氯化钡法在盐湖高锂卤水中高效分离硫酸根的研究

在生产碳酸锂的工艺中,尤其除硫过程中,锂会伴随其它盐类析出,造成锂的大量夹带损失.因此盐湖高锂卤水中硫酸根的脱除对锂的高效富集,提高锂的收率有重大意义.研究以盐湖高锂卤水为原料,通过加入氯化钡,采用化学沉淀法除去卤水中的SO2-4.详细考察了原料配比(SO2-4与Ba2+的摩尔比)、加料方式、加料时间、反应时间、搅拌速...     

赤道东北太平洋沉积物中生物钡的分布特征

分析了赤道东北太平洋海域沉积物中Ba、Ti、Al和有机碳(Corg)的含量。研究表明,研究区沉积物中钡为0.198%~0.792%;采用标准陆源物质扣除法获得的生物钡(Babio)的含量为0.162%~0.764%,占沉积物中总钡含量的81.6%~96.5%,平均为88.7%,其在沉积物中的分布表现为上部一致,下部变化较大;有机碳(Corg)的含量为0.18%~0.58%,并表现为随沉积物深度的增加而降低。沉积物中Babio/Ti的比值表现为东区高于西区,且向高纬度降低的特点,而沉积物中Corg/Ti和Babio/Ti则表现为负相关关系,表明研究区沉积物中钡可能和上层海洋生产力的相关性不明显。     

南极普里兹湾表层沉积物中生物钡的含量与分布

利用中国南极科学考察第21和27航次采集的普里兹湾表层沉积物样品,分析了其中BBa的含量及分布特征,并讨论了控制其分布的相关因素。结果表明:分别利用直接扣除法和分步萃取法获得的BBa含量差别较大,直接扣除法获得的含量明显高于分步萃取法,这是因为扣除法获得的BBa中包含了大量的非生源钡,比如与样品中含砂量有密切联系的铁锰氧化物结合态钡,从而导致在该海域采用直接扣除法缺乏合理性。分步萃取法获得表层沉积物中BBa含量为104—445μg·g-1,平均值为227μg·g-1,呈现明显的空间分布差异,整体分布趋势为湾中心区域较高,浅滩及冰缘区较低。表层沉积物样品中BBa的含量及分布与BSi、OC以及上层水体的叶绿素a和初级生产力情况密切相关,说明上层水体的生物生产状况是BBa分布的主要控制因素。     

酸溶-电感耦合等离子发射光谱法测定密西西比型铅锌矿床矿石中的铅

密西西比型(MVT)铅锌矿床的主要矿物有方铅石、闪锌矿,常伴生有重晶石、萤石等矿物,使得MVT型矿石在酸处理过程中易生成不溶于水和酸的硫酸铅钡复盐,故而检测矿样中铅的含量偏低。本文建立了采用盐酸-硝酸-氢氟酸体系酸溶分解MVT型矿石,电感耦合等离子体发射光谱法(ICP-OES)测定铅含量的分析方法。实验比较了盐酸-硝酸-氢氟酸、盐酸-硝酸-氢氟酸-高氯酸、盐酸-硝酸-硫酸三种酸溶体系的溶样效果,并通过X射线衍射论证了方法的可行性。结果表明,盐酸-硝酸-氢氟酸体系克服了复盐硫酸铅钡和硫酸铅沉淀的生成,适量的氢氟酸促进了Pb SO4的溶解,X射线衍射表征也表明此种酸溶体系的沉淀中不含有Pb SO4,可更彻底地分解MVT型矿石。本方法精密度(RSD)为0.3%~0.6%,实际样品的加标回收率为96.0%~99.2%,铅的最佳检测范围为0.01%~20.0%。     

