电感耦合等离子体发射光谱法(ICP-OES)测定海洋浮游生物中总磷的方法优化

磷作为海洋浮游生物生长必需营养元素之一,其准确测定对海洋生态系统元素循环过程的研究具有重要意义。目前,文献中对于海洋浮游生物中总磷的测定方法报道不多。由于海洋浮游生物生存的高盐海洋环境,高盐基体的存在导致常规检测方法不能准确测定磷的含量。为剔除高盐基体效应及干扰,本文运用微波密闭消解预处理样品,采用电感耦合等离子体发射光谱法(ICP-OES)联合标准加入法建立工作曲线,同时结合样品的特异性,对ICP-OES分析谱线、射频功率、雾化气流速、观测高度、蠕动泵泵速和观测方式等仪器参数进行优化,构建确定了准确测定海洋浮游生物中总磷的优化条件和技术流程。实验结果显示, ICP-OES最佳工作条件为分析谱线P213.617 nm,射频功率1 300 W,雾化气流量0.8 L/min,观测高度14mm,进样泵速1.5 m L/min,观测方式轴向。标准加入法标准曲线相关系数大于0.999,相对标准偏差为1.36%~1.67%,加标回收率为92.6%~94.3%,方法检出限为0.010 mg/L,检测结果具有较高的准确度和精密度,可为海洋浮游生物及其它高基体生物样品中磷含量的准确测定提供技术支持。     

海水中硼的快速测定方法

海水、卤水及废水等样品中微量硼的测定方法很多,其中姜黄素法是测硼灵敏度最高的一种,现已被列入美国《水和废水标准检验法》第13版中。我们以姜黄素-分光光度法测定海水中微量硼时,在标准曲线中加入了与海水样相当的无硼人工海水,消除了阴阳离子的干扰,在半年多的海水中硼的间断性测定试验方面,获得了较满意的结果,其相对标准偏差为3.1％,测一批样品仅需4小时,因此,该法是测定海水中硼的快速准确的较好方法。     

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。     

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。     

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。     

基体改进效应石墨炉原子吸收法测定海水中钼

本文提出EDTA铵盐为基体改进剂.石墨炉原子吸收法直接测定海水中痕量钼的方法.EDTA铵盐有效地降低钼的原子化温度,增大测定钼的灵敏度,消除海水基体及微量元素干扰.用标准曲线法计算钼含量,检测限为0.69μg/l,相对标准偏差为2.5%,回收率为94.3%.     

离线固相萃取螯合富集分离-ICP-MS测定海水中的稀土元素

通过测定条件优化、方法比对等实验建立了一种固相萃取小柱离线螯合富集分离电感耦合等离子体质谱仪测定海水中稀土元素的方法。海水样品通过调节p H后,进入VAC ELUT SPS24 Agilent圆形固相萃取装置,其主要基体物质的去除率高于97%;萃取富集的优化条件是海水样品p H 4.0~7.0,海水进入萃取柱速率2 m L/min,硝酸洗脱液浓度为1 mol/L;方法对稀土元素的加标回收率为83%~108%,14种稀土元素的检出限为0.057~0.613 ng/L,RSD10%;该方法与氢氧化铁共沉淀法富集稀土元素比对测定结果一致,方法具有准确度与精密度高、操作简便快速等优点,可用于海水样品中稀土元素的定量精确测量。     

液相色谱要原子荧光联用测定海水中无机砷和有机砷

本文研究并建立了海水中测定砷形态的液相色谱—原子荧光法。进行了实验参数流动相浓度、pH、流速的优化。在优化的实验条件下，采用Hamilton PRP-X100分析柱在6 min内可以完成三价砷、甲基砷和五价砷3种形态的分离、检测。在载流5% HCl，还原剂2% KBH4、0.5% KOH，进样量100 μL的条件下，三价砷、甲基砷和五价砷的检出限分别为0.31 μg/L、0.52 μg/L和0.36 μg/L。在浓度2~80 μg/L范围内，3种砷形态均有良好的线性关系，相关系数均优于0.999。用本文所建立的方法进行了海水样品中无机砷和有机砷形态的测试，海水中三价砷、甲基砷的含量较低，五价砷稍高，说明海水中砷形态主要以五价砷存在，当加标量为5~10 μg/L，加标回收率在73%~104%之间。该方法操作前处理简单，灵敏度高、运行费用低廉，适用于海水中砷形态的测试。     

