地球化学基准与环境监测实验室分析指标对比与建议   总被引：1，自引：1，他引：0  

王学求  张勤  白金峰  姚文生  刘妹  刘雪敏  王玮 《岩矿测试》2020,39(1):1-14

全球高质量一致性地球化学基准数据和建立全球地球化学一张图平台,是持续监测全球环境变化的定量参照标尺。本文通过对中国、欧洲、美国和澳大利亚汞、镉、钨地球化学数据对比和中国同一实验室间隔15年两次分析数据对比发现:镉元素在不同实验室和同一实验室间隔15年分析的数据是一致的(相关系数0.96),汞元素一致性较差(相关系数0.74),钨元素不具有可比性(相关系数0.56)。镉元素分析结果的高度一致是因为分析方法相同的和检出限相近;汞元素一致性较差,特别是低含量汞存在显著差异,是因为分析方法不同和检出限不同;钨元素在不同实验室不具有可比性是因为实验室分析方法存在显著差异。环境变化量必须大于野外采样误差(REsmpl)和实验室重复样误差(RDlab)之和(RCenv>REsmpl+RDlab),才能确认观测点发生了环境显著变化。因此,必须将采样误差和实验室分析误差降到最低。本文提出实验室分析的6点基本要求:①原始样品过10目筛,使用无污染加工到粒度小于200目;②使用成熟的多方法分析71种元素+其他指标,其中主量组分以玻璃熔片X射线荧光光谱法(XRF)分析为主,微量元素以四酸分解样品,电感耦合等离子体质谱法(ICP-MS)和电感耦合等离子体发射光谱法(ICP-OES)为主要分析技术,配合其他特殊分析方法;③分析检出限必须低于地壳克拉克值,报出率不低于90%;④使用的标准物质必须具有涵盖所有分析元素的认定值;⑤实验室重复样分析相对误差含量小于3倍检出限RD≤40%,大于3倍检出限RD≤20%,主量元素、铁族元素和重金属元素重复样分析相对误差RD≤20%;⑥主量组分SiO2、Al2O3、Fe2O3、FeO、MnO、MgO、CaO、Na2O、K2O、TiO2、P2O5、H2O^+(结晶水)、有机碳、CO2、SO2等15项,或SiO2、Al2O3、Fe2O3、FeO、MnO、MgO、CaO、Na2O、K2O、TiO2、P2O5、LOI(烧失量)等12项加和为99.3%~100.7%。  相似文献   

电感耦合等离子体质谱法测定高锡地质样品中的痕量镉   总被引：1，自引：1，他引：0  

禹莲玲  郭斌  柳昭  赵昕  戴长文  彭君 《岩矿测试》2020,39(1):77-84

应用电感耦合等离子体质谱法(ICP-MS)测定地质样品中的痕量镉,存在多种质谱干扰,通常采用在线或离线方程进行校正,当样品中含锡较高时,采用传统固定系数校正方程,易导致测定结果有明显偏离,甚至结果出现负数。本文针对含高锡的地质样品,应用ICP-MS测定其中的镉,采用氢氟酸-高氯酸-硝酸敞开酸溶消解、硝酸浸提体系处理样品,通过测定~(111)Cd、~(113)Cd、~(114)Cd同位素,研究了干扰元素Sn、In、Zr、Mo对镉测定的影响。结果表明镉与干扰源浓度变化呈非简单的正相关性。①同质异位素Sn或In产生的干扰增值Δ(~(114)Cd/~(114)Sn或~(113)Cd/~(113)In)随干扰源浓度增大逐渐变大,~(114)Sn对~(114)Cd的干扰系数在0.0272～0.0222,~(113)In对~(113)Cd的干扰系数在0.0670～0.0412;②Zr和Mo在测定条件下形成氧化物和多原子复合离子物质对Cd均产生不同程度的质谱干扰。通过测定与样品中干扰源浓度相近的单一标准溶液产生的Cd干扰值,经在线修正干扰系数(γ),建立了精确的校正方程。该方法经标准物质验证,准确度高,相对标准偏差在6.57%～9.94%(n=7),方法检出限为0.03mg/kg,达到了地质分析检测要求,为高锡地质样品中的痕量镉分析提供了依据。  相似文献   

High‐Precision Cd Isotope Measurements of Soil and Rock Reference Materials by MC‐ICP‐MS with Double Spike Correction     

