On-line voltammetric monitoring of dissolved Cu and Ni in the Gulf of Cadiz, south-west Spain

Geochemical processes in estuarine and coastal waters often occur on temporally and spatially small scales, resulting in variability of metal speciation and dissolved concentrations. Thus, surveys, which are aimed to improve our understanding of metal behaviour in such systems, benefit from high-resolution, interactive sampling campaigns. The present paper discusses a high-resolution approach to coastal monitoring, with the application of an automated voltammetric metal analyser for on-line measurements of dissolved trace metals in the Gulf of Cadiz, south-west Spain. This coastal sea receives metal-rich inputs from a metalliferous mining area, mainly via the Huelva estuary. On-line measurements of dissolved Cu, Zn, Ni and Co were carried out on-board ship during an eight-day sampling campaign in the study area in June 1997. A pumping system operated continuously underway and provided sampled water from a depth of ca. 4 m. Total dissolved metal concentrations measured on-line in the Gulf of Cadiz ranged between <5 nM Cu (<3 nM Ni) ca. 50 km off-shore and 60–90 nM Cu (5–13 nM Ni) in the vicinity of the Huelva estuary. The survey revealed steep gradients and strong tidal variability in the dissolved metal plume extending from the Huelva estuary into the Gulf of Cadiz. Further on-line measurements were carried out with the automatic metal monitor from the bank of the Odiel estuary over a full tidal cycle, at dissolved metal concentrations in the μM range. The application confirmed the suitability of the automated metal monitor for coastal sampling, and demonstrated its adaptability to a wide range of environmental conditions in the dynamic waters of estuaries and coastal seas. The near-real time acquisition of dissolved metal concentrations at high resolution enabled an interactive sampling campaign and therefore the close investigation of tidal variability in the development of the Huelva estuary metal plume.

Stripping voltammetric determination of Pb(II) and Cd(II) based on the multiwalled carbon nanotubes-Nafion-bismuth modified glassy carbon electrodes

In this work, a new method for the simultaneous determination of Pb(II) and Cd(II) on the multiwalled carbon nanotubes (MWNT)-Nafion-bismuth modified glassy carbon electrode (GCE) using square-wave anodic stripping voltammetry has been studied. Scanning electron microscopy was used to investigate the characteristics of the MWNT-Nafion-bismuth modified GCE.

Nafion-graphene nanocomposite film as enhanced sensing platform for ultrasensitive determination of cadmium

In this work, an ultrasensitive platform for the detection of cadmium (Cd2+) combining the nafion-graphene nanocomposite film with differential pulse anodic stripping voltammetry (DPASV) analysis was presented. It is found that this sensing platform exhibits enhanced response to the determination of the Cd2+ and has been used to determine the Cd2+ in real sample with good recovery.

Solid-state electrochemiluminescence sensor based on the Nafion/poly(sodium 4-styrene sulfonate) composite film

An effective electrochemiluminescence (ECL) sensor based on Nafion/poly(sodium 4-styrene sulfonate) (PSS) composite film-modified ITO electrode was developed. The Nafion/PSS/Ru composite film was characterized by atomic force microscopy, UV-vis absorbance spectroscopy and electrochemical experiments. The Nafion/PSS composite film could effectively immobilize tris(2,2'-bipyridyl)ruthenium(II) (Ru(bpy)(3)(2+)) via ion-exchange and electrostatic interaction. The ECL behavior of Ru(bpy)(3)(2+) immobilized in Nafion/PSS composite film was investigated using tripropylamine (TPA) as an analyte. The detection limit (S/N = 3) for TPA at the Nafion/PSS/Ru composite-modified electrode was estimated to be 3.0 nM, which is 3 orders of magnitude lower than that obtained at the Nafion/Ru modified electrode. The Nafion/PSS/Ru composite film-modified indium tin oxide (ITO) electrode also exhibited good ECL stability. In addition, this kind of immobilization approach was simple, effective, and timesaving.

