熔片制样-X射线荧光光谱法测定海洋沉积物样品中主次量组分

采用混合熔剂熔融制备样片,用Axios X射线荧光光谱仪测定海洋沉积物样品中SiO2、Al2O3、Fe2O3、MgO、CaO、Na2O、K2O、P2O5、TiO2、MnO、BaO、Ni、Cu、V、Cr和Zn等16种组分,用理论α系数校正基体效应,分析方法的精密度(RSD,n=12)为Cu和Cr小于6%,其余大多数主次量组分小于2%。方法用海洋沉积物国家一级标准物质验证,测定值与标准值相符。     

偏硼酸锂碱熔-电感耦合等离子体质谱法同时测定海洋沉积物中48种元素

海洋沉积物常用的分析方法如敞开消解或高压密闭消解结合电感耦合等离子体质谱(ICP-MS)或电感耦合等离子体发射光谱(ICP-OES)测定,粉末压片或熔片结合X射线荧光光谱法(XRF)测定,分别存在消解不完全、速度慢、检出限高等缺点,导致样品前处理效率低、待测元素少。针对上述问题,本文采用偏硼酸锂为熔剂分解样品,5%硝酸浸取,用ICP-MS法进行测定,建立了一种快速分析海洋沉积物中48种元素的方法。使用海洋沉积物国家标准物质作为高点绘制标准工作曲线,确定了助熔剂偏硼酸锂用量、稀释倍数、各待测元素的分析同位素及内标元素、仪器测定模式及个别元素的干扰校正方程等,得到最佳分解条件及测定条件。结果表明:由于高温损失,P、As、Se、Cd、Hg等元素无法得到准确结果,可改用微波消解等方式前处理后再进行测定;Cu、Zn、Cr、Ni、Co等共计48种元素使用本法均能得到准确结果,各元素方法精密度(RSD)均小于9.7%。本方法应用于分析海洋沉积物国家标准物质GBW07333、GBW07314、GBW07335、GBW07336,测定值和认定值相符;分析海洋沉积物实际样品,各元素加标回收率介于83.6%~118.6%。本方法可测定元素多,极大提高了分析效率,适合大批量样品分析。     

高压密闭消解-电感耦合等离子体质谱法测定海洋沉积物中稀土元素

样品用HNO3-HF高压密闭消解,电感耦合等离子体质谱测定海洋沉积物中15种稀土元素。研究了消解方法、酸体系和质谱干扰对稀土元素测定的影响。结果表明,相比于电热板消解和微波消解,高压密闭消解具有酸用量少、消解完全、消解过程损失少等优点;HNO3-HF体系能有效地分解海洋沉积物样品;利用干扰离子校正方程,能有效地校正Ba和轻稀土元素所形成的多原子离子干扰。15种稀土元素的方法检出限为3～15 ng/g。使用水系沉积物标准物质GBW 07309和GBW 07311、海底沉积物标准物质GBW 07313进行验证,测定值与标准值基本吻合,相对标准偏差和相对误差均低于5%。方法用于长江口沉积物样品的测定,精密度(RSD,n=6)小于5%,加标回收率为95.8%～104%。该方法检出限低,精密度和准确度高,适用于大批海洋沉积物样品的分析。     

熔融玻璃片制样-X射线荧光光谱测定页岩中主量元素

熔融片法制样,用X射线荧光光谱法测定页岩样品中硅、铝、铁、钙、钾、镁、钠7个主量元素,以页岩、岩石、水系沉积物、土壤国家一级标准物质作为校准样品,使用理论α系数和经验系数相结合的方法校正基体效应。方法精密度(RSD,n=12)≤1.50%。分析结果与化学法进行对照基本一致。     

用X射线荧光光谱法测定Cl、S等31个元素

采用硼酸镶边垫底的粉末样品压片制样,用ARL ADVANT′XP＋型X射线荧光光谱仪对土壤和水系沉积物样品中Na、Mg、Al、Si、P、S、Cl等31个组分进行测定。重点研究了Cl和S等元素的测定条件、痕量元素的背景选择和谱线重叠校正问题。使用经验系数法和康普敦散射作内标校正基体效应。经标准物质校验,结果与标准值吻合。方法的检出限、精密度和准确度能满足多目标地球化学调查样品的分析要求。     

