Spatial distribution and behavior of dissolved selenium speciation in the South China Sea and Malacca Straits during spring inter-monsoon period

Selenium(Se) has been recognized as a key trace element that is associated with growth of primary producers in oceans. During March and May 2018, surface water(67 samples) was collected and measured by HG-ICP-MS to investigate the distribution and behavior of selenite [Se(IV)], selenate [Se(VI)] and dissolved organic selenides(DOSe) concentrations in the Zhujiang River Estuary(ZRE), South China Sea(SCS) and Malacca Straits(MS). It showed that Se(IV)(0.14–3.44 nmol/L) was the dominant chemical species in the ZRE, related to intensive manufacture in the watershed; while the major species shifted to DOSe(0.05–0.79 nmol/L) in the MS, associated with the wide coverage of peatland and intensive agriculture activities in the Malaysian Peninsula. The SCS was identified as the northern and southern sections(NSCS and SSCS) based on the variations of surface circulation.The insignificant variation of Se(IV) in the NSCS and SSCS was obtained in March, potentially resulting from the high chemical activity and related preferential assimilation by phytoplankton communities. Contrastively, the lower DOSe concentrations in the SSCS likely resulted from higher primary production and utilization during March. During May, the concentration of Se(IV) remained low in the NSCS and SSCS, while DOSe concentrations increased notably in the SSCS, likely due to the impact of terrestrial inputs from surface current reversal and subsequent accumulation. On a global scale, DOSe is the dominant Se species in tropical oceans, while Se(IV) and Se(VI) are major fractions in high-latitude oceans, resulting from changes in predominated phytoplankton and related biological assimilation.     

基于水淘选分级的长江口及邻近海域表层沉积物中磷的形态分布和迁移转化

磷是一种重要的生源要素,在河口、边缘海的初级生产中发挥重要作用,了解沉积物中磷的形态分布和迁移转化有助于深入了解该区域生态系统动力学。于2013年3月在长江口及邻近海域采集了表层沉积物样品,利用水淘选方法对沉积物进行了分级,并采用化学连续提取法分析了未分级和分级沉积物样品中的6种磷形态含量:可交换态磷、活性有机磷、铁结合态磷、自生磷灰石磷、碎屑磷和难分解有机磷,讨论了该区域沉积物中磷的形态分布、选择性输运过程和迁移转化。沉积物中总磷含量在14.0~18.4 μmol/g,其中碎屑磷是其主要成分,占54.5%,其次是有机磷和难分解有机磷,分别占到15.1%和13.1%。不同粒级沉积物中磷形态含量不同,可交换态磷、活性有机磷、铁结合态磷、自生磷灰石磷和难分解有机磷随粒级增加含量逐渐降低,而碎屑磷主要集中在粗粒级（大于32 μm）沉积物中。基于各粒级磷形态的质量分布,发现小于32 μm粒级的沉积物中各磷形态含量从长江口向浙闽沿岸逐渐增加,向外海方向逐渐减小,而大于32 μm沉积物的变化趋势与此相反,体现了不同形态磷的选择性输运。随粒径增大,总有机碳对有机磷比值（TOC/Or-P）先降低后升高,在大粒级沉积物中,TOC/Or-P比值较高主要是因为陆源有机碳贡献较高,而在小粒级沉积物中,主要是由于有机磷的迁移和转化更为活跃,体现了细颗粒物中有机磷相对有机碳的优先分解。本研究表明,从分级的角度可以对河口、边缘海的磷循环有一个更全面的认识。     