High-sensitivity determination of lead and cadmium based on the Nafion-graphene composite film

Graphene nanosheets, dispersed in Nafion (Nafion-G) solution, were used in combination with in situ plated bismuth film electrode for fabricating the enhanced electrochemical sensing platform to determine the lead (Pb2+) and cadmium (Cd2+) by differential pulse anodic stripping voltammetry (DPASV). The electrochemical properties of the composite film modified glassy carbon electrode were investigated. It is found that the prepared Nafion-G composite film not only exhibited improved sensitivity for the metal ion detections, but also alleviated the interferences due to the synergistic effect of graphene nanosheets and Nafion. The linear calibration curves ranged from 0.5 mu g L-1 to 50 mu g L-1 for Pb2+ and 1.5 mu g L-1 to 30 mu g L-1 for Cd2+. respectively. The detection limits (S/N = 3) were estimated to be around 0.02 mu g L-1 for Pb2+ and Cd2+. The practical application of the proposed method was verified in the water sample determination.

Evaluation of a sequential extraction for the speciation of thorium in soils from Baotou area, Inner Mongolia

Sequential extraction procedures were widely applied for speciation of radioactive elements. In this study, the sequential extraction procedure developed by Martinez-Aguirre was employed for quantification of different chemical forms of thorium in the soil. The total amount of thorium in contaminated soil was much higher by four-fold than the local background value. The soil properties affect the amount of thoriurn and distribution of fractions in contaminated soil. Results showed that the proportion of thorium in soils from Baotou was found as the residual fraction (F5 + F6) > absorbed fraction (F3), coprecipitated fraction (F4) > carbonates fraction (172) and exchangeable fraction (F1) that could be available to plants. The recovery, calculated by ratio of the sum of the six fractions to the pseudo-total content of thorium, was in the range from 96% to 110%. A comparison was carried out between the sequential extraction and the single extraction to evaluate the selectivity of the extractants. It was found that the amount of thorium of absorbed fraction (H) was higher in the single extraction than that estimated in the sequential extraction, possibly duo to transform of the labile form. While for non-residual fraction analysis, the single extraction scheme was a desirable alternative to the sequential extraction procedure.

长江口邻近海域缺氧区营养盐及痕量金属的生物地球化学过程研究

长江口邻近海域夏季底层水体存在世界上面积最大的缺氧带。这为研究河口区氧化还原敏感元素的生物地球化学过程提供了天然的实验场所。为了理解长江河口缺氧带存在的生物地球化学过程，本文以长江口邻近海域缺氧带上覆水体、沉积物及间隙水为研究对象，并对其营养盐及重金属进行研究，目的在于揭示长江口邻近海域缺氧带可能存在的生物地球化学过程，为理解长江河口区的物质循环提供科学证据。通过研究得出如下结论：（1）在水体中盐度是影响营养盐分布的主要因素，在高浊度带存在营养盐释放的现象；（2）底层水存在两种显著不同的生物地球化学过程：当盐度<33 PSU时，营养盐与AOU之间为负相关，影响底层海水营养盐分布的主要因素可能为流场；而当盐度>33 PSU时，营养盐与AOU之间存在正相关，影响营养盐分布的主要因素为颗粒有机质的矿化；（3）溶解态痕量金属存在保守型（Mo、U、Ni）和混合型(Fe、Mn、Cu、Pb、Zn)的分布规律，盐度、浮游生物及溶解氧都是影响溶解态痕量金属分布的重要因素；剔除浊度大于20 NTU的数据，分配系数与浊度为显著正相关；（4）间隙水Fe、Mn剖面表明，长江河口表层沉积物存在剧烈的Fe、Mn还原现象；成岩模型模拟结果显示间隙水Mn的模拟剖面与实际观测剖面吻合较好。间隙水U剖面显示，控制U分布的主要因素与Fe有关，但是其它因素如有机质含量对U、Mo的分布也有影响；（5）间隙水营养盐剖面显示近岸与远岸存在两种不同的生物地球化学过程：远岸海域，间隙水营养盐部面主要受早期成岩的控制；而在近岸海域其它过程如氨化及吸附可能是控制间隙水氮剖面分布的主要因素；模拟剖面与NH4+的实测剖面趋于一致，但是同时暗示表层沉积物受到生物扰动；通量计算结果显示，Si、N、P分别占浮游生物每日所需要营养盐数量的15%、10%及0.1%；（6）对痕量金属的黄铁矿化程度进行了分析，发现长江河口痕量金属的黄铁矿化程度异常低，黄铁矿不是影响痕量金属分布的主要因素；导致低黄铁矿化度的原因与长江河口高沉积速率、贫硫、低有机质有关。

