ICP-OES标准加入法准确测定海水中的硼

硼作为海水中的重要组分,其准确测定对海洋环境生物地球化学过程研究具有重要意义。海水中硼的常用测定方法具有前处理步骤繁琐、耗时长、样品易被污染、灵敏度低等缺点,不适于大批量海水样品的准确测定。为剔除海水高盐基体效应及干扰,本文运用电感耦合等离子体发射光谱法(ICP-OES),将海水样品进行稀释,采用标准加入法建立工作曲线,对海水中硼含量进行准确测定。正交实验显示,ICP-OES最佳工作条件为射频功率1400 W,雾化气流量0.7 L/min,观测高度14 mm,进样泵速1.5 m L/min。标准加入法标准曲线相关系数大于0.999,相对标准偏差为0.76%~1.27%,加标回收率为94.6%~101.8%,方法检出限为1.073μg/L。实际的海水样品分析表明,该方法可消除海水基体干扰,减少测定误差,并且前处理操作简单快速,化学试剂用量少,回收率高,精密度好,灵敏度高,可用于海水及其它高盐样品中硼含量的准确测定。     

等离子体发射光谱法中微量雾化器的应用

应用电感耦合等离子体发射光谱法测定环境或生物样品如悬浮颗粒物、浮游植物和沉积物提取物中金属元素时常面临试样较少的问题。在等离子体发射光谱仪上使用微量雾化器,利用金属元素标准溶液对仪器工作条件如雾化器压力、射频功率、输出泵速、辅助气流量进行了实验,获得最优工作条件为:雾化器压力0.2MPa,射频功率1 150W,输出泵速25r/min,辅助气流量0.5L·min-1。在该工作条件下,与常量雾化器的信号强度、背景值、方法检出限进行比较,信号强度略有降低,背景值明显降低,检出限与常量雾化器相当。应用微量雾化器对海洋沉积物提取样、浮游植物消解样、悬浮颗粒物消解样中的Al、Fe、Mg、Mn、Ti、Ba、Sr、Co、Cu、Ni进行了测定,结果与常量雾化器所测值进行了对比,发现无明显差异,且其背景值降低,减小了元素测定的背景干扰。样品消耗量仅为常量雾化器的1/3或更少,分析效率得以提高,是解决少量环境样品测试的有效方法。     

微量生物碳酸盐ICP-OES 元素分析中的仪器优化

为优化电感耦合等离子体发射光谱仪(ICP-OES)测试微量生物碳酸盐中元素含量的工作条件, 在Thermo-Fisher 公司生产的iCAP 6300 Radial 型ICP-OES 上, 对1 050 组仪器条件、32 种不同组成的标准溶液、36 个谱线对和两种仪器校正工作曲线进行了测试; 借助开源科学计算软件Scilab 数据插值和可视化技术对测试数据进行了比较分析。结果表明, 该仪器测试微量生物碳酸盐中Mg/Ca 和Sr/Ca 比值的最佳条件为: 雾化器, 0.1 mL/min 同心雾化器; 冷却气流量, 缺省设置12 L/min; 辅助气流量, 0.5L/min; 雾化气压力, 0.24 MPa; 蠕动泵速, 16 r/min; RF 功率, 1 000 W; 观察高度, 15 mm; 谱线, Ca373.690 nm, Mg 279.553 nm {121}, Sr 407.771 nm; 仪器校准工作曲线为强度-浓度工作曲线。     

塞曼石墨炉原子吸收法直接测定海水中的铜

本文选择酒石酸消除海水基体对铜信号的干扰,用塞曼石墨炉原子吸收法直接测定海水中的铜。从Cu的原子化曲线可知,加入酒石酸后,背景值减小,Cu原子吸收信号增强,且出现时间提前,表明酒石酸是有效的海水基体改进剂。用P.E.Z3030光谱仪测得双蒸水及海水中的元素Cu的特征质量(m。)分别为12.5pg及12.7pg;检测限分别为0.18μg/L和0.19μg/L,表明基体效应已消除,符合海洋监测要求。可用纯Cu标准溶液作校正曲线,以国家海洋局的两个标准海水样品中的Cu评定本法的准确度,相对偏差为0及-4.6%,与经典的经富集后的FAAS法的结果相比,相对偏差在3.0—6.5％范围内。用不同类型的光谱仪测定了30个海水样品,回收率在89—104％范围内。本法操作简便、快速。     

