TDR测定土壤含水量的标定研究

探讨了TDR测定土壤含水量的原理,并对黑河上游阿柔试验样地取土样进行了土壤体积含水量测定的室内标定试验,得出相关性较好的TDR测定土壤体积含水量的关系式.结果表明:通过室内土样同填建立的,TDR测定的体积含水量与土壤实际含水量相关性很好,可以利用TDR精确的测定土壤含水量,为黑河遥感项目提供精确的地面土壤水分数据,为遥感反演和验证提供基础数据.所得到 的标定结果对于具有相同土质的黑河中游土壤具有参考价值.     

南疆铁门关市土壤pH的测定不确定度评定

本文按照NY/T 1121.2-2006土壤检测中土壤pH测定的实验方法对南疆铁门关土壤中pH测定,然而实验过程中会产生不可避免的不确定度,主要研究了测定的重复性、土样质量、水的体积、缓冲溶液和pH计所带来的不确定度,对比发现水体积和测定的重复性对土壤pH值测定的不确定度影响最大。因此,在测定时可通过使用高精度的量筒以及增加平行试样的次数来降低标准不确定度,以便能够提高实验测试结果的质量和可靠性。     

红外碳硫分析仪测定土壤样品中的碳和硫

应用高频一红外碳硫分析仪,进行了土壤样品中碳、硫的测定,用该仪器测定土壤标准物质中碳、硫的结果与标准值符合。碳和硫11次测定的RSD分别是〈3%和〈10%。     

电感耦合等离子体原子发射光谱法测定土壤中有效硫

采用电感耦合等离子体发射光谱法测定土壤中有效硫,浸提剂分别为：Ca（H2PO2）2-2mol／LHAc（中酸性土壤有效硫）,5mol／LNaHCO3（碱性土壤有效硫）？研究了ICP-AES对有效硫测定谱线的选择以及浸提温度、静置时间等对浸提结果的影响,酸性土壤滤液直接经ICP—AES测定,碱性土壤滤液经酸化后再测定。方法检出限分别为0．32mg／kg,通过对国家土壤有效态一级标准物质测试,测定结果基本一致;GBW07415、GBW07413标准物质11次测定的相对标准偏差（RSD）分别为3．66％、2．59％。     

应用高频红外碳硫仪测定农用地土壤样品中有机质含量

应用高频红外碳硫仪测定农用地土壤样品中的有机质,避免了传统方法中的试样液体转化环节,测定效率高,但存在土壤样品电磁感应低和基体影响较大等问题。本文通过实验优化了样品称样量、助熔剂铁和钨的添加量等测定条件,结果表明：当样品称样量为0.05g、助熔剂铁添加量为0.40g、钨添加量为1.50g时,有机质测定效果最佳。通过土壤标准物质进行验证,方法检出限为0.003%,相对标准偏差（RSD,n=7）小于4%,测定值与认定值的相对误差小于5%,且不同分析人员的测定结果间没有显著差异。采用本法与重铬酸钾容量法对甘肃省农用地土壤样品进行测定,两种方法测定值的绝对误差为-0.25%~0.28%,测定结果之间呈极显著线性正相关（R²=0.9736）,表明两种方法的一致性很好。本方法的检出限、精密度、准确度均满足农用地土壤样品有机质测定要求。     

电感耦合等离子体质谱法测定农业土壤样品中的有效钼

本文采用电感耦合等离子体质谱法,对农业地质土壤样品中有效钼测定进行了深入研究,并成功地建立了一种快速、准确、简便的测定农业地质土壤样品中有效钼的方法。该方法成功地解决了国家农业农村部标准分析方法 NY/T 1121.9—2012土壤检测第九部分:土壤有效钼的测定的局限性。本方法使用了五个国家标准物质,对方法进行了方法验证,十二次测定所得结果的准确度、精密度(平行测定结果允许相对相差≤15%)均符合农业农村部对农业土壤样品的分析测试标准要求。     