X射线荧光光谱法测定重晶石中的硫酸钡方法研究

应用XRF可快速测定重晶石中钡元素的总量,但当测定硫酸钡含量时,由于样品中的碳酸钡计入钡量造成硫酸钡的测定结果不准确,铜、铅、锌等有色金属元素对熔样坩埚会造成损害,需要进行酸处理除去碳酸钡、铅等干扰。而样品经酸处理后不同样品的剩余量不同,造成熔剂与样品的比例不确定,也不能准确测定硫酸钡的含量,因此保证熔剂与样品比例一致是解决该问题的关键。本文优化了样品前处理、熔片制样和仪器工作条件,将一定量样品以10%盐酸和10%硝酸溶解,过滤除去碳酸钡、硫酸钙及铜、铅、锌等有色金属元素,未溶解样品在700℃下灼烧后以氧化铝补充到原取样量,实现了熔剂与样品比例一致,再以硝酸铵作氧化剂,溴化锂和碘化铵作脱模剂,1075℃熔融制片,即可用XRF准确测定硫酸钡的含量。本方法的相对标准偏差(RSD)小于0.4%,检出限为72μg/g,较ICP-OES等方法的检测周期短、干扰元素少,提高了测试效率和分析质量。     

南海西南海域表层沉积物中微量元素Ba的地球化学特征

分析南海西南海域表层沉积物中微量元素Ba的地球化学特征,并探讨生物成因Ba的分布及其与表层海水生产力的关系。南海西南海域表层沉积物Ba总量的变化范围为398~1 270 μg/g,平均值为851 μg/g,从上陆坡到下陆坡,沉积物中的Ba含量逐渐增加;微量元素Ba主要赋存于陆源碎屑相和生物成因相中,且明显受到沉积环境水深和陆源物质输入的影响。生物成因Ba含量的变化范围为30.6~938 μg/g,陆坡区和深海区平均值分别为495 μg/g、349 μg/g,占沉积物Ba总量的54％和51％,总体上,与沉积物Ba总量具有相对一致的分布特征。尽管研究区表层沉积物中Al、Ti成分为典型的陆源碎屑组分,但是,利用大陆上地壳Ba/Al比值和陆坡区沉积物回归分析获得的Ba/Al比值进行生物成因Ba的计算,过高地估算了沉积物中陆源Ba的含量;而采用页岩Ba/Ti比值来估算陆坡区表层沉积物中的生物成因Ba含量显得相对可靠。在深海区,利用经验的Ba/Al或Ba/Ti比值均不能获得有效的生物成因Ba值。因此,在获取沉积物中生物成因钡含量时,需结合各海区的特点选取合适的参数来扣除陆源Ba的含量。     

基体差异对电感耦合等离子体质谱法测定过程中Ba氧化物产率的影响及其对Eu测定结果校正的研究

电感耦合等离子体质谱（ICP-MS） 测定地质样品中稀土元素的过程中,尤其对于高Ba基体的地质样品,由Ba形成 的氧化物和氢氧化物离子对Eu元素会产生质谱峰的重叠干扰,严重影响Eu测定结果的准确度和精确度。通过标准溶液的 条件实验,测定Ba干扰项相对Ba总量的比例（干扰率） 并进行相应的Eu扣除,是一种解决干扰导致Eu测定结果偏高的思 路。然而该干扰率在不同基质溶液中是否一致,且随着Ba含量变化是否稳定目前尚不明确。本文通过对不同基体溶液中Ba 对Eu干扰率的测定（低分辨模式测定）,发现随着溶液中Ba浓度的变化,同一基体溶液中该干扰率较为恒定,而不同基体 溶液中干扰率有明显的差别。这说明在对Eu测定结果进行干扰扣除时,需要利用匹配的基体溶液来获取准确的Ba干扰 率。应用这种方法扣除得到的Eu结果与质谱的高分辨模式（R=10000） 下的测定结果较为一致,数据的重现性也较为理 想。因此,利用基体匹配的方式来进行Ba对Eu的数学扣除是一种可行的方法。     

X射线荧光光谱法测定高锶高钡的硅酸盐样品中主量元素

用百分总和检查硅酸盐岩石全分析数据的质量是分析工作者的传统做法,但对于微量元素含量较高的样品,采用X射线荧光光谱法(XRF)进行测定,如果不考虑微量元素的含量及其对主量元素基体效应的影响,往往会使主量元素含量更加偏离真实值。本文针对Sr、Ba含量较高的硅酸盐样品,通过人工配制标准样品,扩大了Sr、Ba校准曲线的定量范围,主量元素校准中加入Sr、Ba的基体校正系数,达到了主量元素定量更加准确可靠的实际效果。采用此方法分析国家标准物质,各主量元素的精密度(RSD)均小于2%;分析不参加回归的标准物质和人工配制的标准样品,主量元素的测量值与标准值(或参考值)基本一致。该方法可以满足硅酸盐的测定要求,主量元素各项结果的加和能够达到《地质矿产实验室测试质量管理规范》的一级标准(99.3%～100.7%)。     