顺序扫描ICP—AES法测定海水中硼

利用ＩＣＰ—ＡＥＳ方法准确测定海水中元素硼，对射频功率、进样泵速、试样盐度、雾化压力、光谱干扰等多项因素进行考察，选出了最佳工作条件。方法检出限为３μｇ·ｋｇ－１，精度为０．２３％～０．４０％，回收率平均为１００．０４％，相对误差为０．５６％。     

元素分析仪快速测定海洋沉积物TOC和TN的条件优化

报道了在优化样品前处理、燃烧温度、最小加氧量和最佳称样量的基础上,综合构建优化了直接固体进样varioMACRO cube元素分析仪同时测定海洋沉积物样品中总有机碳(TOC)和总氮(TN)的条件,即准确称取20~30 mg沉积物样品用1 mol/L盐酸除去无机碳后,直接进样在燃烧管温度960℃,次级燃烧管温度830℃,还原管温度900℃,氦气压力0.12 MPa,流量600 mL/min,氧气压力0.20 MPa,加氧量22.5 mL仪器条件下,用标准曲线法峰面积获取TOC和TN浓度。结果表明,海洋沉积物中TOC和TN测定的检出限分别为0.0508%和0.0146%,回收率分别为97.7%~100.9%和97.2%~101.1%,对4个实际外海沉积物样测定总有机碳和总氮结果的相对标准偏差(RSD)为0.83%~3.06%和1.33%~3.49%(n=12)。该方法操作简便快速、灵敏度高,具有较好的精密度和准确度,可准确可靠地用于海洋沉积物中总有机碳和总氮含量的测定。     

石墨炉原子吸收法直接测定海洋沉积物和悬浮物中的镉、铅、铜

海洋沉积物和悬浮物样品基体组成十分复杂,而待测元素在样品中的含量也相差甚远,这给分析工作带来了一定的困难.石墨炉原子吸收法虽然具有灵敏度高,取样量少等优点,但存在着严重基体干扰[1-2].因此很多作者不得不采用费时的分离手段或标准加入法进行测定.本文应用自制简易石墨平台和基体改进技术以及峰面积测量相结合,直接测定了海洋沉积物和悬浮物中的镉、铅、铜.方法有效地消除了普遍石墨炉原子吸收测定法分析镉、铅时所遇到的基体干扰,使标准加入法曲线与标准工作曲线的斜率比接近1.0.方法简便快速,稳定可靠。     

海带中12 种元素ICP-OES 检测的三种前处理方法对比研究

运用电感耦合等离子体发射光谱法(Inductively Coupled Plasma-Optical Emission Spectrometry,ICP-OES)比较研究了干法灰化、湿法消解和微波消解3种前处理方法对海带样品中Se、Fe、Mn、Zn、Ca、Mg、P、As、Cd、Cr、Cu和Pb 12种元素含量测定的影响。结果表明,不同前处理方法对微量元素的测定结果会产生不同程度的影响。干法灰化对易挥发元素As等带来明显的负误差;湿法消解由于加入的消解液量大,对低含量的微量元素常带来较大的试剂空白;微波消解法相对于其他两种前处理方法适于样品的快速消解,具有操作简便、试剂用量少、操作误差小等优点,检测结果具备较高的准确度、精密度和回收率,对海带样品微波消解ICP-OES检测的相对标准偏差为0.29%~2.63%,加标回收率为87.3%~103.6%。微波消解是海带等海洋生物样品中微量元素测定较理想的前处理方法。     

秋季南黄海网采浮游生物的生物量谱

对2006年9月南黄海浮游生物网(孔径为70,160,505μm)采集样品内的浮游生物个体大小的粒径分布进行研究,确定各粒级大小的功能群组成,建立2006年秋季调查水域网采浮游生物的生物量谱,比较分析三个特征水域(黄海近岸、黄海中部及黄海和东海交汇区)的浮游生物生物量谱特征参数的异质性。结果表明:三种网采浮游生物粒级范围主要包括100 pg/个~70 ng/个的浮游植物和70 ng/个~62 mg/个的浮游动物。Sheldon型生物量谱为近似连续的波动曲线,标准型生物量谱为线型。总测区的标准生物量谱斜率和截距为-0.74和18.64,各个特征水域,黄海中部为-0.67和15.60、黄海近岸为-0.64和14.34、黄海、东海交汇区为-0.73和18.03。浮游动物种类多样性对标准生物量谱的特征参数具有较显著的影响。     