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。     

重铬酸钾保护氯化钙提取-原子荧光光谱法测定土壤中可提取态汞

为了更好地对土壤中可提取态汞进行测定,针对目前常用的氯化钙提取-原子荧光光谱法测定土壤中可提取态汞的方法存在测定结果偏低和重现性差的问题,对该方法进行优化。研究采用在氯化钙提取液提取可提取态汞的滤清液中加入适量的重铬酸钾作为保护剂,以保护提取液中的汞不被器壁、溶液胶体吸附,从而解决溶液放置一段时间后测定结果偏低和重现性差的问题,同时考察了测定酸度、硼氢化钾浓度、提取温度、提取液浓度、土液比、提取时间和重铬酸钾的加入量对测定结果的影响,并优选出最佳条件：测定酸度为10%(V/V)的盐酸、硼氢化钾的浓度为10 g/L、提取温度为20℃±2℃、提取液浓度为0.01 mol/L、土液比为1∶10、提取时间为60 min、重铬酸钾的加入体积为2.0 mL。试验结果表明,以本试验推荐的最佳条件测定土壤中的可提取态汞,精密度(RSD,n=7)小于5%,相对误差(RE)小于5%,适用于土壤中可提取态汞的测定。     

理论α系数法波长色散X射线荧光测定土壤中的重金属

近年来,重金属带来的土壤污染问题日益严重,快速、准确、有效地测定土壤中重金属种类及含量对土壤重金属污染评估及后续污染防治具有重要意义。本研究建立了波长色散X射线荧光光谱法同时测定土壤样品中铬、铅、锌、铜、钴、镍、锰、钒8种重金属元素含量的检测方法,通过经验法与理论α系数法的结合,优化了实验条件,方法线性良好,准确度与精密度较高,并且极大的简化了测定过程,提高了工作效率。将应用于土壤重金属含量初步评估,与ICP-MS的测定结果吻合度高。土壤监测结果表明,目标区土壤均符合二级土壤限量标准,该区土壤环境质量总体较好。而且该法减少了实验前处理过程中化学试剂的使用,避免了前处理过程中带来的环境污染问题,适用于规模较大的地质、农业、环境监测分析等生产单位进行土壤中重金属元素的快速测定。     

理论α系数法波长色散X射线荧光测定土壤中的重金属

近年来,重金属带来的土壤污染问题日益严重,快速、准确、有效地测定土壤中重金属种类及含量对土壤重金属污染评估及后续污染防治具有重要意义。本研究建立了波长色散X射线荧光光谱法同时测定土壤样品中铬、铅、锌、铜、钴、镍、锰、钒8种重金属元素含量的检测方法,通过经验法与理论α系数法的结合,优化了实验条件,方法线性良好,准确度与精密度较高,并且极大的简化了测定过程,提高了工作效率。将应用于土壤重金属含量初步评估,与ICP-MS的测定结果吻合度高。土壤监测结果表明,目标区土壤均符合二级土壤限量标准,该区土壤环境质量总体较好。而且该法减少了实验前处理过程中化学试剂的使用,避免了前处理过程中带来的环境污染问题,适用于规模较大的地质、农业、环境监测分析等生产单位进行土壤中重金属元素的快速测定。     

Analysis of raw soils and their re-suspended PM10 fractions: Characterisation of source profiles and enrichment factors

In this work, the inorganic chemical profiles of soil samples collected at different sites in the Salentum peninsula (Italy, Apulia region) are discussed. The samples were re-suspended in the laboratory, for PM10 sampling, using a ventilated wooden chamber and were then chemically analysed measuring the abundances of 17 elements. Different land use categories of soils (olive grove, arable land, vineyards, sand, and urban dust) were included in the 50 samples analysed: 45 collected in background areas and five collected in the urban area of Lecce. The objectives were to compare the chemical profiles of raw soil and re-suspended PM10 for different crustal sources and to estimate the potential improvements in the calculation of the enrichment factors of atmospheric PM10. The variability of elemental abundances in samples of the same category of soil collected in different zones was of the same order of magnitude as the differences observed between the various categories of soil. This allows the calculation of a weighted average composition of soil and urban dust and the corresponding weighted average composition of re-suspended PM10. In re-suspended PM10 from average background soil, all of the elements except Ca, Na, K and V have larger abundances with respect to raw soil. In urban dust, this is limited to Ca, V and Mg. The crustal enrichment factors (EFs) of atmospheric PM10 were evaluated by considering different reference elements and different reference tables. Results indicated that it is possible to apply a two-threshold (S₁ and S₂) scheme for the interpretation of EF, with thresholds derived from uncertainty in soil categories and from the choice of the reference element. A specific element is likely of crustal origin if EF < S₁ and likely of anthropogenic origin if EF > S₂. Between the two thresholds, the element can be considered of mixed origin. The thresholds vary according to the geological composition used in the evaluation of EF. If the average composition of local re-suspended soils is used, the thresholds are S₁ = 2 and S₂ = 4. If raw soil is used, the thresholds become S₁ = 5 and S₂ = 10. If the average upper-crust composition from literature data is used, the thresholds further increase to S₁ = 10 and S₂ = 20.     

