一种新的适合富有机质沉积岩的Re-Os同位素分析方法初探

虽然富有机质沉积岩中的Re和Os主要都富集在有机质中,但其中碎屑部分中的Re和Os也会影响其Re-Os等时线的准确度和精度。目前最常用的Cr O3-H2SO4溶样法虽然能尽量避免碎屑物质中Re和Os的溶出,但该方法具有Re流程空白高和环境污染严重等问题。因此,本研究尝试在富有机质沉积岩Re-Os同位素分析中使用H2O2-HNO3溶样来代替Cr O3-H2SO4溶样。本研究利用国际油页岩标样SGR-1b(USGS)为实验研究对象,分别对HCl-HNO3溶样、Cr O3-H2SO4溶样和H2O2-HNO3溶样3种溶样方法进行了对比研究。研究表明,H2O2与HNO3的体积比约为5﹕1的H2O2-HNO3溶液,不仅能保证样品和稀释剂的Re、Os同位素达到同位素交换平衡而且尽可能地避免碎屑物质中Re和Os的溶出。本方法相比于HCl-HNO3溶样,能尽量避免碎屑物质中Re和Os的溶出;而相比于Cr O3-H2SO4溶样,该方法具有本底低、无污染的优点。最后利用H2O2-HNO3溶样方法对广西金秀地区的泥岩样品和广东大宝山地区的碳质页岩样品进行了Re-Os同位素定年分析,分别得到了(404±5)Ma(IOs=1.57±0.13,n=8,MSWD=50)和(211±11)Ma(IOs=0.67±0.09,n=5,MSWD=11.1)的等时线年龄,这一结果与HCl-HNO3溶样得到的结果((412±11)Ma,IOs=1.18±0.38,n=8,MSWD=311;(223±18)Ma,IOs=0.59±0.14,n=5,MSWD=63)在误差范围内一致,但更为精确。     

硝酸水浴消解-冷原子荧光光谱法测定植物中的总汞

汞是有毒的重金属元素，汞污染问题已经引起全世界的关注。植物是陆地生态系统中汞的重要输入与输出途径，通过根系吸收土壤中的汞，通过叶片与大气进行汞交换。植物位于食物链的最底层，它对汞的富集作用威胁着人类与动物的健康与安全。植物总汞的测定是陆地生态系统中汞分析的一项重要内容。目前国内常用的测定植物总汞的方法为直接加热酸消解法，包括HNO3-H2SO4-V2O5法、HNO3-HClO4法和HNO3-H2SO4-HClO4法。然而，这些方法消解过程中试剂加入比例调配操作繁琐。本文在前人试验的基础上，改HNO3-H2SO4混合酸水浴一次消解为HNO3水浴一次消解，降低了取样量，简化了操作步骤。     

X射线粉晶衍射法分析磷化膜不同成分衍射强度比

利用X射线粉晶衍射法对金属板材及其磷化膜进行全谱和区段扫描,在确定镀膜中存在Zn2Fe(PO4)2.4H2O和Zn3(PO4)2.4H2O物相的基础上,求出Zn2Fe(PO4)2.4H2O的(100)和Zn3(PO4)2.4H2O的(020)衍射峰的计数强度,计算出样品磷化膜的磷比,从而判断出磷酸盐配比是否达到工艺要求。     

高铝粉煤灰制备莫来石晶须的实验研究

以高铝粉煤灰、NH4Al(SO4)2.12H2O和NaH2PO4.2H2O等为原料,设计配方研究温度对莫来石晶须生长的影响。运用X射线粉末衍射(XRD)和扫描电子显微镜(SEM)等手段,对莫来石及晶须形成过程进行表征,结果表明:当Al2O3/SiO2摩尔比为0.32,烧结温度1 400℃,保温时间6 h,可获得直径为0.2 mm~0.5 mm,长径比为17~30的莫来石晶须。     

