电感耦合等离子体质谱法(7900 ICP-MS)测定土壤中30种痕量元素

本文中土壤样品利用HNO3-HF-HCl O4混酸消解和王水提取后,采用电感耦合等离子体质谱(ICP-MS)法同时测定了国家标准土壤样品中30种痕量元素(Ba、Be、Bi、Cd、Ce、Co、Cr、Cs、Cu、Ga、Hf、In、La、Li、Mn、Mo、Nb、Ni、Pb、Rb、Sb、Sc、Sr、Ta、Th、Tl、U、V、W、Zn)的含量。其测定值与标准值相符,准确度符合国家标准要求。该方法所有元素的相关系数在0.9990~1.0000之间,各元素的方法检出限均满足要求,相对标准偏差(RSD)≤10%,结果表明该方法满足土壤中痕量元素的分析要求,建立的方法样品前处理程序简单快速,线性范围宽,分析重现性好,结果准确,可以运用于大批量地质样品中痕量元素含量的同时测定。最后用已建立的方法测定了北京某地区的土壤样品,测试结果满意。     

镉同位素分馏及其在示踪土壤镉来源和迁移转化过程中的应用进展

土壤镉污染已成为危害人体健康的主要因素之一,要实现精准、快速和有效地防治土壤镉污染,首先必须厘清土壤中镉的来源及其迁移转化行为。近年来,随着镉同位素分析技术的进步及其分馏机制认识的深入,镉同位素在土壤镉示踪中展示出了巨大的应用潜力。本文在前人研究的基础上,归纳了土壤样品镉同位素分析前处理方法以及测试技术的研究进展。对于基质复杂的土壤样品,高温高压密闭消解和微波消解可以满足其镉同位素测试要求。在分离纯化镉回收率足够、干扰元素去除彻底的情况下,应用多接收电感耦合等离子体质谱(MC-ICP-MS)分析镉同位素并采用标准-样品匹配法、外标法或双稀释剂法进行质量歧视校正,均可获得较高精度的土壤镉同位素组成数据。同时,本文概括了土壤多个潜在镉源的镉同位素组成以及典型过程(风化淋滤、吸附、沉淀/共沉淀、络合)镉同位素分馏方向与程度。结合最新研究成果,总结了镉同位素在示踪土壤镉来源及其迁移转化过程中的应用。在未来的工作中,需进一步开发和优化高精度镉同位素分析方法,建立土壤镉同位素指纹图谱,揭示土壤多组分、多界面过程中的镉同位素分馏机制和特征。     

某固体废弃物场地环境因子监测与分析

本次对某固体废弃物场地环境调查,采用钻孔取样方式,采集了土壤和地下水样品,土壤样品和地下水样品分别选取了45项监测因子和35项监测因子进行测试.通过分析测试结果表明,场地中土壤样品重金属监测因子大多超标,地下水水质划归Ⅴ类.本研究为同类环境调查监测因子的选取及分析评价提供了依据与借鉴.     

固体直接进样-电热蒸发电感耦合等离子体质谱联用分析土壤中的重金属元素

为解决高基质土壤样品中痕量重金属元素检测前处理操作繁琐、样品易二次污染或损失等问题,本文建立了采用固体直接进样-电热蒸发-车载电感耦合等离子体质谱定量分析环境现场土壤样品中Cr、Cu、Zn、As、Cd、Hg和Pb元素的分析方法。该方法采用高温电热蒸发石墨炉作为原子化器,样品称量后经梯度升温选择性蒸发,再结合双通道伴热传输石英管、两路氩气在线稀释、ICP-MS瞬时扫描、基体匹配外部校正等策略,有效解决了土壤直接进样过程中传输效率低、基体效应大的问题。在优化的仪器条件下,按照实验方法称取20mg土壤标准物质GBW07401、GBW07406、GBW07407、GBW07430和GBW07456建立外部校正曲线,样品中7种元素的标准曲线线性相关系数≥0.999;并按照实验方法测定了杭州市滨江区两处田间土壤样品中Cr、Cu、Zn、As、Cd、Hg和Pb,相对标准偏差(RSD)7%,相对误差5%,检出限为1.2～32.0ng/g,回收率为91.0%～113.0%。该方法是一种有实用价值的现场样品分析技术,适合现场中大批量土壤样品的分析监测。     