Chronology of landscape evolution and soil development in the upper Flinders River area,Queensland, based on isotopic dating of Cainozoic basalts

Victorian granites containing more than 750 ppm Ba are almost entirely confined to the region between a line from Geelong to Swan Hill and the Wonnangatta Fault Zone. Granite Ba contents normalised to 70% SiO₂ range from 620 to 733 ppm in western Victoria, 719 to 1560 ppm in central Victoria and 493 to 689 ppm in eastern Victoria. Melting of Ba-rich (meta)sedimentary rocks in the lower – middle crust is implicated in the petrogenesis of central Victorian S types, at least. Thus, granite geochemistry supports the concept of some sort of (largely concealed) Ba-rich Selwyn Block beneath central Victoria, although the boundaries that have been proposed for the block are modified here. There is a strong possibility that the Selwyn Block is an exotic terrane emplaced by northwest-directed strike-slip movement during the Bindian Orogeny. Such movement appears to have been controlled by the previously postulated Baragwanath Transform and another fundamental fault here called the Ulrich Transform. Asthenospheric upwelling related to movement on the Ulrich and Baragwanath Transforms may be the explanation for the twin belts of 400 Ma plutonism occurring to the west of the former and to the east of the latter. The southern extension of the Ulrich Transform may be the Tamar – Tiers structure in Tasmania. Plate-tectonic models suggesting Ordovician – Silurian subduction in Victoria need to be carefully revisited given the possibility of Siluro-Devonian exotic terrane emplacement.     

Factors Controlling Precipitation of Barite and Witherite and Genesis of the Ankang–Xunyang Barium Deposits, Shaanxi, China

The barium deposits in Ankang and Xunyang counties,Shaanxi Province,China,occur in the northernmost part of the world-class barium metallogenic belt in south Qinling.The deposits are hosted by the Lower Silurian carbonaceous siliceous rocks,with a unique combination of barite and witherite.The homogenization temperatures of fluid inclusions in the barite are mainly concentrated between 135 and 155 ℃,whereas those from the witherite have two peaks of 165-175 ℃,and 215-225℃,respectively.Laser Raman analysis of fluid inclusions indicates that the vapor phase of fluid inclusions in barite is dominated by H_2O,although some contains N_2,H_2S,and CH_4.The compositions of the vapor and liquid phases of fluid inclusions in witherite can be divided into two end-members,one dominated by H_2O without other volatiles,and the other containing CH_4,C_2H_6,C_3H_8,C_2H_4,and C_6H_6 in addition to H_2O.CO_2,H_2S,and some CH_4 are interpreted as products of chemical reactions during mineralization.Organic gases(CH_4,C_2H_6,C_3H_8,C_2H_4,and C_6H_6) in the fluids were critical in the formation of barium sulfate versus carbonate.The δ~(34)S values of barite range from 38.26‰ to54.23‰(CDT),the δ~(34)S values of sulfides coexisting with barium minerals vary from 22.44‰ to25.11‰(CDT),and those in the wall rock from 11.60‰ to 19.06‰(CDT).We propose that the SO_4~(2-)generally experienced bacterial sulfate reduction in seawater before mineralization,and some SO_4~(2-)also experienced thermochemical sulfate reduction in hydrothermal system during mineralization.The δ~(13)C values of witherite range from-27.30‰ to-11.80‰(PDB),suggesting that carbon was sourced from organic substances(like CH_4,C_2H_4,and C_2H_6).The formation of witherite was possibly associated with thermochemical sulfate reduction,which caused the consumption of the organic gases and SO_4~(2-) in the hydrothermal solutions,consequently inhibiting barite formation.The important conditions for forming witherite include high fluid temperatures,high Ba~(2+) concentrations,CO_2 in the fluids,low HS~- concentrations,and the subsequent rapid diffusion of H_2S during thermochemical sulfate reduction of the fluids.