Distribution of calcifying and silicifying phytoplankton in relation to environmental and biogeochemical parameters during the late stages of the 2005 North East Atlantic Spring Bloom

The late stage of the North East Atlantic (NEA) spring bloom was investigated during June 2005 along a transect section from 45 to 66 degrees N between 15 and 20 degrees W in order to characterize the contribution of siliceous and calcareous phytoplankton groups and describe their distribution in relation to environmental factors. We measured several biogeochemical parameters such as nutrients, surface trace metals, algal pigments, biogenic silica (BSi), particulate inorganic carbon (PIC) or calcium carbonate, particulate organic carbon, nitrogen and phosphorus (POC, PON and POP, respectively), as well as transparent exopolymer particles (TEP). Results were compared with other studies undertaken in this area since the JGOFS NABE program. Characteristics of the spring bloom generally agreed well with the accepted scenario for the development of the autotrophic community. The NEA seasonal diatom bloom was in the late stages when we sampled the area and diatoms were constrained to the northern part of our transect, over the Icelandic Basin (IB) and Icelandic Shelf (IS). Coccolithophores dominated the phytoplankton community, with a large distribution over the Rockall-Hatton Plateau (RHP) and IB. The Porcupine Abyssal Plain (PAP) region at the southern end of our transect was the region with the lowest biomass, as demonstrated by very low Chla concentrations and a community dominated by picophytoplankton. Early depletion of dissolved silicic acid (DSi) and increased stratification of the surface layer most likely triggered the end of the diatom bloom, leading to coccolithophore dominance. The chronic Si deficiency observed in the NEA could be linked to moderate Fe limitation, which increases the efficiency of the Si pump. TEP closely mirrored the distribution of both biogenic silica at depth and prymnesiophytes in the surface layer suggesting the sedimentation of the diatom bloom in the form of aggregates, but the relative contribution of diatoms and coccolithophores to carbon export in this area still needs to be resolved.

Environmental changes reflected by sedimentary geochemistry in recent hundred years of Jiaozhou Bay, North China

Sediment geochemical technique was employed to assess how the sediment records reflect the environmental changes of Jiaozhou Bay, a semi-enclosed bay adjacent to Qingdao, China. In the past hundred years, Jiaozhou Bay has been greatly impacted by human interventions. A dated core sediment by Pb-210 chronology was analyzed for trace metals including Li, Cd, Cr, Pb, Cu, Ni, Co, Zn together with C, N, P and BSi. Based on the research, the development of Jiaozhou Bay environment in the past hundred years can be divided into three stages: (1) before the 1980s characterized by relatively low sedimentation rate, weak heavy metal pollution and scarce eutrophication; (2) from the 1980s to 2000, accelerating in the 1990s, during which high sedimentation rates, polluted by heavy metals and the frequent occurrence of red tide; (3) after 2000, the period of the improvement of environment, the whole system has been meliorated including the heavy metal pollution and hypernutrification. (c) 2006 Elsevier Ltd. All rights reserved.

