薄膜吸附制样-波长色散X射线荧光光谱法测定卤水中的溴

溴主要以离子形式分布在地壳水圈的溴化物型卤水、卤化物硫酸盐型卤水中,目前应用波长色散X射线荧光光谱(WDXRF)测定卤水中的溴,主要采用粉末载体压片法前处理待检样品,制样工作量大,制样均匀性和制样过程中的污染都会影响准确度,方法实用性不强。本文借助薄膜吸附前处理卤水样品,通过优化筛选薄膜材料及卤水取样量,确定移取50μL卤水样品滴于Ф=40 mm的3#层析滤纸的圆心位置,自然晾干后高压压平来前处理待检样品,采用人工配制标准样品校正溴的标准曲线,用WDXRF测定溴的含量。钾钠钙镁氯和硫酸根等共存离子的影响可以忽略,方法检出限(3σ)为0.95 mg/L,精密度(RSD,n=11)不大于0.8%,加标回收率为99.4%~101.2%。本方法操作简便,不需要使用化学试剂,解决了现行卤水中溴的分析方法流程复杂、分析成本高的问题。     

能量色散X射线荧光光谱法测定卤水中痕量溴铷砷

用模拟卤水建立了能量色散X射线荧光光谱法测定卤水中溴、铷、砷痕量元素含量的方法.实验表明,方法可以直接取样测定,适用于大批量样品的测试分析.方法的精密度RSD(n＝15)小于1%,加标回收率为86.8%～101.6%.卤水中溴、铷、砷的测定结果与比色法、原子吸收和原子荧光法结果相符.     

碰撞反应电感耦合等离子体质谱法直接测定卤水中的溴碘

目前使用电感耦合等离子体质谱法(ICP-MS)测定环境水样中的溴和碘,方法较为成熟,但应用于高盐卤水中溴碘的检测研究很少见报道.本文针对柴达木盆地盐湖卤水矿化度高、钾含量高的特点,建立了ICP-MS直接测定卤水中溴和碘的方法.采用碰撞反应接口(CRI)模式,以H2为碰撞气体,降低了检测过程中的多原子离子质谱干扰(例如39K40 Ar+对79Br+的干扰);选用Rh作内标元素,校正高盐样品引起的基体效应、仪器漂移等非质谱干扰;通过延长快泵冲洗时间消除测定过程中的记忆效应.在优化的实验条件下,盐湖卤水样品稀释200倍后用ICP-MS测定,方法检出限溴为0.036μg/mL,碘为0.027 μg/mL;方法精密度(RSD,n=12)溴为2.77％,碘为2.19％;加标回收率溴为91.6％ ～ 106.1％,碘为94.4％ ～ 107.7％.本方法也可应用于钾含量高的岩盐样品中溴和碘的测定.     

X射线荧光光谱法测定土壤和沉积物中的锰

X射线荧光光谱法(XRF)是测定土壤和沉积物中锰的重要方法,具有制样简单、非破坏性测定、检测速度快等优点。目前用于建立工作曲线的土壤和沉积物标准物质的锰含量最高为2490mg/kg,采用XRF法测定受污染土壤和沉积物中的锰含量时易超出工作曲线测定范围。本文将锰标准溶液定量加入到土壤标准物质中,制备锰含量更高的校准样品,工作曲线的测定上限范围由2490mg/kg提高至3780mg/kg。该方法测定不同含量标准物质中锰含量的结果均在认定值范围内,实际样品的加标回收率为97.8%～108.3%,高含量锰的实际样品测定值与电感耦合等离子体发射光谱法测定值的相对偏差小于5.7%,相对标准偏差(RSD)小于0.4%(n=7)。实验结果表明该法测定锰含量高的土壤和沉积物的准确度和精密度良好。     

溴-酚红比色法中氯离子的干扰实验

溴酚红比色法测定水中Br是一个快速简便的方法,在GB8538.38-87和地矿部地下水标准检验方法中都推荐此法.该方法多用于淡水分析,但对于卤水中含有大量的Cl-是否干扰Br的测定未有报道,目前卤水中分析Br均采用溴-品红比色法,但此方法明显比溴-酚红比色法流程长,操作手续     

稀氨水密封溶解—电感耦合等离子体质谱测定土壤沉积物及生物样品中的碘溴

介绍了一个适合于电感耦合等离子体质谱直接测定土壤、沉积物和生物样品中碘、溴的快速简单的样品前处理方法。样品在φ(NH3·H2O)=10%的水溶液中,于190℃下密封分解18h,溶液适当稀释后放置澄清,用电感耦合等离子体质谱法直接测定溶液中的碘、溴。选用126Te作为内标,补偿基体效应和仪器漂移对分析结果的影响。碘、溴的方法检出限(10σ,DF=100)分别为0.01μg/g、0.04μg/g。用土壤、水系沉积物以及头发等标准物质验证了方法的准确度及精密度,绝大多数样品分析结果在标准值的允许误差范围内。对国家一级标准物质10次测定的RSD为2.0%～8.6%。但方法分析岩石样品结果偏低,不适用于岩石样品的分析。     