玻璃熔片制样X射线荧光光谱法测定矾土中主次量组分

建立了玻璃熔片-X射线荧光光谱测定进出口矾土中主、次量组分的分析方法,用可变α系数校正元素基体效应,同时进行谱线重叠校正。利用高纯化学试剂配制合成标准参考物质,球磨机混匀,熔融玻璃片法制备系列校准样片,用X射线荧光光谱法对样品中的二氧化硅、三氧化二铁、三氧化二铝、氧化钙、氧化镁、氧化钾、五氧化二磷、二氧化钛进行测定。方法回收率为98.1%~111.0%,经国家铝矾土标准物质GBW 07178、GBW 07179验证,结果与标准值基本一致。建立的方法解决了测试过程中标准样品种类和数量不足的难题。     

熔融制样-X射线荧光光谱法测定硅酸盐样品中主量元素

采用熔融制样,以四硼酸锂-偏硼酸锂(质量比为67∶33)作熔剂,溴化铵作脱模剂,硝酸铵作氧化剂制备玻璃熔片。选用土壤、岩石、水系沉积物等国家标准物质拟合校准曲线,用经验系数法校正元素间的基体效应,各组分的线性相关系数均达到了0.999以上。使用日本理学ZSX PrimusⅡ型光谱仪对样品中SiO_2、Al_2O_3、TFe_2O_3、TiO_2、K_2O、Na_2O、CaO、MgO、MnO、P_2O_5等10种组分进行同时测定,分析结果与标准物质认定值或化学方法结果相符,相对标准偏差(RSD,n=12)小于5%,准确度和精密度均已达到地质矿产行业标准规范要求。方法简便、快速、准确、高效且绿色环保,满足了硅酸盐样品中主量元素快速分析测试的需求。实验表明,利用X射线荧光光谱法对硅酸盐主要成分含量进行同时分析是可行的。     

四酸溶样电感耦合等离子体发射光谱法测定地质样品中的钪

分析地质样品中钪的含量,国家标准方法是采用过氧化钠熔融,过滤分离后电感耦合等离子体发射光谱法（ICP-AES）测定,过程繁琐,样品前处理引入大量盐类且分析结果精度不高,不能适应当前矿产勘查快速准确检测的需要。本文建立了采用硝酸、盐酸、高氯酸和氢氟酸处理样品,ICP-AES测定地质样品中钪的分析方法。选择5%盐酸为溶液介质,干扰元素含量低于2%时运用干扰因子校正法（IEC）优化谱线强度以及适量稀释溶液降低基体效应,提高了分析的准确度和精密度。方法测定范围宽（0.00003%~10%）;检出限为0.0016 μg/mL,优于国家标准方法检出限（0.004 μg/mL）;方法回收率为97.0%~99.3%,方法精密度（RSD,n=6）为0.4%~2.3%;国家一级标准物质的测定值和标准值吻合,分析结果准确可靠。虽然酸溶法不能完全溶解所有类型的地质样品,但对区域环境条件要求不高、简便快捷,本法以酸溶法替代碱熔法处理样品,避免了待测组分和干扰物质的引入,对ICP-AES测定钪的稳定性有较大改善,适用于批量快速分析地质样品中的钪元素。     

粉末压片-波长色散X射线荧光光谱法测定地球化学样品中氯的方法研究

在对比已有相关分析方法的基础上,建立了粉末压片-波长色散X射线荧光光谱法测定地球化学样品中氯元素的分析方法.采用岩石、沉积物和土壤等78种国家一级地球化学标准物质作为校准系列建立校准曲线;利用经验系数法进行基体效应校正,利用含量校正法进行谱线重叠干扰校正;总结了地球化学样品中氯元素测定值随测定次数的变化规律及原因.结果表明:氯的检出限为7.95μg/g;分析3种国家一级地球化学标准物质12次,得到测定值的相对标准偏差均小于10％;采用国家一级地球化学标准物质验证方法准确度,测定值与标准物质认定值相吻合,测定平均值与标准物质认定值的对数差值的绝对值(?lgω)均小于或等于0.02,满足多目标区域地球化学调查规范的要求.     