蒸馏分离-电感耦合等离子体质谱法测定地球化学样品中痕量钌和锇

建立了蒸馏分离-电感耦合等离子体质谱法测定地球化学样品中痕量钌和锇的分析方法。进行了蒸馏温度和时间、氧化剂、吸收液等条件的选择,消除了等离子体质谱法测定钌和锇的干扰。样品用过氧化钠熔融,酸化后以高锰酸钾-过硫酸钾-氯化钠作为同时蒸馏钌和锇的氧化剂,采用20 mL 50 g/L水合肼溶液同时吸收从混合物中分离出来的痕量钌和锇,用电感耦合等离子体质谱法测定。方法的检出限Ru为0.020 ng/g,Os为0.015 ng/g;方法加标回收率Ru为94.0%~102.7%,Os为96.0%~102.4%;精密度为4.72%~9.58%(n=12)。方法经国家一级标准物质验证,钌和锇的测定结果与标准值相符。     

电感耦合等离子体发射光谱法同时测定地质样品中次量钨锡钼

研究了电感耦合等离子体发射光谱同时测定地质样品中次量钨、锡、钼的方法。为了避免基体干扰,采用氢氟酸低温分解试样,蒸干除硅,硅以四氟化硅的形式挥发除去。为了减小盐分,用少量过氧化钠熔融未被分解完全的试样残渣,热水提取,盐酸酸化,电感耦合等离子体发射光谱法同时测定钨、锡、钼。方法相对标准偏差(RSD,n=12)为钨10.80%,锡6.67%,钼8.33%。标准曲线线性浓度上限为:三氧化钨30.0 mg/L,锡40.0 mg/L,钼40.0 mg/L。方法经国家一级标准物质验证,分析结果与标准值相符。     

熔融制样-X射线荧光光谱法测定电气石中12种主次量元素

电气石是一类含硼的铝硅酸盐矿物,化学成分复杂、化学稳定性强,不易湿法分解,B_2O_3含量较高,导致其主次量元素的同时测定存在一定困难。本文采用熔融法制样,建立了X射线荧光光谱法测定电气石Na_2O、MgO、Al_2O_3、SiO_2、P_2O_5、K_2O、CaO、TiO_2、V_2O_5、Cr_2O_3、MnO、TFe_2O_3等主次量元素的分析方法。样品与四硼酸锂-偏硼酸锂-氟化锂(质量比为4.5∶1∶0.4)混合熔剂的稀释比例为1∶10,消除了粒度效应和矿物效应;在缺少电气石标准物质的情况下,选择土壤、水系沉积物及多种类型的地质标准物质绘制校准曲线,利用含量与电气石类似的标准物质验证准确度,测定结果的相对标准偏差小于4.2%。采用所建方法测定四种不同类型电气石实际样品,测定值与经典化学法基本吻合。本方法解决了电气石不易湿法分解和硼的干扰问题,测定结果准确可靠,与其他方法相比操作简便,分析周期短。     

Assessment of As and Cd contamination in topsoils of Northern Ghorveh (Western Iran): role of parent material, land use and soil properties

The aim of this study was to investigate the influences of land use, parent materials (rock types) and soil properties on total arsenic and cadmium concentrations in the agricultural soils. A total of 87 surface (0–20 cm) soil samples were collected from four types of land use: irrigated farming, rangeland, dry farming and orchard. The average concentrations of the analyzed elements in topsoil were 84.426 mg As/kg and 3.289 mg Cd/kg. In addition, the pH, organic matter (OM), cation exchange capacity (CEC), soil grain sizes and CaCO₃ were measured for each sample. The results indicated that land use had no significant effect on As and Cd concentrations. Our findings indicated that the Cd concentrations were influenced by bedrock composition, but for As there were no significant differences between various soil parent materials (bedrocks). Soil pollution was assessed on the basis of pollution index (PI), comprehensive pollution index (P _n ) and geoaccumulation index (I _geo). Calculated indices showed high-pollution levels for As and low- to moderate-pollution levels for Cd.     