硅酸盐体系的化学平衡:(2)反应热力学

通过具体的应用实例,系统介绍了在矿物材料学研究中硅酸盐体系的多相平衡反应热力学的基本原理。对硅酸盐体系的典型多相平衡反应进行了热力学计算,包括:(1)微晶玻璃制备过程中的硅酸盐熔融反应;(2)霞石正长岩和高铝粉煤灰利用技术中的硅酸盐烧结反应;(3)S iO2-CaO-H2O体系和KA lS i3O8-CaO-H2O体系雪硅钙石、硬硅钙石的水热晶化反应;(4)高铝粉煤灰和霞石正长岩烧结产物的溶解反应;(5)Na[A l(OH)4]-A l(OH)3-H2O体系和Na2SO4-Ca(OH)2-H2O体系中α-A l(OH)3和CaSO4.2H2O的析晶反应。研究成果可望对矿物材料制备实验方案设计、工业生产过程优化及改进产品性能提供理论指导,同时为同类材料学研究提供借鉴。     

碳酸盐岩地层中B元素测试方法——一种改进的ICP-AES方法

为解决碳酸盐岩地层中B元素分析困难的问题,采用HF-HNO3-HClO4-H3PO4溶样,电感耦合等离子体发射光谱法测定碳酸盐地层中的B元素。该方法的特点是,在溶样体系中加入适量H3PO4避免B元素的挥发损失,并对H3PO4最佳用量进行了试验。方法检出限3.8×10-6(10SD),用国家一级标准物质进行准确度、精密度验证,精密度(RSD)小于6.44%,准确度(ΔlgC)小于0.087。该方法还可以同时测定Be、Ba、Cr、Cu、Co、Ni、Pb、Mo、V、Mn、Li、Zn、Ga等十几种元素,也适用于土壤、岩石、水系沉积物其它样品中B等多元素同时测定。运用该方法测试了西南天山哈拉奇地区碳酸盐地层中B、Co、Ni、Cu、Zn、Pb、Ba等元素,并对其地质意义进行了简要探讨。     

原子荧光光谱法测定地质样品中的痕量锗

分析了溶矿过程中HNO3、H2SO4、HClO4、H3PO4等对Ge的影响，采用AgNO3滤气装置消除气相干扰，测定了地质样品中的痕量锗，方法检出限为0．06μg／g，用土壤国家一级标准物质GBW 07401～GBW 07408验证方法，结果与标准值相符，其相对标准偏差(RSD，n=12)为3．66％～6．11％。     

四元体系K_2SO_4-K_2B_4O_7-K_2CO_3-H_2O 273K时介稳相平衡研究

采用等温蒸发法研究K2SO4-K2B4O7-K2CO3-H2O四元体系在低温273K时的介稳固液相平衡关系,测定了介稳平衡液相的溶解度和密度。研究发现,该四元体系273K时的介稳平衡相图有3个固相结晶相区分别为K2SO4,K2B4O7.4H2O和K2CO3.3/2H2O;3条单变量曲线E1E,E2E和E3E;一个共饱点E,在共饱点E处的液相中各盐的溶解度分别为K2CO3(43.46%),K2SO4(2.52%)和K2B4O7(3.10%);研究结果表明K2CO3对K2B4O7和K2SO4有强烈的盐析作用。实验证明在富含硼钾的扎布耶盐湖卤水中,低温平衡条件下硫酸钾和硼酸钾极易从溶液中结晶析出,而碳酸钾则由于溶解度大,介稳性强,即使在低温条件下也难以从溶液中析出。     

中国首次发现的水磷钙铀矿

内蒙古二连盆地2082砂岩型铀矿床中的主要工业铀矿物为水磷钙铀矿(Tristramite)。该矿物在中国是首次发现。其矿物颗粒细小,与黄铁矿、白铁矿等硫化物、黑色炭屑紧密共生。颜色为灰黑色—黑色,不透明,反射光下呈灰色—暗灰色、均质、无内反射。13个电子探针分析数据得出的平均化学成分为UO241.60%,CaO 14.50%,P2O522.71%,SO31.33%,FeO 0.81%。按照除磷以外阳离子数和为1计算的经验化学式为:(Ca0.589U0.351Fe0.026Na0.016Al0.009Y0.007)0.998[(PO4)0.729(CO3)0.225(SO4)0.038(SiO4)0.008]1.00.1.75H2O。简化式可以写成(Ca,U4+,Fe)[(PO4)(CO3)].2H2O。通过X射线衍射数据,用SHELXTL PC进行晶胞参数精修得到的六方晶胞,其参数为a=b=(0.69030±0.00129)nm,c=(0.63300±0.00083)nm。     