Meng‐Shu Liu  Qun Zhang  Yingnan Zhang  Zhaofeng Zhang  Fang Huang  Hui‐Min Yu 《Geostandards and Geoanalytical Research》2020,44(1):169-182

This study presents a high‐precision Cd isotope measurement method for soil and rock reference materials using MC‐ICP‐MS with double spike correction. The effects of molecular interferences (e.g., ¹⁰⁹Ag¹H⁺, ⁹⁴Zr¹⁶O⁺, ⁹⁴Mo¹⁶O⁺ and ⁷⁰Zn⁴⁰Ar⁺) and isobaric interferences (e.g., Pd, In and Sn) to Cd isotope measurements were quantitatively evaluated. When the measured solution has Ag/Cd ≤ 5, Zn/Cd ≤ 0.02, Mo/Cd ≤ 0.4, Zr/Cd ≤ 0.001, Pd/Cd ≤ 5 × 10^?5 and In/Cd ≤ 10^?3, the measured Cd isotope data were not significantly affected. The intermediate measurement precision of pure Cd solutions (BAM I012 Cd, Münster Cd and AAS Cd) was better than ± 0.05‰ (2s) for δ^114/110Cd. The δ^114/110Cd values of soil reference materials (NIST SRM 2709, 2709a, 2710, 2710a, 2711, 2711a and GSS‐1) relative to NIST SRM 3108 were in the range of ?0.251 to 0.632‰, the δ^114/110Cd values of rock reference materials (BCR‐2, BIR‐1, BHVO‐2, W‐2, AGV‐2, GSP‐2 and COQ‐1) varied from ?0.196‰ to 0.098‰, and that of the manganese nodule (NOD‐P‐1) was 0.163 ± 0.040‰ (2s, n = 8). The large variation in Cd isotopes in soils and igneous rocks indicates that they can be more widely used to study magmatic and supergene processes.  相似文献   

中国黄、渤海海水中溶解镉的形态研究          下载免费PDF全文

任艺君  李力  王小静  甄晓桐  刘季花 《海洋科学进展》2020,38(2):263-275

黄、渤海是我国重要的海洋经济渔业开发区域,海水中痕量金属的含量及其存在形态会对海洋环境、海洋渔业产生重要影响。随着近年我国痕量金属采集与分析测试技术的发展,数据的准确性有了新的提升。2016-06—07采集黄、渤海40个站位的海水样品,测定其溶解态金属Cd的总浓度,并应用电化学方法(阳极溶出伏安法)分析Cd存在形态。结果表明,渤海海水中的总溶解态Cd浓度是南黄海海水中的2~3倍,这可能与渤海海水停留时间较长,水深较浅,周边较多河流输入有关。20%~92%以上的溶解态Cd是以有机络合物形态存在,以自由离子态存在的Cd浓度不超过100 pmol/L,低于Cd对浮游生物的毒性阈值。渤海比黄海的金属配体浓度高出2倍以上,高值出现在黄河口周围海域,表明黄河水携带较多有机配体输入。推测我国近海有机配体来源可能包括陆源输入、沉积物再悬浮的解析过程以及藻类分泌。研究还表明,黄、渤海海水中溶解态Cd的有机配体络合常数较其他海域的稍高,这与我国近海废、污水排放的有机络合配体类型有关。  相似文献   