ICP-AES测定海洋生物体中13种元素的微波消解条件优化

报道了微波密闭消解正交试验条件优化电感耦合等离子体发射光谱法(ICP-AES),同时测定8种海洋生物体中硒、铁、锰、锌、钙、镁、锶、砷、镉、铬、铜、铅和镍等13种元素含量的实验结果。优化后的样品消解条件为加入的HNO3V:H O2 2V=6.0 mL:1.0 mL,第二步程序升温温度为170℃,消解时间20 min;测定标准曲线相关系数大于0.999,相对标准偏差为0.30%~2.55%,加标回收率为92.0%~104.8%,方法检出限为0.0010~0.0468μg/g。结果表明,优化后方法测定操作简便、具有高的灵敏度、准确度和精密度,且能多元素同时测定,适合于海洋生物样品中这些元素含量的准确测定,并可为评估海产品食用安全提供科学依据。     

能量色散X射线荧光光谱法测定海洋碎屑沉积物中28种元素

采用粉末样品压片制样,利用Epsilon3能量色散X射线荧光光谱仪(EDXRF)对我国边缘海碎屑沉积物中28种主量元素和微量元素进行测定。使用33个海洋沉积物、深海沉积物、水系沉积物、三角洲沉积物和岩石标样等国内外标准物质建立标准曲线,采用仪器软件的数学模式校正基体效应和元素间的谱线重叠效应。经国家标准物质检验,分析结果与标样值吻合;元素的检出限为0.02~124.14μg·g-1;精密度(RSD)均小于9%。对我国边缘海碎屑沉积物样品进行分析,其测定值与重量法、电感耦合等离子体光谱法和电感耦合等离子体质谱法的测定值基本一致。鉴于Epsilon3 EDXRF具有体积小、多元素同时快速分析、准确度高和精密度好的优点,可考虑作为船载仪器,在科考现场测定海洋沉积物的元素含量,对于及时指导海上工作、撰写航次报告具有重要作用。     

Determination of cosmogenic 32P and 33P in environmental samples

Understanding phosphorus dynamics in marine environment is of great importance, and appropriate tracers for phosphorus cycling in oceans are invaluable. In this study, two methods were developed for extraction, purification, and determination of naturally occurring 32P and 33P in rainwater, marine plankton and sediments using both a low-level beta counter (LBC) and an ultra-low-level liquid scintillation spectrometer (LSS). Blanks, chemical yields and counting efficiencies were quantified for both methods. The chemical purification of 32P and 33P separated by both procedures was validated by their decay curves. The absorber thickness of aluminum for LBC was assessed as 39.2 mg/cm 2 . 32P and 33P specific activities in some rain samples were determined by both methods and showed good consistent results. The advantage of the LSS over the LBC is apparent in its high counting efficiency and in determining samples with high concentration of stable phosphorus. However, when measuring environmental samples with low concentration of stable phosphorus, such as rainwater, both methods can be used and each has its distinct advantage.     

高压密闭消解-电感耦合等离子体光谱和质谱联合测定海洋地质样品中52种元素

An improved analytical method to determine the content of 52 major, minor and trace elements in marine geological samples, using a HF-HCl-HNO_3 acid system with a high-pressure closed digestion method(HPCD), is studied by an inductively coupled plasma optical emission spectrometry(ICP-OES) and an inductively coupled plasma mass spectrometry(ICP-MS). The operating parameters of the instruments are optimized, and the optimal analytical parameters are determined. The influences of optical spectrum and mass spectrum interferences, digestion methods and acid systems on the analytical results are investigated. The optimal spectral lines and isotopes are chosen, and internal standard element of rhodium is selected to compensate for matrix effects and analytical signals drifting. Compared with the methods of an electric heating plate digestion and a microwave digestion, a high-pressure closed digestion method is optimized with less acid, complete digestion,less damage for digestion process. The marine geological samples are dissolved completely by a HF-HCl-HNO_3 system, the relative error(RE) for the analytical results are all less than 6.0%. The method detection limits are 2–40μg/g by the ICP-OES, and 6–80 ng/g by ICP-MS. The methods are used to determine the marine sediment reference materials(GBW07309, GBW07311, GBW07313), rock reference materials(GBW07103, GBW07104,GBW07105), and cobalt-rich crust reference materials(GBW07337, GBW07338, GBW07339), the obtained analytical results are in agreement with the certified values, and both of the relative standard deviation(RSD) and the relative error(RE) are less than 6.0%. The analytical method meets the requirements for determining 52 elements contents of bulk marine geological samples.     