安徽省泗县山头金刚石砂矿中指示矿物特征研究

安徽省泗县山头地区分布着金刚石砂矿,其金刚石来源一直存在争议,尤其是在安徽省宿州栏杆地区发现了碱性基性岩型的金刚石后,一些学者认为栏杆地区可能是砂矿的来源.本文对山头金刚石砂矿中指示矿物(石榴子石和铬铁矿)进行了电子探针分析,结果显示石榴子石矿物化学式A32+B23+(SiO4)3中的A主要由Mg2+、Fe2+和Ca2+离子占位,B主要由Al3+离子和少量的Mn3+离子占位,以铁铝榴石(Alm)为主,其次是镁铝榴石(Pyp),属于铁铝-镁铝-钙铝石榴子石系列的G3、G4石榴子石;铬铁矿中Cr2O3的含量绝大多数大于40 wt％,MgO的含量平均在8 wt％左右,TiO2含量在0.11～2.26 wt％之间,属于中铬-铬铁矿,与山东、辽宁金伯利岩中发现的中铬-铬铁矿成分基本一致,说明其物源并非来自栏杆地区碱性基性岩型金刚石原生矿.     

亚钛还原钒酸铵微量滴定法测定矿石中微量铀方法的改进

根据亚钛还原钒酸铵滴定法的测定原理,对样品溶样、过滤洗涤、还原氧化、滴定等操作方法做了改进。磷酸-盐酸-过氧化氢混合酸低温溶解样品,离心分离过滤,亚钛还原UO22+,过量亚钛用次溴酸钠氧化,尿素亚硝酸钠混合液进一步氧化未被次溴酸钠氧化的微量低价杂质。在小体积(10 mL)范围内,用低浓度钒酸铵标准溶液进行滴定操作测定微量铀,滴定终点清晰,相对标准偏差(RSD,n=5)为0.05%~0.07%,方法测定下限为0.001%,适于矿石和矿渣中0.001%~0.01%铀的测定。方法简便、快速,能满足生产和科研的需要。     

硫酸铵溶液淋滤-电感耦合等离子体质谱测定离子相稀土分量的方法优化

离子吸附型稀土中离子相稀土的准确测定对稀土矿体资源评价具有重要意义。离子相稀土以羟基或水合羟基的形式吸附在黏土矿物上,可与强电解质(Mg~(2+)、NH_4~+等)交换解吸进入溶液。前人以硫酸铵为淋滤液,实现了离子相稀土的解吸、提取,但在溶液浓度、浸取过程等方面选择各异,淋滤浸取率(60%～90%)差异大,未形成高效、统一的浸取方法,不利于离子相稀土元素的精确测定。本文通过对比实验规范了硫酸铵淋滤离子相稀土的各项淋滤参数(固液比、硫酸铵浓度、样品最佳称样量、浸泡时间),减少了淋滤过程中离子相稀土的损失,浸取率达到88%～98%,进而利用ICP-MS测定离子相稀土分量。方法检出限为0. 05～5. 11 ng/g;三类岩性离子吸附型稀土样品的精密度为:火山岩1. 80%～10. 01%,变质岩1. 06%～7. 27%,沉积岩1. 72%～7. 58%。协作实验室的分析结果验证了本方法的可靠性和准确性。本方法操作简便,分析效率高,为建立相关的行业标准乃至国家标准奠定了基础。     