季节性氧湖泊微量金属元素的界面地球化学行为

沉积物表层几厘米范围经常呈现某些微量金属元素富集的现象，过去常笼统地认为这是工业革命以来人为污染不断加剧的证据。但近来的研究却证明强烈的早期成岩作用可以在一定程度上造成微量金属元素在沉积物中的再迁移现象，使得其环境记录失真。因此沉积物中元素分布记录不能完全反映对流域输入的物质组成特征。另外，在一定条件下，沉积物中部分金属元素也可再次向上覆水体释放，造成“二次污染”问题，严重威胁到湖泊／水库的水质安全，成为埋藏在湖泊深处的一颗“定时炸弹”。各种地球化学过程在沉积物一水界面附近造成的重金属元素的源／汇效应因此日益受到人们的重视。近年来贵州红枫湖水质季节性恶化事件频繁出现，作为贵阳市饮用水源的阿哈湖水质也开始出现季节性恶化趋势。紧迫的环境问题及重要的科学意义促使我们系统开展了红枫湖、啊哈湖沉积物一水界面微量金属的地球化学行为研究。两湖都是黔中地区人工水库，具有岩溶湖泊的共性，也具有明显的区别。红枫湖湖水具有典型的岩溶水化学特征，湖水中度富营养化；而啊哈湖受矿山废水的影响，同时由于近年的人工石灰投放等原因，造成该湖湖水具有极硬水、硫酸盐型水特征，矿化度达到600tng／L。我们对上述两湖进行了详细研究，获得了如下的研究成果：1．硫酸盐还原细菌（SRB）及铁还原细菌（DIRB）的计数直观地指示了有机质早期成岩过程中各电子受体依次利用的分带性：即硫还原（锰还原）叶铁还原。孔隙水中硫酸根及溶解铁分布与SRB和D工RB的分布吻合。沉积物孔柱的模拟实验、各类还原性微生物计数及与孔隙水中铁锰、硫酸根分布的综合分析证实了微生物的作用是厌氧环境中各种还原反应的不可缺少的因素，界面附近氧含量的变化是引起水质恶化的基本外因。模拟实验的结果还解释了铁、锰、硫在季节性缺氧湖泊中的循环机理。2．微生物计数及生物大分子分析证实了上层沉积物（0-10厘米）是微生物活跃最为强烈的区域，易降解有机质在此区域被降解。红枫湖沉积物有机质降解持续的深度较深〔达到10cm），而啊哈湖沉积物有机质降解持续深度较浅，仅为4厘米，这主要是由于两湖都是季节性厌氧型湖泊，红枫湖在缺氧季节，有机质厌氧降解所需的电子受体迅速消耗，使得缺氧季节该湖有机质降解速率相对缓慢；啊哈湖受到大量煤矿废水注入，水体及沉积物中硫酸根、铁锰含量异常高，并在厌氧季节里为微生物厌氧呼吸提供充足的电子受体，因而易降解部分有机质在表层迅速被氧化，而且该湖沉积速率相对较慢，有机质有相对充裕的时间在上层被降解，避免了被掩埋的命运。3．啊哈湖沉积物孔隙水及界面水δ13CDIC及DIC浓度的分析，显示啊哈湖沉积物产甲烷过程很弱或不明显。这主要是受到硫酸盐还原作用的抑制。从δ34SSO42-SO42-相关关系及硫酸盐还原菌分布特征，可以在深度上划分为两种还原过程及硫同位素分馏过程：慢速还原阶段（6厘米以下），硫同位素分馏程度较大，最大分馏达13．71％。分馏因子约为1.024-1.026之间；快速还原阶段（0-6厘米），硫同位素具有明显分馏，最大达到38‰，这与快速还原过程硫同位素分馏较小的规律相反，主要原因是由于表层同时出现有还原态硫的氧化反应．产生较负的δ34S-so41，δ34S-SO42--SO42-的变化反映出混合过程。通过研究我们进一步还推断，采样点沉积物下部还有煤矿硫源的输入。4．两湖沉积物中铁、锰、硫的还原作用发生位置都具有季节性沿沉积深度上下迁移的特性，部分微量金属元素扩散通量因此发生季节性变化。受沉积物中铁锰含量的控制，红枫湖沉积物一水界面铁锰循环作用比啊哈湖弱。啊哈湖锰含量很高，导致界面附近锰的循环剧烈且远强于铁的循环，并在一定程度上引起部分微量金属在沉积物上层强烈富集。5．通过红枫湖后五沉积物剖面研究，我们发现各种微量元素由于其自身不同的地球化学性质差异，早期成岩过程对其在沉积物中的垂直分布特征的改造程度是不同的。①锰具有明显的向上富集趋势，铁在沉积物中的分布特征的后期改造作用就比较弱。②钻、镍分布的后期改造程度与铁相似，从总量来看再迁移程度比较弱。③铜、锌在早期成岩过程中逐渐向沉积物中上部富集，这主要是与铜锌强烈的亲硫性引起的。钥的表层富集现象最为明显，沉积后再迁移效应显著。由其含量在上层沉积物中的两重峰值，可以指示界面剧烈的锰循环及界面下硫酸盐还原作用对它的联合控制。6．与红枫湖相比，啊哈湖沉积物金属元素再迁移特征有很大的不同：①通过部分微量金属元素地球化学相态分析，各相态微量金属分布主要服从其总量分布特征。②沉积物稀土配分模式明确指示了啊哈湖成湖基底的位置，即沉积物－水界面下18-19厘米以下。③通过Ti、Zr、ΣREE＋Y等的分析也显示了成湖前原始基底的存在位置，同时它们在沉积物中的含量变化特征还反映了该湖扩容后陆源输入的减少。④在沉积深度上铁锰及部分微量金属元素出现明显的分离现象。⑤通过相关性分析，Fe与Cu，U、Mn与Pb，C0，Ni，Cd，Zn等都存在很好的相关性，表明它们之间具有相似的界面地球化学行为。Fe型元素与Mn型元素分布差异的原因可以简约的概括为：锰的界面循环极为强烈，导致再迁移程度很高；而铁的循环相对较弱，又容易受到上层硫酸盐还原作用的抑制，因此再迁移程度不高。此外，由岩溶地区湖泊较强的酸中和能力及近年来的人为石灰投放，沉淀PH不同导致微量金属元素间发生分离，引起下游大坝处金属元素的输入差异。因此，啊哈湖大坝附近沉积物中微量金属元素的分布特征应受到沉积后再迁移和受 pH控制的煤矿废水输送差异联合制约。