奉化南岙长寿村地质环境特征

通过区域性土壤样品测试结果的统计分析,研究了浙江奉化南岙长寿村所处区域土壤的地质环境背景;针对性地补充采集了土壤、稻谷、萝卜、大头菜、芋艿、水、人体毛发样品,进行生命有益、有害元素的测试。运用因子分析及对比分析的方法,研究长寿村的地质环境特征。研究结果认为,高含量的生命有益元素及低含量的有害元素组合在岩石—土壤—食物—人体系统中的循环起到了至关重要的作用。     

土壤和沉积物中22种有机氯农药和8种多氯联苯的气相色谱分析

近年来地下水、土壤和沉积物等介质中有机氯农药和多氯联苯分析方法的改善主要集中在样品前处理和分析测试条件等方面,而探讨布点、采样等方面的整套方法较少。本文建立了一套适用性较广的气相色谱法同时测定土壤和沉积物中22种有机氯农药和8种多氯联苯,方法检出限为0.09~0.48 ng/g,平均空白回收率为58.7%~133.7%。针对布点、采样、运输、保存、提取、净化、浓缩、仪器测试、数据处理和提交报告整个过程阐述了方法的有效性和实用性;并对提取、净化、测试等多个环节提供了两种或更多的选择,使方法具有更大的灵活性。本文提出,布点前应根据踏勘样品和前人资料考虑采集不同深度的样品;样品的布点、采集和制备均需选择样品,它们共同决定了样品的代表性;分析方法要灵活运用,对于很少检出的目标化合物可采用允许共峰但分析快速的方法,如果有检出再采用针对性的方法分别测定;样品的测定序列不应为了节约分析成本而过于简单。     

个旧锡多金属矿区水体酸碱性测量及形成机制

以云南个旧锡多金属矿区所测38个水样pH值为依据，探讨在矿区表生环境中酸碱度的形成机理。pH是研究物理化学条件变化的重要指标，目前已有很多关于土壤、水的pH测试方法，也做了很多的实验数据来表述各类土壤和水的酸碱度，在此基础上描述产生该结果的原因。但是大部分的酸碱度数据都是直接引用了测试结果，并没有对测试条件（如温度等）、样品采集情况以及采集区的气候，采集时间等可能影响测试结果的因素进行说明，以至于他人在直接引用结果时存在问题。以前大量关于矿山酸碱度的报道都是研究煤矿矿山酸碱度环境，本文对个旧地区金属矿山所能涉及和采集到的各类型样品酸碱度进行了测试，通过测试结果探讨造成酸碱度结果的原因。     

发射光谱法定量测定岩矿、土壤中的Ag,B,Sn

对土壤中的银、硼、锡测定通常用光谱法,以焦硫酸钾、氟化钠、三氧化二铝和碳粉为缓冲剂,改善各元素的蒸发行为,采用较短的摄谱时间,大大降低光谱背景,以锗作为内标元素,实现了试样中银、硼、锡的同时定量测定,方法应用于岩石、土壤等地质样品测试中并取得了满意的结果。     

云南省会泽县金红矿区土壤热释汞测量对比研究及找矿预测

本文通过对标准样品的重量和时间测试实验,在云南会泽县金红铅锌矿区已知剖面开展温度实验,找出土壤热释汞的最佳测试条件,从而排除影响该方法找矿预测的干扰因素,建立一套适合该区土壤热释汞找矿预测的标准方法。利用该方法实验结论,对该区土壤样品做了300℃和650℃两个温度的条件下的平面异常对比,结合该区地质背景分析验证300℃这个温度条件适合于该区土壤样品测试分析,并在此温度条件下对该区进行找矿预测评价。     

电感耦合等离子体质谱法测定黑土地样品中铅、铜、镉、镍元素

电感耦合等离子体质谱广泛应用于地质样品中的多种微量元素分析,而本文着重讲述了ICP-MS对黑土地样品中的铅,铜,镉,镍四种元素的分析和探讨,主要采用封闭压力酸溶法溶解黑土地土壤样品,以Rh单元素标准溶液作为内标和基体,匹配混标溶液作为标准进行样品测定,对有证标准样品和空白进行多次实验测试,测定结果表明能够达到相关测试要求,极大的节约了时间成本,也为黑土地中其他元素分析奠定了基础。     