祁连山大雪山地区大气PM2.5细粒子中可溶性离子特征

为了研究祁连山大雪山地区大气PM_2.5细粒子中可溶性无机离子组分的变化特征, 于2010年7月至2011年7月在祁连山冰川与生态环境综合观测站附近采集46个大气PM_2.5的Telfon滤膜样品, 并应用离子色谱对可溶性离子进行了分析.结果显示: 所测样品的阴、 阳离子中, SO₄^2-、 NO^-₃、 Ca²⁺和NH⁺₄的质量浓度分别为1.54μg·m^-3、 0.38μg·m^-3、 0.73μg·m^-3和0.22μg·m^-3, 累计约占到水溶性离子总量的88%.可溶性离子浓度呈现出春夏季节明显高于秋冬季节的特征, 夏季的浓度最高, 其次是春季、 冬季和秋季. Cl^-、 Ca²⁺、 Na⁺和Mg²⁺之间的相关性极高, SO₄^2-和NO^-₃与大部分阳离子的相关性都很高, 说明大部分硫酸盐是来自于中亚沙尘源区的自然源, 而并非是通过人类活动造成的一次污染物通过二次反应过程得到的. NH⁺₄仅与SO₄^2-通过相关性检验说明, 该地区NH₃主要中和了大气中硫酸并生成(NH₄)₂SO₄.该地区的大气环境主要来源于自然源的影响, 但夏季风期间人为污染排放已经不可忽视, 这也得到HYSPLIT后向轨迹模式的计算验证.     

Investigation of ammonia removal from polluted waters by Clinoptilolite zeolite

Ammonia nitrogen compounds in the wastewaters and effluents have harmful effects on water resources. Ion exchange with zeolites is a separation process for ammonia removal from effluents. The objective of this research was to study the efficiency of an ammonia removal and the factor affecting to this process. The Clinoptilolite was obtained from Semnan mines at the north part of Iran. The samples were grounded and sieved based on the U.S. standard mesh number 20, 30, 40 and conditioned by ammonia sulfate and sodium chloride solutions. The characteristics of samples for ammonia removal and the selectivity sequence for adsorbing interfering cations were then determined. Results shown that the average ion exchange capacity of zeolite in batch and continuous systems were 6.65–16 and 16.31–19.5 mg NH₄ ⁺ /g zeolite weight, respectively. In study on the zeolite for selective cations showed the ranking of K⁺, NH₄ ⁺, Na⁺, Ca²⁺ and Mg²⁺ respectively. Results indicated that high level of regeneration (95–98%) might be achieved with NaCl solution. Based on the results, Clinoptilolite may be effective applied in wastewater treatment, both from technical and economical aspects.     

碳氮源对P.Fluorescens吸附和还原U(Ⅵ)的影响研究

为探讨不同碳氮源对培养基中铀酰离子的络合形态及荧光假单胞菌对铀吸附和还原作用的影响,本文以查氏培养基为基础,将蔗糖替换为葡萄糖或将硝酸钠替代为氯化铵,采用Visual MINTEQ分析研究铀酰离子络合形态。研究结果表明,碳氮源的种类对微生物生长无影响。U(Ⅵ)浓度为10 mg/L时,3种培养基中铀酰离子的主要络合形态均为UO2PO-4。U(Ⅵ)浓度为50~200 mg/L,查氏和葡萄糖碳源培养基中铀酰离子主要络合形态均为UO2(SO4)2-2。氯化铵氮源培养基中,U(Ⅵ)浓度为50 mg/L时铀酰离子的主要络合形态为UO2HPO4(aq),浓度为100~200 mg/L时主要是UO2Cl2(aq)。荧光假单胞菌对U(Ⅵ)耐受浓度高达100 mg/L,当U(Ⅵ)浓度达到200 mg/L时,菌体失活。荧光假单胞菌为活体时,对U(Ⅵ)的吸附率为84.02%~92.59%,还原率为3.32%~10.94%,不同碳氮源对铀吸附和还原的影响较小。荧光假单胞菌为死体时,对铀的吸附率为24.33%~39.05%;非葡萄糖碳源培养基中,对铀的还原率为37.50%~44.58%,含还原性葡萄糖的培养基条件下U(Ⅵ)的还原率为53.12%。还原性葡萄糖与荧光假单胞菌对铀的还原为协同作用。荧光假单胞菌为活体时,培养基成分被微生物充分利用,两者协同作用不明显。     