电感耦合等离子体发射光谱法测定锌精矿中的二氧化硅

采用碱熔酸化方法处理样品,选用金为内标元素,电感耦合等离子体发射光谱法测定锌精矿中的二氧化硅。研究了熔融试样时引入的基体元素钠对被测元素的干扰情况,结果表明基体效应明显存在,且随着钠量的增加,基体效应显著增强,仪器稳定性严重降低,影响测定结果的准确度。内标校正法有效克服了基体效应及仪器波动产生的影响。研究结果表明,二氧化硅的检出限为0.006 3 mg/L,测定范围为0.02%~10%,对矿石标准物质进行测定,结果与标准值一致,方法精密度(RSD,n=5)小于2%。     

I–P<Subscript>2</Subscript>O<Subscript>5</Subscript> diagrams as an indicator of depositional environment in marine sediments: preliminary findings (Sri Lanka)

The concentrations of Br and I in marine sediments have been used to categorize the sedimentary environments of different coastal regions of the world with respect to organic matter contents. The present study uses the concentrations of Br, I and P₂O₅ of different marine settings as a new proxy to interpret the depositional environments. A total of 150 coastal lagoon sediment samples (suspended sediments, surface sediments and sediment cores) were analyzed for Br, I and P₂O₅ concentrations by X-ray fluorescence spectrometry. They were compared with the Br, I and P₂O₅ concentrations of the 2004 Indian Ocean tsunami sediments. Sediments from various sources are separately clustered in I–Br plot and a trivial negative correlation is found for the whole plot. A similar correlation pattern exists in the I–P₂O₅ diagram. This correlation is explained by the distribution of marine plants (higher and lower) in different sedimentary environments of the coastal profile. Therefore, the concentration of I and its relation to P₂O₅ can be used as a tool to identify sediment depositional environments in marine settings.     

Direct Current Plasma Emission Spectrometric Determination of Major, Minor and Trace Elements in Microwave Oven Acid Leachates of Powdered Whole Coal Samples

Major concentrations of Al₂O₃, Fe₂O₃, MgO, CaO, Na₂O and K₂O, minor levels of TiO₂, P₂O₅ and thirty petrologically, geochemically and environmentally significant trace elements have been determined in microwave oven acid leachates of whole powdered coal samples by direct current plasma‐atomic emission spectrometry (DCP‐AES). A single sample preparation procedure was suitable for all the determinations with no additional dilution step for major elements solution. Dried samples (0.5 g) were treated in low‐pressure PFA digestion vessels with HF/HCl/HNO₃/HClO₄ acids to quantitatively extract the analytes from the bulk material, while leaving the major part of organic matrix as a residue. The major constituents of geological samples, in particular the easily ionised elements (EIEs) such as alkali and alkaline earths, may complicate the instrumental determinations in DCP‐AES because of differential enhancements of elemental emission intensities and stray light interferences. Taking account of these factors, the coal matrix is considered to have very low major oxide totals as compared to many other common geo‐environmental and related materials (rocks, sediments, soil, ashes etc.). The sample size employed here, while yielding a relatively concentrated solution to cover a wide range of elemental determinations, provided a sample matrix that significantly diminished interferences for DCP measurements. The need for closely matching the unknowns and calibrators was eliminated except for overall acidity and an excess quantity of caesium for EIE buffering. Calibration of the spectrometer was accomplished by simple aqueous single element solutions as high concentration calibrators in addition to a reagent blank as a low concentration calibrator. Two point working curves were established to allow for the maximum concentrations of each element expected in the unknowns. The precision of determinations under routine conditions as well as the reproducibility of the leaching and precision of instrumental measurements have been evaluated. Relative standard deviations (RSD) were of 1–2% for those elements whose concentrations in solid samples were well above the limits of quantification. Method detection limits in the buffered solutions were also evaluated. To evaluate the accuracy of the microwave oven‐DCP method a suite of eight certified coal reference materials of differing rank, were analysed with good agreement with the certified and/or available published data. Results are presented for the uncertified major oxides in the AR series reference materials.     