低成熟生油岩中某些萜类化合物

本文报道了在低成熟生油岩抽提物中的萜类化合物近20种。文中列出了这些化合物的特征质量碎片离子、分子量、分子式及定名。     

High temperature infrared spectra of hydrous microcrystalline quartz

A series of in-situ high temperature infrared (IR) measurements of water in an agate sample and in a milky quartz has been conducted in order to understand the nature of water in silica at high temperatures (50–700?°C) and the dehydration behavior. IR absorption bands of water molecules trapped in the milky quartz showed a systematic decrease in intensities and a shift from 3425?cm^?1 at 50?°C toward 3590?cm^?1 at 700?°C without any loss of water. This indicates a change in IR absorption coefficients corresponding to different polymeric states of water at different temperatures. The broad 3430?cm^?1 band in the agate sample also showed a systematic decrease in IR intensity and a band shift toward higher frequency with increasing temperature (～700?°C). This indicates that the agate sample also contains fluid inclusion-like water. For this agate sample, a dehydration of loosely hydrogen-bonded molecular water occurred at lower temperatures (<200?°C). At higher temperatures (>400?°C), sharp bands around 3660 and 3725?cm^?1 (3740?cm^?1 at 50?°C) due to surface silanols, appeared. This indicates dehydration of H₂O molecules that are hydrogen bonded to surface silanols. SiOH species in the agate are divided into three groups, namely SiOH group located at structural defects, surface silanols hydrogen bonded to each other and free surface silanols. Former two dehydrate below 700?°C and the dehydration rate of the SiOH at structural defects is faster than the other. IR spectra show that SiOH species decrease continuously even after the dehydration of most of H₂O molecules. All these results provide realistic bases for the change in physicochemical states of different OH species in silica at high temperatures.     

微波诱导等离子体原子发射光谱法测定汞的研究

研究了以常压低功率氩微波诱导等离子体为激发源的原子发射光谱测定Hg的方法。采用超声雾化、水冷凝、浓H_2SO_4吸收去溶的进样方法,考察了微波前向功率、载气流速、KCl和NH_4Cl浓度、酸度等因素对Hg发射强度的影响。方法已用于试样分析。     

X射线荧光光谱法测定土壤样品中碳氮硫氯等31种组分

利用新型的ZSX Primus Ⅱ型X射线荧光光谱仪采用粉末压片法直接测定土壤样品中的C、N、S、Cl等31种元素。各元素分析晶体为N采用RX45，C采用RX61，Na、Mg采用RX25，C1、S、P采用Ge，Si、Al采用PET，其余元素均采用LiF200。结果表明，方法的检出限、精密度和准确度对绝大多数元素而言，均可满足多目标地球化学调查样品分析的质量要求：     

平阴县土壤地球化学基准值与背景值研究

平阴县土壤地球化学调查是按每1km^2采集1件表层样,4km^2组合成1件分析样,每4km2采集1件深层样,16km^2组合成1件分析样,分析测试Ag,As,Au,B,Ba,Be,Bi,Br,C,Cd,Ce,C1,Co,Cr,Cu,F等54元素或指标;统计了这些元素或指标的土壤地球化学基准值与背景值等参数;研究了区内土壤地球化学基准值、背景值与全国、黄河下游流域土壤及平原区、丘陵区土壤的差异;对比区内土壤地球化学基准值与背景值变化,认为区内大部分元素或指标在表层土壤中的含量继承了土壤母质,后期人类活动对其影响较小,但C,Cd,C1,Hg,P,N,S,Se,Corg等元素或指标在表层土壤中已明显富集,表明表生作用和人类活动等因素已对这些元素或指标的含量变化与分布分配产生明显影响。     

The CO2 absorption method as an alternative to benzene synthesis method forC dating

A fast and economical routine sample preparation system is described for direct counting of¹⁴C for hydrological purposes. The method employs commercially available CO₂ absorbers, such as Carbosorb, and liquid scintillation counters. The maximum error involved individual analyses is about ±4pmc (1 δ) on the Beckman counter and about ±2 pmc on the Quantulus counter with a resulting detection limit of 21,000–29,000 a for the Beckman LS7500 and 1220 Quantulus, respectively for a counting time of 1000 min. To avoid physical weighing procedures, an indirect method is presented to determine the grams of C absorbed in the counting solution by using the H-# quench monitor technique available in the Beckman liquid scintillation counters. On one sample preparation system at least five samples can be prepared per normal working day. The applicability of the CO₂-absorption method is discussed with reference to two field sites and with reference to comparisons with data obtained on the same samples measured with conventional techniques.     