火焰发射光谱法测定氯化物型湖卤水中钾和钠

氯化物型湖卤水中一般呈现高钠低钾的分布状态,实验配制了合理的钾钠分布比例的标准系列,原水样不需特殊处理,通过逐级稀释,采用最高标准调节能量,火焰发射光谱法直接测定湖卤水中的钾和钠,在标准曲线上查得被测离子的质量,然后换算成钾和钠的含量.方法用于氯化物型湖卤水中钾和钠的测定,回收率为91%～116%,精密度(RSD,n=7)小于1%.     

王水水浴消解-电感耦合等离子体质谱法测定土壤中的硒

随着富硒产品关注度越来越高,对土壤中硒含量测定的研究也越来越受到人们的重视。应用传统电感耦合等离子体质谱法(ICP-MS)测定土壤样品中的硒时,受到的基体效应和多原子离子干扰比较显著,准确测定硒含量的难度较大。本文建立了采用50%王水-沸水浴消解体系,ICP-MS测定土壤样品中硒含量的方法,实验中采用动能歧视模式(KED)消除质谱干扰,选用~(103)Rh元素作为在线加入内标以消除仪器信号漂移。用该方法对有证土壤标准物质进行分析,其结果均在不确定度范围内,测定值与认定值的相对误差介于-2.01%～2.99%之间,相对标准偏差(RSD)小于6.60%,检出限为0.012μg/g,测定下限为0.048μg/g。应用该方法与国家环境保护标准方法(HJ680—2013)对20个土壤实际样品进行比对分析,其结果基本一致。该方法适合于分析测定地质等行业大批量土壤样品中的硒。     

地质样品中痕量溴的间接极谱法测定

提出了一种简便,灵敏的测定地质样品中痕量溴的新方法。半熔法分解样品,利用溴催化高锰酸钾氧化碘化钾的反应,在催化反应进行到一定时间后,用四氯化碳萃取未反应的游离碘,在水相中测定碘酸根的导数极谱波,间接测定溴的含量,本法测定溴的检出限为０．１８μｇ／ｇ,ＲＳＤ为５．７％。标准物质分析结果与推荐值一致。     

用离子选择电极测定岩石和土壤中的碘

用碘离子选择电极可以快速而十分准确地测定岩石和土壤中的碘(作为碘化物)。当取一克样品时,测出的浓度可小至0.5ppm,其精密度约为25%相对标准偏差。当溴的浓度大于5ppm时,可用同样方法测定溴。本方法值得进一步研究,作为化探的一个工具。     

高盐度地下水~(14)C测年样品采集技术探讨

高盐度地下水 (卤水 ) 14 C样品采集是同位素水文地质界的一个难题。罗布泊钾矿区卤水的化学组成特征是 :平均矿化度为 35 3.5 g/L ,SO2 -4的质量浓度 4 4 .0 3g/L ,HCO-3 的质量浓度为0 .2 71g/L。为此 ,文中借鉴一般地下水 (淡水或微咸水 ) 14 C样品的采集原理 ,设计出一套真空取样装置。其操作步骤是 ,首先通过调节卤水的 pH值 ,使得水中的无机碳以CO2 气体的形式溢出 ,然后 ,导入装有NaOH与BaCl2 混合溶液的样品瓶中 ,在野外获得高盐度卤水14 C测年样品。罗布泊卤水测试结果表明 ,这一流程有效地解决了硫酸盐干扰问题 ,卤水14 C样品质量可靠。该技术可为高盐度地下水测年提供有效手段 ,对低盐度地下水14 C取样也具有重要的推广使用价值。     

Determination of Bromine and Iodine in U.S.G.S. Standard Marine Mud (MAG-1)

The concentrations of bromine and iodine in USGS reference material MAG-1 were determined by standard addition with secondary-source x-ray fluorescence spectrometric detection. Three determinations of bromine in the same sample yielded 311, 309 and 346 μg Br/g solid. The iodine content was found to be 380 μg I/g solid. The determination of bromine in a second bottle of MAG-1 (266 ± 9 μg Br/g) indicated that a large variation in halogen concentration may exist between samples of this reference material.     