Geochemistry of a Tidal Transgressive Heterolithic Succession：The Ituzaingo Formation （Middle Miocene）,Argentina

Geochemical analysis by means of XRF and ICP-AES was carried out on 35 selected saples,Major and trace elements were determined.They were:CaCO3,P2O5,Fe2Oe,TiO2,SiO2,Al2O3,CaO,K2O,MnO,Rb,Cs,Ga,Zr,Ta,Nb,Sr,Ba,Cr,Ni,Zn,Pb,Cu,V and B.The country rocks studied were of sandy-muddy lithofacies.belonging to a typical tide marine transgressive heterolithic succession of Middle Miocee age.They are called the Ituzatingo Formation.The formation outcrops in northeastern Argentina on the left of the Parana River Valley.The depositional setting largely depends on the outstanding internal structures and textures(i.e.,herringbone cross stratification,tidal bindles,reactivation surfaces).In the study area.loessial friable sediment was used as geochemical background because it overlies shallow marine sediments.The results show significant differences.Boron is absent in loessial sediments.On the other hand .several trace elements such as vanadium and chromium are concentrated in the shallow marine sediments.These results may be useful to discernuncertain beds in the area studied.     

The relation between Li, V, P2O5, and Al2O3 contents in marls and mudstones as indicators of environment of deposition

The contents of Li, V, P₂O₅, and Al₂O₃ in marls and mudstones collected from three different formations, cropping out in northern Iraq, showed that the ratios of Li/Al₂O₃, V/Al₂O₃, and P₂O₅/Al₂O₃ in these rocks can be used to discriminate environments of deposition of these formations. Relatively high values of the above ratios characterize the deep marine Shiranish environment while lowest values characterize freshwater environment of deposition of the Injana rocks. Despite that marls of the Fatha formation were deposited in marine lagoonal environment, the ratios P₂O₅/Al₂O₃ and V/Al₂O₃ could not be discriminated from the freshwater Injana mudstones. The well-known phenomenon that marine surface water and down to a depth of 50 m almost lacks soluble P explain this behavior. In such water, almost all the soluble P is consumed by surface organism rendering it unavailable for adsorption by the sediments. The high salinity of the lagoonal environment prevented adsorption of soluble V on clay minerals because of its inability to compete with other species of much higher concentrations.     

Spatial trends in the geochemical composition of sediments in the Panuco River discharge area, Gulf of Mexico.

Major and trace elements, organic matter, carbonates, loss of ignition, grain size, gravel, sand, silt, clay, and qualitative mineralogical composition were determined on surficial marine sediments sampled during the stormy (February), dry (May), and rainy (September) seasons in the coastal area adjacent to Panuco River discharges into the Gulf of Mexico. The sediments supplied by the river move in a north-east direction, and are deposited in the north-east extreme of the studied area. Terrigenous sediments show a strong association of Al₂O₃ with Fe₂O₃, Na₂O, K₂O, P₂O₅, Rb, Cu, Zn, organic matter, clay, and grain size (Mz). Mineralogical analysis shows that they are formed by quartz, kaolinite, montmorillonite, illite-montmorillonite and biotite. The highest metal concentration of Cu (25 mg/kg), Zn (155 mg/kg), Pb (50 mg/kg) and organic matter (1.26%) was observed in the sampling points located very close to the river mouth. A statistical analysis was done with the information contained in the variables. Five significant factors explain 77% of the total variance: factor 1 is due to sediments from a terrigenous source, factor 2 corresponds to sediments from a biogenous source, factor 3 is associated to sediments with heavy minerals, factor 4 is due to Co concentration, and factor 5 is due to Ni concentration. The sediments supplied from the river had a short-term local impact on the sediment distribution, as observed by the carbonate and heavy mineral concentration of the sediments.     