X射线荧光光谱法同时测定土壤样品中碳氮等多元素

报道了采用粉末压片制样-X射线荧光光谱法测定土壤样品中C、N、S、Cl、Br、Hf、Mo、Sn、Se、Na、Mg、Al、Si、P、K、Ca、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ga、As、Rb、Sr、Y、Zr、Nb、Ba、La、Ce、U、Th、Pb等38种元素的分析方法。着重研究了C和N的分析条件、存在问题和注意事项。所拟方法的检出限，精密度和准确度大多数满足覆盖区多目标地球化学调查样品分析质量的要求。     

Are C1 chondrites chemically fractionated? a trace element study

Six C1 chondrite samples and a C2 xenolith from the Plainview H5 chondrite were analyzed by radiochemical neutron activation for the elements Ag, Au, Bi, Br, Cd, Ce, Cs, Eu, Ge, In, Ir, Lu, Nd, Ni, Os, Pd, Pt, Rb, Re, Sb, Se, Sn, Tb, Te, Tl, Yb, and Zn. The data were combined with 9 earlier analyses from this laboratory and examined for evidence of chemical fractionation in C1 chondrites.A number of elements (Br, Rb, Cs, Au, Re, Os, Ni, Pd, Sb, Bi, In, Te) show small but correlated variations. Those of the first 8 probably reflect hydrothermal alteration in the meteorite parent body, whereas those of Sb, Bi, In, and Te may at least in part involve nebular processes. Br and Au show systematic abundance differences from meteorite to meteorite, which suggests hydrothermal transport on a kilometer scale. The remaining elements vary from sample to sample, suggesting transport on a centimeter scale.There is no conclusive evidence for nebular fractionation affecting C1 's. Though C1 chondrites have lower $\text{Zr}\text{Hf}$ and $\text{Ir}\text{Re}$ ratios than do other chondrite classes, these ratios vary in other classes, suggesting that those classes rather than C1's are fractionated. Three fractionation-prone REE—Ce, Eu, and Yb have essentially the same relative abundances in C1's and all other chondrite classes, and hence apparently are not fractionated in C1's. We did not confirm the large Tb and Yb variations in C1's reported by other workers.We present revised mean C1 abundances for 35 elements, based on the new data and a critical selection of literature data. Changes are generally less than 10%, except for Br, Rb, Ag, Sb, Te, Au, and the REE.The Plainview C2 xenolith has normal trace element abundances, except for 3 elements falling appreciably above the C2 range: Rb, Cs, and Bi. Hydrothermal alteration may be the reason for all 3, though nebular fractionation remains a possibility for Bi.     

Uranium/thorium dating of Quaternary carbonates

Gustavsson, J. E. & Högberg, S. A. C.: Uranium/thorium dating of Quaternary carbonates. Boreas, Vol. 1, pp. 247–274. Oslo, 1st December, 1972.
The U/Th methods and particularly the theory of the ²³⁰Th-deficiency method are reviewed. The closed system question is discussed against the background of the growth and structure of the molluscan shells measured. The choice of the half-life value for ²³⁰Th, 75,200 years, is accounted for in a review of the five half-life determinations known to the authors. The measurement procedure starts with the mechanical and ultrasonic cleaning of the sample. Small portions are taken for X-ray analysis. The sample is then divided into two parts. One is treated chemically to separate the uraninium and the thorium, in order to determine the ratio between the activities of the uranium isotopes and to determine the content of ²²⁶Ra. The other part of the sample is used to make the total measurement on the uranium and thorium isotopes simultaneously from the same part of the sample without any chemical pretreatment.     

In-situ IR measurements of OH species in quartz at high temperatures

The nature of OH species in natural clear quartz was investigated by means of in-situ IR measurements over the temperature range –185 to 1000 °C. Reversible thermal behavior of OH species was examined for a sample pre-heated to 1000 °C for 1 hour. At room temperature, the IR spectrum of the quartz sample examined includes an intense absorption peak at 3379 cm^–1 which has been assigned to an OH stretching vibration associated with Al substituting for Si (OH(Al)). The major spectral changes of the OH(Al) bond involve a systematic shift of its peak position and a decrease in its integral absorbance with temperature. A quasi-linear increase of the peak position from –185 to 400 °C is interpreted to be due to the change in the vibrational frequency of OH(Al) with hydrogen bond (H bond) distance. At higher temperatures, the IR frequency shows only a slight change, indicating a small influence of the H bond. On the other hand, the gradual decrease of the integral absorbance of OH(Al) with temperature indicates a decrease of this defect’s molar absorptivity without any reduction in defect concentration. This is interpreted to result from a decrease in dipole moment of OH(Al) with temperature. A sudden shift of the vibrational frequency from 3396 to 3386 cm^–1 between 550 and 560 °C and a constant value of the integral absorbance from 535 to 570 °C were considered to be related to the change in H bond distance during the structural transformation of α-quartz to its β-form. The local environment of OH(Al) begins to change at temperatures below 570 °C, where the crystallographic α–β transition occurs. Received: 18 February 1998/ Accepted: 10 July 1998