的存在对测定的干扰较严重。在系统地研究了 SO42 - 和 NO3- 对氯同位素测定影响的基础上 ,定性地给出了在 SO42 -和 NO3-影响下 ,部分仪器聚焦参数的变化 ,并对影响的机理做了一些解释。着重探讨了不产生影响的 SO42 - 和 NO3- 的最高浓度及 SO42 - 和 NO3- 的消除方法 ,以期指导相关的工作