泥蚶(Tegillarca granosa)重组铁蛋白富集重金属离子的特性及化学传感器的研究

利用泥蚶(Tegillarca granosa)铁蛋白原核表达工程菌获得的重组铁蛋白,通过圆二色光谱分析蛋白二级结构,扫描电镜和电感耦合等离子质谱研究重组铁蛋白富集Fe~(2+)、Mn~(2+)、Cd~(2+)、Cr~(3+)、Hg~(2+)、Pb~(2+)和As~(3+)等7种重金属离子的特性,同时探索利用重组铁蛋白修饰丝网印刷电极,设计和制备重组铁蛋白检测Pb~(2+)和Cd~(2+)浓度的电化学生物传感器。结果表明复性成功的铁蛋白多为完整的?-螺旋结构,而复性不成功的蛋白聚集体则多为无规卷曲。重组铁蛋白的直径和形态与富集的离子种类有关。泥蚶铁蛋白对单一金属离子Fe~(2+)和Mn~(2+)的富集凸显优势。对两种混合金属离子的富集大多表现为竞争关系。但重组铁蛋白对Hg~(2+)和As~(3+)混合组的富集量明显高于单一金属离子组的富集量,对Hg~(2+)和As~(3+)混合组的富集表现出协同促进作用。重组铁蛋白传感器对Pb~(2+)和Cd~(2+)溶液的最低检测限为10μg/L。     

牛角塘伴生型镉矿床特殊的成矿环境

牛角塘伴生型镉矿床镉的富集程度高,比克拉克值高4~5个数量级,比工业品位高十几倍至上百倍。早寒武世清虚洞期牛角塘地区处于台缘滩丘环境,在清虚洞组中上部形成了藻丘建造,发育了含藻类、藻球粒、藻鲕粒、核形石和生物碎屑的白云岩,是该矿床最主要的容矿岩性单元。矿体普遍呈似层状、透镜状和脉状产出,矿体产状与容矿围岩的产状基本一致,矿体的分布受清虚洞组藻丘建造以及有利岩性组合的联合控制,具明显的层控、相控、岩控的特点。藻丘建造还可能提供了部分矿源。镉的超常富集、成矿与麻江古油藏的成藏演化具有一定的关系:一是牛角塘矿床成矿年龄为433~510 Ma,即加里东运动的中晚期,而加里东运动中晚期是麻江古油藏的油气活动时期,麻江古油藏的早期演化阶段与牛角塘镉矿的成矿期大体是重合的,成藏应略早于成矿,成矿是在古油藏液态烃仍然存在的情况下进行的,且成矿期有可能一直延伸至油藏被破坏以后;二是油藏流体为成矿提供具还原性质的成矿流体和部分硫源。特殊的岩相古地理环境和古油藏为牛角塘矿床镉的富集和成矿提供了有利条件。     

土壤重金属连续提取方法的优化

重金属在污染土壤中的形态分布决定着重金属的迁移性和危害的程度。土壤重金属形态分析应用最多的是Tessier和BCR连续提取法。Tessier和BCR连续提取法没有考虑土壤样品的特征。美国环保署危险废物浸出毒性鉴别标准法虽然考虑土壤pH值,但没有划分形态。采集不同pH土样,结合Tessier、BCR和毒性浸出鉴别方法的特征,优化出针对不同pH值土壤的连续提取方法,将土壤中重金属划分为活性态、次生碳酸盐结合态、次稳定态和稳定态。用优化的连续提取方法对土样进行连续提取,重金属回收率为85%~115%。优化连续提取方法的结果与Tessier和BCR结果对比显示优化连续提取方法克服了Tessier连续提取法对非石灰质土壤提取过量BCR连续提取法对石灰质土壤提取不足的缺点。优化后的连续提取方法数据稳定可靠,可作为重金属形态分析方法使用。     

Source speciation resolving hydrochemical complexity of coastal aquifers

There is a growing concern of seawater intrusion to freshwater aquifers due to groundwater overexploitation in the eastern coastal belt of Southern India. The problem becomes complex in the regions where industrial effluents are also contaminating the freshwater aquifers. In order to understand the hydrochemical complexity of the system, topographic elevation, static water level measurements, major ion chemistry, ionic cross plots, water type contours and factor analysis were applied for 144 groundwater samples of shallow and deep sources from Quaternary and Tertiary coastal aquifers, located within the industrial zone of 25 km² area near Cuddalore, Southern India. The ionic cross plots indicates dissolution of halite minerals from marine sources and seawater mixing into inland aquifers up to the level of 9.3%. The factor analysis explains three significant factors totaling 86.3% of cumulative sample variance which includes varying contribution from marine, industrial effluent and freshwater sources.     