Source of sediments and metal fractionation in two Chinese estuarine marshes

The Changjiang and the Jiulong Estuaries, located in eastern and southeastern China, respectively, have different geomorphologic and tidal processes as well as anthropogenic development in their associated watersheds. Sediments in the Changjiang estuary mostly consist of SiO₂, CaO and MgO (mean percentages of 63.9, 4.34 and 2.35%), whereas sediments from the Jiulong estuary mostly consist of Al₂O₃, Fe₂O₃ and organic matter (mean percentages 19.2, 6.82 and 4.14%). The Jiulong estuarine sediments contain more than twice the concentrations of Pb, Zn, Cu, than those from the Changjiang estuary. In the Jiulong estuary, these heavy metals are associated with carbonates and organic matter, whereas in the Changjiang estuary, they are associated with residual fractions or clay. Sediments from the Changjiang estuary, mostly sediments with little organic matter, do not efficiently sequester anthropogenic-derived trace metals. In contrast, sediments from the Jiulong estuary consist of a mixture of fluvial and marine matter which can sequester heavy metals contributed by larger landscapes with industrial and municipal wastewater.     

渤海湾西岸QX02孔Ⅱ海的识别及OSL年龄

以渤海湾沿海低地的QX02孔为研究对象,进行了沉积岩石学分析和底栖有孔虫统计,结合加速器质谱~(14)C测年和光释光(optically stimulated luminescence,OSL)测年,探讨了该孔记录的第Ⅱ海相层埋深和形成时代。第Ⅱ海相层厚度11.4m,记录相对海面高度-26.83~-15.43m。AMS~(14)C年龄表明,Ⅱ海形成于MIS 3早期、甚至更早。OSL年代学研究显示,Ⅱ海样品等效剂量离散度较高,并且主要集中在2个区间,计算得到新、老2个年龄阶段。基于OSL测年原理的常规判断,认为较老的83.5~62.6ka阶段系受曝光不充分组分的影响,通常采用较年轻的51.9~39.9ka阶段为QX02孔的Ⅱ海沉积年龄。但是,较老的一组年龄从新的视角,暗示了可能的原始沉积过程及相应的海侵发生时间,因而具有重要的年代学和沉积学意义。     

Denitrification pathways and rates in the sandy sediments of the Georgia continental shelf,USA

Denitrification in continental shelf sediments has been estimated to be a significant sink of oceanic fixed nitrogen (N). The significance and mechanisms of denitrification in organic-poor sands, which comprise 70% of continental shelf sediments, are not well known. Core incubations and isotope tracer techniques were employed to determine processes and rates of denitrification in the coarse-grained, sandy sediments of the Georgia continental shelf. In these sediments, heterotrophic denitrification was the dominant process for fixed N removal. Processes such as coupled nitrification-denitrification, anammox (anaerobic ammonium oxidation), and oxygen-limited autotrophic nitrification-denitrification were not evident over the 24 and 48 h time scale of the incubation experiments. Heterotrophic denitrification processes produce 22.8–34.1 μmole N m^-2 d^-1 of N₂ in these coarse-grained sediments. These denitrification rates are approximately two orders of magnitude lower than rates determined in fine-grained shelf sediments. These lower rates may help reconcile unbalanced marine N budgets which calculate global N losses exceeding N inputs.     

X射线荧光光谱法分析不同类型岩石中10种主量元素的测试能力验证

以28个不同类型岩石标样作外标,用玻璃熔片法制样,采用经验系数法进行基体校正,建立了X射线荧光光谱法(XRF)测定不同类型岩石中硅铝钙镁等10种主量元素的分析方法。该方法被用于参与GeoPT分析测试能力验证,15年来分析了23个不同类型的岩石验证样品。经验证该方法对SiO_2、Al_2O_3、K_2O和CaO具有非常好的分析效果(所有测定结果的|Z|2);对于MgO、MnO、TiO_2和Na_2O四个元素,尽管各有一个样品的分析结果的|Z|2,这主要是样品与标样的基体差异较大造成了低含量样品测定结果超差,但依然可获得好的分析效果;当TFe_2O_31.0%,P_2O_5含量在0.08%~0.80%区间时,分析结果的|Z|2,满足分析期望。总体上所建立的XRF分析方法稳定,可满足应用地球化学实验室测试不同类型岩石中10种主量元素的分析期望。