高原湖泊微藻和微量金属元素的相互作用过程及实验模拟研究

微量金属元素的微藻生物地球化学主要通过研究微藻与微量金属元素的各种相互作用，在时空上了解微藻在微量金属元素的分布、迁移和富集等过程中所起的作用，以及由此引起的微藻本身的成分、结构、形态和功能在不同地球化学环境中的变异等。地球化学环境变化及由此产生的生态环境效应是目前研究的科学热点之一。工业革命以来，人为活动强烈地改变了地球表层的局部乃至全球的微量金属元素含量，对生物的正常生长乃至人类的健康构成了潜在的威胁。作为初级生产力，浮游藻类在水生生态系统中占有重要地位；它通过生物积累、光合作用及生物矿化，驱动着C、N、Si、P、O、，S、Fe等元素在水体内部的生物地球化学循环；微藻对环境变化敏感，能够很好的响应微量金属元素生物地球化学行为的变化。目前有关湖泊微量金属元素地球化学及浮游植物生态学的研究较多，但浮游植物和微量金属元素相互作用规律的系统研究较少，对湖泊微量金属元素复杂的生物地球化学行为的解释仍缺乏实验依据。本论文研究了高原湖泊阿哈湖、百花湖和红枫湖的微量金属元素和微藻的时空分布特征，探讨了两者之间的相互关系；研究了小球藻和衣藻对微量金属元素的生物吸收和生物吸附特征：研究了微量金属元素对微藻生理生化因子（生长速度和碳酸醉酶胞外酶）的影响；分析了微藻和微量金属元素的相互作用规律，为湖泊微量金属元素生物地球化学行为的解释提供科学依据。通过上述研究，获得了以下几点认识：1．阿哈湖、百花湖和红枫湖的微藻生物量在2002年出现了两个高峰，一个在春季，一个在秋季；这是水温、光照、营养源和捕食等多种因素综合作用的结果。百花湖和红枫湖的微藻以蓝藻和绿藻为主；阿哈湖的微藻春季以蓝藻和绿藻为主，秋季以硅藻为主。阿哈湖和红枫湖的叶绿素a含量在垂直方向随深度增加呈下降趋势，表层浮游藻类较多。2．阿哈湖、百花湖和红枫湖2002年过滤水中微量金属Co、Ni、Cu、zn、M。含量的月变化各不相同；其变化是微藻和降水等多种因素综合作用的结果。降水（酸雨）腐蚀湖泊流域的碳酸盐岩，其中的微量金属元素被溶解，随河流输入湖泊，影响了微量金属元素在湖水中的含量（如三个湖中的cu，阿哈湖中的Mo）。百花湖和红枫湖的蓝藻和绿藻的生物量变化与微量金属元素C。、Cu、zn、M。的含量变化正相关，可能是因为这些微量金属元素在某些程度上限制了蓝藻和绿藻的生长；阿哈湖的硅藻的生物量变化与微量金属元素的含量变化负相关，可能是由于硅藻对它们的富集造成了两者之间的负相关关系。浮游藻类通过吸附、吸收和富集溶解态微量金属元素，影响其在垂直方向的分布。溶解态微量金属元素在垂直方向的分布趋势并不完全相同，其垂直分布特征是本身的浓度大小、浮游藻类和湖底微生物等诸多因素共同作用的结果。3．微藻对微量金属元素生物吸附的平衡时间因对微藻处理方式的不同而不同。单离子体系和多离子体系中衣藻对同一微量金属的吸附情况不同，多离子体系中微量金属元素对吸附作用位点的相互竞争造成了这种差异。