The impacts of common ions on the adsorption of heavy metal

Researches on the impact of common ions onto sediments are of great importance for the study of the heavy metal adsorption mechanisms. Considering the surface sediments from the relatively clean reach in the Baotou section of the Yellow River as the adsorbent, this work presents the impacts of common ions (Na⁺, Mg²⁺, K⁺, Ca²⁺, Cl⁻, SO₄ ²⁻, and NH₄ ⁺) on heavy metals (Cu²⁺, Zn²⁺, Cd²⁺, and Pb²⁺) adsorption. The experimental results reveal that the adsorptive capacities of the heavy metals are controlled by different adsorption mechanisms in different ion concentration ranges. With the increase of the ionic strength, the adsorption of the heavy metals increases for the compression of the electric double layer, whereas decreases for the decreasing of the ionic activities of the heavy metals. The competitive adsorption and complexations between the heavy metals and common ions are also important factors controlling the heavy metal adsorption. According to the experimental results and the real concentration of common ions in the Baotou section of the Yellow River, the increase of the concentrations of Na⁺, Mg²⁺, K⁺, and Ca²⁺ would cause the increase of Zn²⁺ adsorption and reduce the Zn pollution. The NH₄ ⁺ from the industrial discharge of the tributaries has a strong impact on the heavy metal adsorption.     

Effects of poor quality irrigation waters on the nutrient leaching and groundwater quality from sandy soil

Sodium (Na⁺) in poor quality irrigation water participate in ion-exchange processes results in the displacement of base cations into solution and a raised concentration in groundwater. Knowledge of the rate of decrease of nutrients from soils resulting from poor water quality application is essential for long-term planning of crop production while minimizing the impact on groundwater quality. In this study, we examined the effect of sodium adsorption ratio (SAR) of irrigation water on nutrients leaching and groundwater quality in columns of sandy soil. Three types of irrigation waters at three NaCl–CaCl₂ solutions with the following levels of SAR (5, 15, and 30) were synthesized in laboratory. With the application of solutions, exchange occurred between solution Na⁺ and exchangeable cations (Ca²⁺, Mg²⁺, and K⁺), resulting in the displacement of these cations and anions into solution. Increasing the level of SAR from 5 to 15 and 30 resulted in increase in the average exchangeable sodium percentage (ESP) of the soil from 10.4 to 20.3, and 32.5, respectively. Adverse effect of high Na⁺ concentration in the solutions on raising ESP was less pronounced in solution having low SAR. Leaching of Ca²⁺, Mg²⁺, K⁺, and P from soil with the application of solutions represents a significant loss of valuable nutrients. This sandy soil showed the high risk for nutrients transfer into groundwater in concentrations exceeding the groundwater quality standard. Irrigation with poor quality water, which is generally more sodic and saline than regional groundwater, increases the rate of sodification and salinization of shallow groundwater.     

Weathering of phlogopite in simulated bioleaching solutions

The purpose of this study was to examine structural alterations of finely ground phlogopite, a trioctahedral mica, when exposed to acid, iron- and sulfate-rich solutions typical of bioleaching systems. Phlogopite suspensions were supplemented with ferrous sulfate and incubated with iron- and sulfur-oxidizing bacteria (Acidithiobacillus ferrooxidans) at 22 °C. As bacteria oxidized ferrous iron, ferric iron thus formed partially precipitated as K-jarosite. K-jarosite precipitation was contingent on the preceding ferrous iron oxidation by bacteria and the release of interlayer-K from phlogopite. This chemically and microbially induced weathering involved alteration of phlogopite to a mixed layer structure that included expansible vermiculite. The extent of phlogopite weathering and structure expansion varied with duration of the contact, concentration of ferrous iron and phlogopite, and the presence of monovalent cations (NH₄⁺, K⁺, or Na⁺) in the culture solution. NH₄⁺ and K⁺ ions (100 mM) added to culture suspensions precipitated as jarosite and thereby effectively prevented the loss of interlayer-K and structural alteration of phlogopite. Additional Na⁺ (100 mM) was insufficient to precipitate ferric iron as natrojarosite and therefore the precipitation was coupled with interlayer-K released from phlogopite. When ferrous iron was replaced with elemental sulfur as the substrate for A. ferrooxidans, the weathering of phlogopite was based on chemical dissolution without structural interstratification. The results demonstrate that iron oxidation and the concentration and composition of monovalent ions can have an effect on mineral weathering in leaching systems that involve contact of phlogopite and other mica minerals with acid leach solutions.     