经济海藻羊栖菜（Sargassum fusiforme）幼体对镉胁迫的响应特性     

张甜甜  洪旻姮  吴明江  陈斌斌  马增岭 《海洋学报(英文版)》2020,39(10):147-154

镉(Cd)是水生生态环境中常见的重金属污染物,通常会抑制植物的生长,减少生物量,对植物产生毒害作用。为了研究羊栖菜幼苗对海水中Cd胁迫的抗氧化响应特性,我们在天然海水和Cd加富(100 μmol·L^-1)海水两种不同的Cd浓度下培养羊栖菜幼体。实验结果表明:Cd加富胁迫显著抑制了羊栖菜幼苗生长,使藻体颜色变暗。此外,高Cd处理显著降低了羊栖菜中的色素含量,生长速率,过氧化物酶(POD)活性,脱氢抗坏血酸(DHA)含量和谷胱甘肽还原酶(GR)活性。相反,高Cd处理显著促进了藻体内的Cd元素积累、对Cd₂⁺吸收速率,并增加了其暗呼吸/净光合速率比值(R_d/P_n),抗坏血酸(Vc)含量,可溶性蛋白质(SP)含量,且还原型谷胱甘肽(GSH)以及羊栖菜的超氧化物歧化酶(SOD)和过氧化氢酶(CAT)活性均显著增加,但对丙二醛(MDA)的影响不显著。虽然羊栖菜幼苗增加了其抗氧化活性并促进AsA-GSH循环,以产生H₂O₂并维持健康的新陈代谢,但高Cd胁迫显著限制了幼苗的光合作用,降低了其光合色素,抑制了其生长,并使其藻体颜色发生变化。海水中高浓度的Cd对羊栖菜幼苗具有毒性作用,并且极大地增加了这种海藻的食用风险。  相似文献   

Spatial and temporal distribution of cadmium and copper in water and zooplankton in the Bahía Blanca estuary,Argentina     

Melisa Daiana Fernández Severini  Sandra Elizabeth BottéMónica Susana Hoffmeyer  Jorge Eduardo Marcovecchio 《Estuarine, Coastal and Shelf Science》2009

Cadmium and copper in the dissolved and particulate phase and in zooplankton were determined in the Bahía Blanca estuary during six surveys from March to December 2005. Temperature, pH, salinity, dissolved oxygen, suspended particulate matter, particulate organic matter and chlorophyll-a were also considered. Dissolved Cd was below the detection limit (0.2 μg L⁻¹) for almost the entire study period whereas Cu concentrations (0.5–2.4 μg L⁻¹) indicated a continuous dissolved Cu input. Particulate Cd concentrations ranged from below the detection limit (<0.01) to 28.6 μg g⁻¹ d.w. while particulate Cu ranged from below the detection limit (<0.04) to 53.5 μg g⁻¹ d.w. Cd in mesozooplankton ranged from below the detection limit (<0.01) to 37.4 μg g⁻¹ d.w. Some of the Cd levels were higher than those reported for other aquatic ecosystems. Cu in the mesozooplankton ranged from 1.3 to 89.3 μg g⁻¹ d.w., values which were within the reported values or higher than other studies. The log of the partition coefficients (log (K_d)) of Cd was 0.04, while log (K_d) for Cu ranged from −0.39 to 2.79. These values were lower than both those calculated for other estuaries and the typical coefficients for marine environments. The log of the bioconcentration factor (log BCF) of Cd was 1.78, indicating that Cd concentration was higher in the zooplankton than in the dissolved phase. Log BCF of Cu ranged from 1.15 to 3. The logs of the biomagnification factors (log BMF) of Cd were low, with a range between −3.45 and 2.21 and those for Cu ranged from −0.1 to 3.35. Positive values indicate biomagnification while negative values indicate biodiminution. In general, no significant dissolved Cd concentration appeared to be present in the Bahía Blanca estuary and Cu values did not indicate a critical environmental status. The particulate phase seemed to be the major carrier for Cd and Cu and TPCu values were within the normal values for an anthropogenically stressed estuary but not for a strongly polluted system. This fraction was the most important metal source for the mesozooplankton. Moreover, the highest metal concentrations were in the mesozooplankton since most of the bioconcentration and biomagnification factors were positive, especially for Cu.  相似文献   

Effects of iron limitation on intracellular cadmium of cultured phytoplankton: Implications for surface dissolved cadmium to phosphate ratios     

Erin S. Lane  David M. Semeniuk  Robert F. Strzepek  Jay T. Cullen  Maria T. Maldonado   《Marine Chemistry》2009,115(3-4):155-162