The trace element geochemistry of marine biogenic particulate matter

Plankton samples have been carefully collected from a variety of marine environments for major and trace-chemical analysis. The samples were collected and handled under the rigorous conditions necessary to prevent contamination of the trace elements. Immediately after collection, the samples were subjected to a series of physical and chemical leaching-decomposition experiments designed to identify the major and trace element composition of the biogenic particulate matter. Emphasis was placed on the determination of the trace element/major element ratios in the various biogenic phases important in biogeochemical cycling.The majority of the trace elements in the samples were directly associated with the non-skeletal organic phases of the plankton. These associations include a very labile fraction which was rapidly released into seawater immediately after collection and a more refractory component which involved specific metal-organic binding. Calcium carbonate and opal were not significant carriers for any of the trace elements studied. A refractory phase containing aluminum and iron in terrigenous ratios was present in all samples, even from remote pelagic environments. This non-biogenic carrier contributed insignificant amounts to the other trace elements studied.The plankton samples were collected from surface waters with a wide range in the dissolved trace element/nutrient ratios, however, the same elemental ratios in the bulk plankton samples were relatively constant in all these environments. The bulk compositions and the rapid release of the metals and nutrient elements (specifically phosphorus) from the plankton after collection were used to examine the systematics of depletions of the dissolved elements from surface waters. These elemental ratios were combined with known fluxes of the major biogenic materials to estimate the significance of the plankton in the vertical flux of the trace elements. In parallel with the major surface ocean cycles of carbon and nitrogen, significant fractions of the trace elements taken up by primary producers must be rapidly regenerated in order to explain the observed elemental compositions and fluxes.     

Determination of Fe,Ni, Cu,Zn, Cd and Pb in seawater by isotope dilution automatic solid-phase extraction—ICP-MS

A thorough understanding of the biogeochemical cycling of trace metals in the ocean is crucial because of the important role these elements play in regulating metabolism in marine biotas and thus, the climate. However, a precise and accurate analysis of trace metals in seawater is difficult because they are present at extremely low concentrations in a high salt matrix. In this study, we report an analytical method for the preconcentration and separation of six trace metals, Fe, Ni, Cu, Zn, Cd and Pb, in seawater using a seaFAST automatic solid-phase extraction device, analysis by a triple quadrupole collision/reaction technique with inductively coupled plasma mass spectrometry (ICP-MS), and quantification by the isotope dilution technique. A small volume (10 mL) of seawater sample was mixed with a multi-element isotope spike and subjected to seaFAST procedures. The preconcentrate solution was then analyzed using the optimized collision/reaction cell mode of ICP-MS, with NH₃ gas for Fe and Cd with a flow rate of 0.22 mL/min and He for Ni, Cu, Zn and Pb with a flow rate of 4.0 mL/min. The procedure blanks were 130 pmol/L, 3.0 pmol/L, 6.8 pmol/L, 37 pmol/L, 0.29 pmol/L and 0.42 pmol/L, for Fe, Ni, Cu, Zn, Cd and Pb, respectively. The method was validated using five reference materials (SLRs-6, SLEW-3, CASS-6, NASS-7 and GEOTRACE-GSC), and our results were consistent with the consensus values. The method was further validated by measuring full-water-column seawater samples from the subtropical Northwest Pacific Ocean, and our results demonstrated good oceanic consistency.     