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。     

等离子质谱(ICP-MS)对高含量元素硫样品中微量元素分析的前处理方法比较

如何去除元素硫高含量样品的背景硫,是测定该类样品中微量元素成功的关键.通过分别对样品进行燃烧和升华两种前处理方法的研究对比,得出用升华的方法处理自然硫样品对于其微量元素的测定可靠性大,所测定微量元素回收率的优良率是68%,燃烧法处理后测定微量元素回收率的优良率是64%.而且前者优良回收率的范围是79.9%~120.5%,明显高于后者的优良回收率范围76.2%~98.0%.对于这样的结果,温度是主要的控制因素.燃烧法处理样品温度条件较难控制,升华法则可以较严格的控制温度,从而减少被测元素的散失,能得到较为理想的数据.     

Assessing the Validity of Seismo-Acoustic Predictor Equations for Obtaining Seabed and Sub-Surface Sediment Physical Properties

The interdependence between the seismo-acoustic properties of a marine sediment and its geotechnical/physical parameters has been known for many years, and it has been postulated that this should allow the extraction of geotechnical information from seismic data. Though in the literature many correlations have been published for the surficial layer, there is a lack of information for greater sediment depths. In this article, a desktop study on a synthetic seafloor model illustrates how the application of published near-surface prediction equations to subsurface sediments (up to several tens of meters burial depth) can lead to spurious predictions. To test this further, acoustic and geotechnical properties were measured on a number of sediment core samples, some of which were subjected to loading in acoustically-equipped consolidation cells (oedometers) to simulate greater burial depth conditions. For low effective pressures (representing small burial depths extending to around 10 meters subsurface), the general applicability of established relationships was confirmed: the prediction of porosity, bulk density, and mean grain size from acoustic velocity and impedance appears generally possible for the investigated sedimentary environments. As effective pressure increases through, the observed relationships deviate more and more from the established ones for the near-surface area. For the samples tested in this study, in some instances increasing pressure even resulted in decreasing velocities. There are several possible explanations for this abnormal behavior, including the presence of gas, overconsolidation, or bimodal grain size distribution. The results indicate that an appropriate depth correction must be introduced into the published prediction equations in order to obtain reliable estimates of physical sediment properties for greater subsurface depths.     

海上大直径钢管桩打桩过程中桩周土强度弱化研究

海上大直径钢管桩打桩过程中,桩周土体受到强烈扰动而发生强度弱化,掌握桩周土体强度弱化规律对于准确预测打桩过程、保证工程安全具有重要意义。为研究土体强度弱化规律,开展了环剪试验模拟打桩对桩周土体的扰动,测试土体强度随剪切速率的变化规律,建立了描述土体强度弱化规律的拟合公式,引入到打桩分析软件中。研究结果表明：土体的强度折减程度不仅与土体本身的性质有关还受到土体的埋深和剪切速率的影响,埋深越深土体强度折减程度越低,剪切速率越高土体强度折减越高,在打桩分析中可采用这里推荐的线性折减方法来模拟不同深度处土体强度的折减规律。     

Interannual Sea Level Variations and Annual Tides in the Northwestern Pacific

Specific properties of the interannual sea level variations and annual tides in the Northwestern Pacific were studied. Several tide stations were monitored. The monthly mean sea level for the year of 1995 was analyzed at each tide station. A seismic event in 1995, some tectonic activity around the subject area, and the Kuroshio (the oceanic western boundary current) may possibly contaminate results which would have occurred from the astronomical annual tide alone.     