A model to estimate the depositional brine depths of ancient halite rocks: Implications for ancient subaqueous evaporite depositional environments

A model is derived which allows a more general approach to the interpretation of bromine profiles in halite rocks than is possible with the models of Kuhn or Holser. Allowing for an open system, with influx and reflux, reduces the depth of brine necessary to generate a given salt deposit. Even very small and regular bromine gradients, which historically have been interpreted as the result of deposition from deep brine bodies, can be generated in an open system from brine no more than a few tens of metres deep. The bromine gradient produced from a given depth of brine is strongly dependent on the composition and amount of influx, but less so on the composition of brine already in the basin. A Zechstein profile is analysed which in a closed basin would require brine 2665 m deep. It can equally be modelled by influx of normal seawater which fully replenishes a basin no more than 140 m deep. A somewhat irregular profile from the Paradox Basin, instead of requiring a basin 100–400 m deep, can be modelled as being produced by deposition from brines only 10 m deep. Reflux in both cases can only be a few per cent of influx at a maximum.     

柴达木黑北凹地早更新世新型砂砾层卤水水化学特征与成因

柴达木黑北凹地深部砂砾石层内的承压水是近期在柴达木西部新发现的规模巨大的孔隙卤水,水位埋深8~24 m,接近地表;富水性中等偏强;矿化度较高,KCl含量达到可开发利用的要求,井采时不易结盐,可作为后续开发钾盐的备选区域.离子统计分析结果显示,TDS、Cl-、Na+、Cs+、B₂O₃、Ca2+、Mg2+、Sr+、NO₃-、Rb+在卤水中的浓度变化幅度小,分布较均匀;SO₄2-的变化幅度大,分布极不均匀;Br-、I-、Li+、K+变化幅度和均匀程度介于二者之间;Na+、Cl-、Ca2+、Sr2+、TDS呈正态负偏高峰态,K+、SO₄2-、Li+呈非正态正偏高峰态.成分聚类分析图中,K+、SO₄2-、Li+首先聚为一亚类,Cl-、TDS、Na+聚为一亚类.从离子含量变化曲线图中可以看到,该孔隙卤水从东至西,Na+、Cl-含量和变化趋势相同,且它们与TDS、B₂O₃的变化趋势相同.K+、SO₄2-、Mg2+三种组分含量较一致,变化趋势相同,且同时与Li+的变化趋势相同.孔隙卤水钠氯系数C_Na/C_Cl值为0.85~0.96,溴氯系数为0.01~0.34,与盐岩溶滤卤水接近.在Na+、K+、Mg2+//Cl--H₂O四元体系和Na+、K+、Mg2+//Cl-、SO₄2--H₂O五元体系25 ℃介稳相图中反映出2种析盐规律,一种为硫酸镁亚型,另一种是氯化物型.其形成可能与化学沉积层中高矿化度晶间卤水与砂砾石层中原始孔隙(淡)水相互作用有关.      

粉末压片——X射线荧光光谱分析中区域地球化学样品制备和标准曲线建立的几点认识

本文针对粉末压片——X射线荧光光谱法在区域地球化学样品测试中样品制备和标准工作曲线建立两个方面容易出现的技术问题进行了讨论,分析了样片制备方法、样片厚度、表面状况以及试样均匀性与粒度效应对测试结果的影响,并对标准曲线建立中标准样品的选择原则、仪器工作条件的优化及科学合理进行曲线拟合等做了较为详细的介绍,提出了消除测量误差的方法与手段,对X射线荧光光谱分析人员有一定的参考价值。     

塔里木盆地西部卤水地球化学特征及成钾远景预测

在塔里木盆地的地质发展史上，尤其是在白垩纪和第三纪，经历了多次新特提斯海的海进和海退，带来了大量成盐物质，再加上后期持续干旱的气候条件和适宜的岩相古地理条件，使塔里木盆地沉积了一套厚层石盐岩、膏泥岩、碳酸盐岩以及泥质岩等，为钾盐资源的形成奠定了一定物质基础，同时由于受地质构造和中生代盆地断裂的控制所形成的若干次级盆地，加上适宜的古地理环境，使其具备了钾盐矿床形成的基本条件。通过野外实地考察取样，采集岩盐及卤水样品共300多件，用于实验分析的共142件（卤水43件）。通过对塔里木盆地西部卤水的地球化学特征分析，讨论了寻找钾盐的直接指标K+含量和各种地球化学特征系数，探讨了塔里木盆地的成盐模式、卤水浓缩阶段和成钾可能性，得出:塔里木盆地的钾盐远景区是喀什凹陷和阳霞凹陷；依据溴和硼含量以及各种特征系数值与正常卤水浓缩值比较，可知塔里木盆地是溴和硼等微量元素含量较少的地区，不能完全依靠这些特征参数来判断塔里木盆地的卤水浓缩程度和钾盐资源状况，同时也说明了塔里木盆地是一个成盐环境相对比较复杂的地区。     