多离子体系中，死藻细胞对Cd、zn、cu、Co、Mn的吸附量的大小顺序与它们的原子量的大小顺序一致，这可能是在各种微量金属元素的相互竞争中，死的藻细胞优先选择原子量大的金属；活藻细胞对Cd、Fe、C。、Zn（Ni）的吸附量的大小顺序与它们的离子密度的大小顺序正好相反，这可能是由于活的藻细胞的生物调节作用使其优先选择离子密度小的金属。4．在单离子体系和多离子体系中，不论是活的藻细胞还是死的藻细胞，小球藻对各种微量金属的吸附量大于或相当于衣藻的吸附量；小球藻和衣藻对各种微量金属的吸附量一般随金属浓度的升高而增大。在单离子体系中，衣藻和小球藻对每种微量金属的生物吸收速度随浓度的变化趋势相似，一般是随金属浓度升高吸收速度先增加后减小，但增加和减小分界线处吸收速度对应的金属浓度大小各不相同；小球藻和衣藻对Mn、Fe、C。、Cu、zn（藻必需的微量金属营养元素）的吸收速度大于对Ni、Cd的吸收速度；这主要是因为同一藻类维持新陈代谢所需各种金属的量不同，对不同微量金属毒害的承受程度（生物调节能力）也不同；不同藻类对同一微量金属的需求量和毒害的承受程度也不相同。在单离子体系小球藻和衣藻对各种微量金属的吸附和吸收中，随着浓度的增加，吸收过程比吸附过程更快的达到饱和状态。5．各种微量金属对小球藻和衣藻生长的影响情况因金属种类和藻的种类的不同而不同。Cd·Cu、Ni、zn对小球藻和衣藻生长的毒害较大，而且对衣藻的影响比小球藻的影响大·随各种微量金属浓度的增加，小球藻和衣藻生长速度的变化趋势一般表现为先增大后减小，和它们对各种微量金属的吸收速度的变化趋势一致：可见吸收到藻细胞体内的微量金属的量和它们对细胞生长的影响有密切．的关系，藻细胞的生物调节在这个变化趋势中起了重要的作用。6．阿哈湖和红枫湖微藻碳酸醉酶胞外酶活性明显高于衣藻的CA。活性，主要是因为c入的活性与环境中HcO3一的浓度有关。cd、zn、cu和Pb对微藻c人的活性的抑制效应因金属浓度的不同而不同，而且抑制作用因微藻种类的不同而不同。微量金属元素对CA活性的影响主要通过三个途径：①．直接与CA这一含zn蛋白酶作用；②．间接影响藻细胞内CAe的新陈代谢：③．直接改变cA。的生物活性（例如Pb）。低浓度的Fe、Mn、Co 、Ni和cd刺激了衣藻碳酸配酶胞外酶（cAe）的活性，高浓度的各种金属抑制cAe的活性；cu和zn对衣藻cAe的抑制作用比其它金属离子的强。衣藻对Fe和Mn影响CAe的生物调节作用明显，其次是Co和Ni。7．微藻是影响高原湖泊微量金属元素地球化学行为的重要因素，影响情况因微藻种类而有所差异。微藻能强烈地改变环境中微量金属元素的含量，微量金属元素含量的变化也影响了微藻的生理生化功能。微藻和微量金属的相互作用因微藻和金属种类的不同而不同；这种种类差异性是造成微量金属元素生物地球化学行为复杂性的主要原因之一。