This study compares intracellular Cd content (Cd:C) of cultured marine phytoplankton grown under various Fe levels, with estimated particulate Cd:P ratios derived from regression slopes of Cd versus PO₄³⁻ relationships from a global dataset. A 66-fold difference in Cd:C ratios was observed among the seven species grown under identical Fe concentrations, with oceanic diatoms having the highest Cd quotas and prymesiophytes the lowest. Interestingly, all species significantly increased their Cd:C ratios under Fe-limitation (on average 2-fold). The global data set also showed that the mean estimated Cd:P ratio of surface water particulates in HNLC (high nutrient low chlorophyll) regions were approximately 2-fold higher than non-HNLC regions. A sequence of events are proposed to explain high Cd:P ratios in HNLC waters. First, the seasonal relief from Fe-limitation in HNLC regions leads to blooms of large chain forming diatoms with high intrinsic Cd:P ratios. These large blooms may, in theory, deplete surface water CO₂ and Zn concentrations, which ultimately, would result in increased Cd uptake. Eventually these blooms will run out of Fe, which has been shown to further increase intercellular Cd via growth biodilution and increased Cd uptake through non-specific Fe(II) transporters. Ultimately, Fe-limited diatoms with enhanced Cd quotas will sink out of surface waters leading to pronounced regional differences in Cd:P ratios between HNLC and non-HNLC waters in the global ocean.  相似文献   

Behavior of Cu, Ni and Cd during nutrient depletion in a spring bloom in Funka Bay     

Isao Kudo  Katsuhiko Matsunaga 《Journal of Oceanography》1998,54(6):619-627

The concentrations of Cu, Ni and Cd were determined in Funka Bay during a spring phytoplankton bloom, consisting of diatoms. Just after the bloom, both dissolved Cd and nutrients were removed in the euphotic zone. However, the removal ratio of Cd to phosphate was very different from that in seawater. The removal of Cd took place at a Cd/phosphate ratio of 0.07×10⁻³, which was lower than in seawater before the bloom (0.25×10⁻³), leading to an increase in this ratio in seawater exceeding 0.7×10⁻³ at the end of the bloom. Elevated concentrations of Cd and phosphate were observed in the deeper layer after the bloom due to the decomposition of detrital materials produced in the bloom. The ratio of Cd/phosphate in the regeneration step was 0.24×10⁻³ which was different from the removal ratio of 0.07×10⁻³. These observations suggest that the high Cd/phosphate ratio in the regeneration would reflect a relatively high regeneration rate of Cd than that of phosphate. No significant decrease in Cu and Ni concentrations was observed during the development of the bloom, suggesting that biological removal of these metals was not so significant during the spring bloom. The concentrations of Cd, Cu and silicate in surface waters increased after the bloom with decreasing salinity due to the influence of a spring thaw.  相似文献   

Effect of salinity on heavy metal mobility and availability in intertidal sediments of the Scheldt estuary   总被引：8，自引：0，他引：8  

G. Du Laing  R. De Vos  B. Vandecasteele  E. Lesage  F.M.G. Tack  M.G. Verloo 《Estuarine, Coastal and Shelf Science》2008,77(4):589-602

The effect of the flood water salinity on the mobility of heavy metals was studied for intertidal sediments of the Scheldt estuary (Belgium). Soils and sediments of 4 sampling sites were flooded with water of different salinities (0.5, 2.5, and 5 g NaCl L⁻¹). Metal concentrations were monitored in pore water and surface water. To study the potential effects of flood water salinity on metal bioavailability, duckweed (Lemna minor) was grown in the surface water. The salinity was found to primarily enhance the mobility of Cd and its uptake by duckweed. Cadmium concentrations in pore water of soils and sediments and surrounding surface waters significantly exceeded sanitation thresholds and quality standards during flooding of initially oxidized sediments. Moreover, the effect was observed already at lower salinities of 0.5 g NaCl L⁻¹. This implies that risks related to Cd uptake by organisms and Cd leaching to ground water are relevant when constructing flooding areas in the brackish zones of estuaries. These risks can be reduced by inducing sulphide precipitation because Cd is then immobilised as sulphide and its mobility becomes independent of flood water salinity. This could be achieved by permanently flooding the polluted sediments, because sulphates are sufficiently available in the river water of the brackish part of the estuary.  相似文献   

Groundwater protection from cadmium contamination by permeable reactive barrier in Qian'an of Jilin,China     

Alkali Mohammed 《东北亚地学研究》2008,(4)

This research studies the reliability of an activated carbon permeable reactive barrier in removing cadmium from a contaminated shallow aquifer.Laboratory tests have been performed to characterize the equilibrium and kinetic adsorption properties of the activated carbon in cadmium-containing aqueous solutions.A 2D numerical model has been used to describe pollutant transport within a groundwater and the pollutant adsorption on the permeable reactive barrier(PRB).In particular,it has been considered the case...  相似文献