四种酸体系对微波酸溶-电感耦合等离子体质谱法测定固体废物中16种金属元素含量的影响

微波酸溶消解方法是测定固体废物中金属元素最主要的前处理方法,消解时使用不同的酸体系对测定结果有较大的影响。本文以国家土壤标准样品、固体废物标准样品和固体废物实际样品为材料,比较了在硝酸-盐酸、硝酸-氢氟酸、硝酸-盐酸-双氧水、硝酸-盐酸-氢氟酸-双氧水4种酸体系下,16种金属元素测定结果的差异以及在硝酸-盐酸和硝酸-盐酸-氢氟酸-双氧水酸体系下各元素的精密度和准确度。研究表明:一些土壤基体中加入氢氟酸能使Mo和Sb的回收率提高40%左右,固体废物样品中只有Sb的回收率能提高33%~50%。对于含氢氟酸的酸消解体系,改变硝酸和盐酸的比例,其测定结果没有明显差异;对于元素含量相差悬殊的铬渣样品,由于空间电荷效应,高浓度的Cr对V的测定有抑制作用。从方法的准确度和精密度来看,硝酸-氢氟酸-盐酸-双氧水的消解效果最好。     

N-nitrodimethlyamine in natural and drinking water of high cancer incidence regions of Guangdong,China

The Guangdong province of China contains the most clearly described high-incidence of hepatocellular carcinoma (HCC) and nasopharyngeal carcinoma (NPC) areas in the world. The geographical heterogeneity of cancer incidence in the region suggests that many carcinogenic risk factors might be present in the regional geochemical environment. This paper presents the concentrations of a wide range of known carcinogens in two high cancer incidence areas in Guangdong and compared them to a low cancer incidence area in the same province. N-Nitrosamines, NO₃⁻, NO₂⁻, and ammonium were detected in groundwater, surface water, and drinking-water. The concentrations of the 7 trace metal and metalloid elements As, Cd, Ni, Cu, Pb, Zn, and Hg were determined in surface soil samples and all water samples. The results show that, compared with the guidelines or limit values for drinking-water quality in the world, the high cancer incidence areas have hazardous high levels of N-nitrodimethlyamine (NDMA) in all kinds of water. Oppositely, the low cancer incidence area has a safe low level of NDMA in water bodies. The levels of NO₃⁻, NO₂⁻, and ammonium in water have the same character, although they have different expression between the two high-risk areas. The distribution of the 7 tested trace elements in surface soil has no significant correlation with cancer incidence. On the other hand, high concentrations of carcinogenic N-Nitrosamines in drinking-water and natural water bodies were identified for the first time in the high NPC and HCC incidence area.     

电感耦合等离子体发射光谱法和火焰原子吸收光谱法连续测定化探样品中12个元素

建立了地质化探样品中不同含量和检出限要求的12个元素的连续测定方法。样品经一次取样,用盐酸-氢氟酸-硝酸-高氯酸溶样,电感耦合等离子体发射光谱法测定铜、铅、锌、钴、镍、镉、锶、钡、钒、锰后,加碘化钾-甲基异丁基甲酮萃取分离,火焰原子吸收光谱法测定银、镉。银、镉的相对标准偏差(RSD,n=12)分别为6.5%、4.7%。与现行分析方法相比,建立的方法灵敏度和精密度高、准确度好,降低了生产成本,缩短了检测时间,尤其适合大量化探样品的测定。     

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.     

土壤中重金属元素电感耦合等离子体质谱定量分析方法的研究

分别采用HNO3-HF、HNO3-HF-HCl和HNO3-HF-H2O2三种消解体系,通过微波和PTFE密封罐电热板对土壤标准物质进行前处理,采用电感耦合等离子体质谱(ICP-MS)对样品中的重金属元素Cr、Ni、Cu、Zn、As、Cd和Pb进行定量分析。探讨了前处理试剂(主要为HNO3、HCl和HF)以及土壤基体效应对Cr、Ni、Cu、Zn、As、Cd和Pb定量分析的影响。研究结果表明,前处理试剂对Cr、Ni、Cu、Zn、As、Cd和Pb的定量分析具有不同程度的影响;对于土壤基体,在三种消解体系下均可观察到基体抑制效应;采用PTFE密封罐电热板消解方法前处理,待测元素及相同元素不同同位素的方法空白和检出限均较低,效果整体优于微波消解法。特别是HNO3-HF-HCl消解体系,通过选用52Cr、60Ni、65Cu、66Zn、75As和206Pb等同位素,重金属元素Cr、Ni、Cu、Zn、As、Cd和Pb的测定值均能保证在标准值的允许误差范围内,可以满足大批量土壤样品中重金属元素同时定量分析的需要,为高效准确地开展土壤的风险评估以及为土壤的修复治理提供科学依据。