Major ion composition and seasonal variation in the Lesser Himalayan lake: case of Begnas Lake of the Pokhara Valley, Nepal

The Begnas Lake in the Pokhara Valley is one of the threatened habitats in Nepal. The major ion chemistry explains the status of most of the inorganic nutrients and their possible sources. However, the earlier studies mostly cover limnological investigations, and phytoplankton and zooplankton diversity. Thus, the present study has been conducted to investigate the geochemical processes and to examine the seasonal variation of chemical composition within Begnas Lake. The results showed that SO ₄ ^2- , PO ₄ ^3- , and NO ₃ ^- increased compared with the previous values. The domination of Ca²⁺, Mg²⁺, and HCO ₃ ^- explains the influence of carbonate weathering on the major ion concentration. In general, pH and dissolved oxygen decreased with the depth of water-column, while electric conductivity, total dissolved solids, HCO ₃ ^- , Cl^-, H₄SiO₄, K⁺, Mg²⁺, Ca²⁺, Mn²⁺, and Fe increased. Among the cations, the predominance of Ca²⁺ and Mg²⁺ as characterized by high (>0.6) (Ca²⁺ + Mg²⁺)/(Tz⁺) and (>0.8) (Ca²⁺ + Mg²⁺)/(Na⁺ + K⁺) equivalent ratios, also suggests prevalence of carbonate weathering. The low value of (Na⁺ + K⁺)/Tz⁺ ratio shows deficiency of Na⁺ and K⁺, suggesting low contribution of cations via aluminosilicate weathering. The C-ratio suggests a proton source derived both from oxidation of sulfide and dissolution and dissociation of atmospheric CO₂ during different seasons. Though the major hydro-chemical parameters are within permissible limit, the increase in trophic state of the lake suggests that inherent biogeochemical processes make the limiting nutrients available, rendering eutrophic effect. Therefore, further comprehensive studies incorporating sediment–water interaction ought to be carried out to explain the ongoing phenomena and curb the eutrophication process in the lake.     

我国海洋地质分析测试技术

21世纪是海洋开发和利用的新世纪,随着国家对海洋地质调查工作的日益重视,海洋地质分析测试技术迎来了快速发展时期。本文对我国海洋地质分析测试技术的最新进展进行了简要评述:为满足海洋区域调查、海岸带地质调查的需要,建立了以大型分析仪器为主的多元素同时分析海洋地质样品的快速高效分析方法体系;针对新能源天然气水合物样品,开展了异常识别测试技术和应用测试技术研究,建立了用离子色谱法快速测定孔隙水中阴离子Cl^-、Br^-、SO₄^2-和阳离子Na⁺、NH₄⁺、K⁺、Ca²⁺、Mg²⁺ 的方法,开发出了以声学、电阻、时域反射(Time Domain Reflectometry, 简称为TDR)三种探测技术为主的适用于天然气水合物模拟实验的探测新技术;对于海洋沉积物中有机污染物样品,采用复合固相萃取净化柱,对海洋沉积物萃取液样品进行净化分离,依次选用正己烷和正己烷－二氯甲烷混合液淋洗固相萃取净化柱,可有效保留基体杂质,实现了海洋环境地质调查中基质复杂沉积物样品的同时净化、分离与测试,可显著提高实验效率;同时在大洋矿产样品分析技术、海洋地质标准物质研制、船载与原位化学探测技术等方面也取得了重要进展。本文还提出在海洋调查和监测的应用中,船载及原位测试技术将愈趋重要,加强海洋化学传感器的性能和检测集成化技术是今后的一个重要发展方向。