Phylogenetic diversity and phenotypic characterization of cultivable bacterioplankton isolated from polar oceans

A set of 27 marine planktonic bacteria isolated from the polar regions was characterized by 16S rDNA sequencing and physiological and biochemical testing. More than half of these bacteria were positive for caseinase, gelatinase and 13-glucosidase, and could utilize glucose, maltose or malic acid as carbon source for cell growth. Twelve isolates expressed nitrate reduction activities. Except for one antarctic isolate BSwlO175 belonging to Actinobacteria phylum, these isolates were classified as γ-Proteobacteria, suggesting that γ-Proteobacteria dominated in cultivable marine bacterioplankton at both poles. Genus Pseudoalteromonas was the predominant group in the Chukchi Sea and the Bering Sea, and genus ShewaneUa dominated in cultivable bacterioplankton in the Prydz Bay. With sequence similarities above 97%, genus Psychrobacter was found at both poles. These 27 isolates were psychrotolerant, and significant 16S rDNA sequence similarities were found not only between arctic and antarctic marine bacteria （ 〉 99% ）, but also between polar marine bacteria and bacteria from other aquatic environments （ ≥ 98.8% ）, including temperate ocean, deep sea, pond and lake, suggesting that in the polar oceans less temperature-sensitive bacteria may be cosmopolitan and have a bipolar, even global, distribution at the species level.     

Flow Cytometric Analysis of Coastal Lagoon Bacterioplankton and Picophytoplankton: Fixation and Storage Effects

The effect of different fixation and storage protocols on the flow cytometric (FCM) simultaneous analysis of bacterioplankton and phytoplankton in coastal seawater samples (Mediterranean coastal lagoons) was investigated. FCM measurements (cell number, fluorescence and scatter characteristics) were obtained through DAPI staining. Three fixatives [glutaraldehyde (GA), formaldehyde (FA) and paraformaldehyde (PFA)] and two storage (3 months duration) methods (5 °C and −196 °C) were tested. Two dominant populations were detected in studied samples: bacteria and eukaryotic picophytoplankton. Adding fixatives (2% final concentration) appears necessary to obtain FCM exhaustive counts of all the bacteria and phytoplanktonic cells. This was related to the permeation effect of fixatives which allowed a better DAPI staining of the cells. Maximum fluorescence, i.e. optimal staining of the cells was obtained with FA or PFA, and significant lower fluorescences with GA. Fixed samples stored at 5 °C induced rapid cell loss. Only storage in liquid nitrogen of samples fixed with FA or PFA, allows mid-term (≥4 months) preservation of bacteria or picophytoplankton cell numbers, and limited evolution of DAPI-induced fluorescence and scatter characteristics.     

Estimation of Sediment Properties during Benthic Impact Experiments

Sediment properties, such as water content and density, have been used to estimate the dry and wet weights, as well as the volume of sediment recovered and discharged, during benthic impact experiments conducted in the Pacific and Indian Oceans. The estimates show that the weights of dry (355-1332 t) and wet sediment (1651-4888 t) recovered during the experiments, are not only a function of the total duration and distance covered during the experiment, but also depend on water content and density of the sediment. Estimation of dry sediment and its volumetric ratio in the discharge, are key parameters for calculating the discharged volume. The estimated volume of wet sediment recovered (1427-4049 m 3 ) as well as discharged (2693-6951 m 3 ) during the experiments, provide important inputs to evaluate the sediment resettlement and migration. Using these estimates, the average depth of excavation on the seafloor, can also been calculated. However, the stages of sediment recovery and discharge are expressed differently in some of the experiments. In order to standardize these, different stages have been identified, and definitions of certain terms have been suggested, for use in the future. The methods of calculating different properties, as well as weight and volume of discharged sediment are described in the paper for use in other applications concerning deep-sea discharges.     

A Tidal Flow Model for the Gulf of Kachchh, India

A vertically integrated model has been used to study the tidal circulation and currents in the Gulf of Kachchh along the west coast of India. The model is fully nonlinear and uses a semiexplicit finite difference scheme to solve the basic hydrodynamic equations on a staggered grid. The model is forced by prescribing the tides along the open boundary of the model domain. The flow is simulated both with and without the presence of the proposed tidal barrage across the Hansthal Creek in the Gulf of Kachchh. The results show a considerable change in the behavior of the tidal flow in the presence of the barrage.