Species transformation of trace elements and their distribution prediction in dyestuff residue incineration

The release of heavy metals from the combustion of hazardous wastes is an environmental issue of increasing concern. The species transformation characteristics of toxic heavy metals and their distribution are considered to be a complex problem of mechanism. The behavior of hazardous dyestuff residue is investigated in a tubular furnace under the general condition of hazardous waste pyrolysis and gasfication. Data interpretation has been aided by parallel theoretical study based on a thermodynamic equilibrium model based on the principle of Gibbs free energy minimization. The results show that Ni, Zn, Mn, and Cr are more enriched in dyestuff residue incineration than other heavy metals (Hg, As, and Se) subjected to volatilization. The thermodynamic model calculation is used for explaining the experiment data at 800 degrees C and analyzing species transformation of heavy metals. These results of species transformation are used to predict the distribution and emission characteristics of trace elements. Although most trace element predictions are validated by the measurements, cautions are in order due to the complexity of incineration systems.

Determination of multiple trace elements in seawater using chelation ion chromatography and ICP-MS

An off-line chelation system combined with ICP-MS technique was developed for the quantitative determination of trace elements in seawater, namely V, Co, Ni, Cu, Zn, Mo, Cd, Pb, U and rare earth elements(REEs). The system was built based on an ion chromatography equipped with MetPac((R)) CC-I chelation columns which had a strong selective chelation to these target elements within a pH range 5.2-5.6. Acidified seawater samples and NH4Ac(2 mol/L) were blended to meet suitable pH before being injected into the chelation column, thus target elements were retained while alkali and alkaline metals were excluded. Then chelated elements were eluted by HNO3 (1 mol/L) and samples were collected for ICP-MS analysis. Varying the ratio of input( gen. 200 mL) to output( gen. 5 mL), the target elements which were concentrated as 40 times as their concentrations were far beyond instrumental quantification limits. At last, a certificated seawater CASS-4 was introduced and our detected values were in good agreement with those certified values.

A meso elastoplastic constitutive model for polycrystalline metals based on equivalent slip systems with latent hardening

A meso material model for polycrystalline metals is proposed, in which the tiny slip systems distributing randomly between crystal slices in micro-grains or on grain boundaries are replaced by macro equivalent slip systems determined by the work-conjugate principle. The elastoplastic constitutive equation of this model is formulated for the active hardening, latent hardening and Bauschinger effect to predict macro elastoplastic stress-strain responses of polycrystalline metals under complex loading conditions. The influence of the material property parameters on size and shape of the subsequent yield surfaces is numerically investigated to demonstrate the fundamental features of the proposed material model. The derived constitutive equation is proved accurate and efficient in numerical analysis. Compared with the self-consistent theories with crystal grains as their basic components, the present theory is much simpler in mathematical treatment.