青海省察尔汗盐湖卤水中有效硒的测定

针对氯化物型卤水,用氯化镧作为共沉淀剂进行分离富集,在盐酸介质中,用氢化物发生-原子荧光光谱法测定卤水中的有效硒。结果表明,方法检出限为0.008μg/L,硒的含量在0~100μg/L范围内呈线性关系,标准加入回收率为97.5%~101.9%。方法准确可靠。     

Evaluation of the performance of a new freeze desalination technology

The use of desalination technologies which produce concentrated brines is acutely limited by inadequate waste brine disposal mechanisms such that the brine does not contaminate fresh water resources. The treatment of highly saline brine using freeze desalination technique trade marked as HybridICE? technology was investigated at pilot scale. The capacity of the HybridICE? process to generate fresh water by freeze desalination of brine was investigated in this study. Brine samples to feed into the HybridICE process unit were prepared in tanks with volume capacities between 1.0 and 10.0 m³ by dissolving common salt into tape water. The effects of refrigerant temperature, initial brine concentration, energy consumption were evaluated in relation to product ice quality. Feed brine samples were processed in batches in a closed system where it was continuously re-circulated to generate product ice and more concentrated residual small volume of brine stream. The quality of ice produced could be turned into potable water it terms of its low total dissolved salts and conductivity. The salt removal, based on the average chloride concentration in the ice samples, was 96 %. The energy utilization efficiency amounted to an average of ZAR 10.0/m³ water assuming energy cost of ZAR 0.39/kWh. The HybridICE? technology was shown to be a better option than other desalination technologies currently in use, in terms of energy utilization and cleaner by-products.     

四川自贡地区地下卤水锂矿化特征及靶区预测

锂作为一种新能源、新材料,对国民经济建设及国防安全保障具有重要的战略意义。卤水中液体锂为锂资源的主要来源之一。四川盆地自贡地区地下卤水资源丰富,但开发利用方式较为单一。前人对自流井背斜卤水中的锂资源研究较少,但已有数据均表明局部卤水中Li⁺含量达单独开采工业品位的2~4倍,具有较高的开采价值。近年来,对自贡地区的地下卤水资源分布情况进行了调查,对有利地区采集的样品进行了分析,结果表明: 锂资源已达边界品位的3~4倍、最低工业品位的2倍以上; Li⁺与Na⁺、K⁺、$NH^{+}_{4}$、Cl^-含量呈明显的正相关,卤水中Na⁺、K⁺、$NH^{+}_{4}$、Cl^-的含量可作为Li⁺含量的间接指示; 降低卤水中Mg/Li值能够有效控制提锂成本; 相比于黄卤,黑卤有较低的Mg²⁺和较高的Li⁺、Na⁺、K⁺、$NH^{+}_{4}$及Cl^-。通过综合分析认为,邓井关背斜的轴部黑卤密集分布地区可作为锂资源的找矿靶区。     

Strontium distribution and celestite occurrence in Zechstein (Upper Permian) anhydrites of West Poland

The previous study showed that the Zechstein (Upper Permian) anhydrites have about 0.2% strontium with a remarkably small sample scatter. Our study of three lower Zechstein anhydrite units (Lower Anhydrite, Upper Anhydrite and Basal Anhydrite) from West Poland indicate that although often the Sr content is 0.1–0.2%, there are common deviations. In particular, a considerable part (28%) of the studied samples is characterized by lower values (<0.1%), and on the other hand ca. 15% of samples are Sr-enriched, and in those samples celestite was recorded. Particular anhydrite levels differ especially in the frequency of samples showing great Sr content. The greatest variation was found in the Lower Anhydrite. This agrees well with the conclusion derived from the sedimentological studies indicating that there was the greatest differentiation of depositional environments during the deposition of the Lower Anhydrite. The Sr content is a good indicator of brine concentration during the gypsum precipitation and it seems that the subsequent gypsum–anhydrite transformation itself does not affect the strontium distribution. The histograms of Sr content in the Basal Anhydrite indicate a slightly higher brine concentration than it was during the Lower Anhydrite deposition, and the latter in turn was higher than brine concentration during the Upper Anhydrite sedimentation. Celestite veins are clearly diagenetic in origin. The form of celestite occurrence and the increased strontium content (1% or more) indicate an additional source of ions that occurred outside the anhydrite series. In the case of the Lower Anhydrite, the supposed additional source of Sr was related to aragonite-to-calcite transition and squeezing of CaCl₂ brines from reefs into anhydrite series due to increased pressure. For the Basal Anhydrite this source could be related to brines derived from the Older Halite deposits.