防腐高效溶样罐-ICP-MS测定海洋生物体中微量元素

为明确海洋生物体中微量元素的含量状况，开发了一种适合海洋生物体中微量元素准确测定的分析方法。研究采用防腐高效溶样罐对GBW08517（海带Saccharina japonica）与GBW08571（贻贝Mytilus coruscus Goyld）2种国内海洋生物标准物质进行2种不同前处理方法的消解实验，然后应用电感耦合等离子质谱仪（ICP-MS）测试了包括稀土元素在内的33个微量元素。实验结果表明，除个别元素外，测试结果均与标准值相符合，且前处理方法1消解的生物样品测试结果更加准确和稳定。使用防腐高效溶样罐优化了生物样品处理的消解方法，能有效去除生物样品中的有机基体，使ICP-MS充分发挥优势。与以往的消解方法相比，在生物消解中效果优于微波消解，前处理方法1还具有易操作、处理效率高、低试剂消耗、安全性强、避免样品污染等优点。     

两个大洋多金属结核标准物质中27种元素的等离子体质谱法测定

从样品制备、仪器操作参数最佳化、内标补偿等几方面着手,利用两个标准物质(GSPN-2,GSPN-3)发展了大洋多金属结核中27种元素的等离子体质谱(ICP-MS)测定方法.这27种元素包括Ba,Ce,Co,Cu,Dy,Er,Eu,Gd,Ho,La,Li,Lu,Mo,Nd,Pr,Sb,Sc,Sm,Tb,Th,Tm,U,V,W,Y,Yb和Zn.各元素测定值与保证值相当吻合.对GSPN-2和GSPN-3,Ba,Sb,Sc,Y,Zn等5种元素可用外标校准法准确测定,其平均回收率(n=3)在91.4%～106.9%之间;可用内标(103Rh)校准法准确测定其他22种元素,其平均回收率(n=3)在89.4%～110.2%之间;各元素3次测定的相对标准偏差(RSD)为0.0%～11.0%.     

海水悬浮颗粒物中不同形态磷的测定

分别采用硫酸过硫酸钾作为氧化剂进行高压消解和用浓度为1 mol/dm³盐酸浸泡提取,然后用磷钼蓝分光光度法测定海水悬浮颗粒物、沉积物中的总磷和无机磷,用差减法得到有机磷。悬浮颗粒物总磷(PTP)和无机磷(PIP)质量浓度分别为(632.4～651.7)×10^-6和(436.6～452.6)×10^-6时,其相对标准偏差小于1.44%。悬浮颗粒物总磷、无机磷和有机磷的回收率分别为97.2%～101.3%,97.8%～100.4%和97.3%～102.3%。所建立的分析方法可用于海水、河口水悬浮颗粒物及沉积物中不同形态磷的测定。     

海洋沉积物孔隙水中痕量金属元素的测试分析方法

孔隙水是沉积物-海水界面链接沉积物颗粒和上覆水体的一个重要过渡相态,针对其研究可更好地了解痕量金属在固-液界面的早期成岩过程。近年来,针对孔隙水中痕量元素研究的方法较为匮乏,为此建立了一种分析测定海洋沉积物孔隙水中7种痕量金属元素(Mn、Cu、Zn、Ni、Cd、Co、Pb)的方法,该方法使用Nobias PA1树脂进行富集分离,再使用电感耦合等离子体质谱(ICP-MS)进行测试,可针对孔隙水中的痕量金属元素进行准确分析。通过实验结果发现该方法最优实验条件为: Nobias PA1树脂富集时的pH值为5.5~6.0,洗脱酸浓度为1.3 mol/L硝酸,体积为1 mL。同时,样品需进行紫外消解4 h以上以分解有机络合物,该消解步骤对Cu和Co这两种元素尤其重要。该方法通过加标回收获得Mn、Cu、Ni、Co和Pb的回收率在92%~100%, Zn和Cd的回收率分别为72%和82%; Mn、Cu、Zn、Ni的方法检出限范围为0.03~0.53 nmol/L, Cd、Co、Pb的方法检出限范围为2.66×10^-3~8.60×10^-3 nmol/L,满足孔隙水中痕量金属浓度的测试需求。同时,根据检出限计算的结果显示,孔隙水样品只需1 mL,即可应用该方法进行测试。应用该方法测试了一根采集于北黄海中部沉积物短柱的孔隙水样品,测试结果显示其垂相分布合理、较符合早期成岩过程规律。此研究为分析海洋沉积物孔隙水中痕量金属元素提供了一种准确而简便的方法。