ANC,BNC and mobilization of Cr from polluted sediments in function of pH changes

During the manufacturing of chromate salts (1972–1992) large quantities of Chromite Ore Processing Residue (COPR) were released into a decantation pond east of the former chemical plant of Porto-Romano (Durres, Albania), giving rise to yellow colored pond sediments. These Cr(VI) bearing sediments were deposited upon Quaternary silty-clay lagoonal sediments rich in iron oxides and organic matter. The pH values in these lagoonal sediments vary around 6.6, while in the pond sediments, it is mainly acidic (due to the presence of the sulfur stock piles in the area and the release of the H₂SO₄ from the activity of the former chemical plant), varying between 1.4 and 3.8. Continuous leaching of the COPR waste resulted in yellow-colored surface water runoff. The prediction of pH changes in the different types of sediments based upon acid/base neutralizing capacity (ANC/BNC) jointly with the quantitative data on release of heavy metals and especially Cr is considered an important advantage of the pH_stat leaching test if compared to conventional leaching procedures. Thus, factors controlling the leaching of Cr(VI), Cr(III), Ca, Al, Fe, Mg from the COPR were investigated by means of pH_stat batch leaching tests and mineralogical analysis. Moreover, mathematical and geochemical modeling complemented the study. The COPR in the area contain very high concentrations of chromium 24,409 mg/kg, which mainly occurs as Cr(III) (75–90%) as well as Cr(VI) (25–10%). The leaching of Cr(VI) occurs in all the range (2–10) of the tested pH values, however, it decreases under acidic conditions. Beside some reduction of Cr(VI) to Cr(III), the Cr(VI) content of the leachtes remains relatively high in the acidic environment, while the limning of Cr(VI) pond sediments will increase the release of the latter specie. The leaching of the Cr(III) occurs strictly under acidic conditions, whereby limning of these sediments will give rise to the lower solubility of Cr(III). The key mineral phases responsible for the fast release of the Cr(VI) are: the chromate salts (i.e. sodium chromate and sodium dichromate), while sparingly soluble chromatite (CaCrO₄) and hashemite (BaCrO₄) release Cr(VI) very slowly. Thus, pH and mineral solubility have been identified as key factors in the retention and the release of the hexavalent CrO₄ ²⁻ and Cr₂O₇ ⁻ from the COPR-rich pond sediments.     

Contamination,chemical speciation and vertical distribution of heavy metals in soils of an old and large industrial zone in Northeast China

Heavy metal pollution of soils has become a major concern in China as a consequence of rapid urbanization and industrialization in recent years. However, the evaluation on soil heavy metal pollution in Shenyang, the largest heavy industrial base city in China, has not yet been conducted. In this study, accumulation, chemical speciation, and vertical distribution Cu, Zn, Pb and Cd in soils were studied and pollution condition was assessed in Tiexi Industrial District of Shenyang, the largest and oldest industrial zone in Northeastern China. The results showed that in topsoil, the average concentration of total Cu, Zn, Pb, and Cd was 209.06, 599.92, 470.19 and 8.59 mg kg⁻¹, respectively, much higher than the national threshold limit. The values of pollution index and integrated pollution index showed that the pollution level was Cd > Cu > Zn > Pb, and Cd, Cu and Zn belong to heavy pollution level. The residual, Fe and Mn oxide-bound, and organic-bound species accounted for about 90%, while carbonate-bound and exchangeable species accounted for about 10%. This study indicates that the soils in the industrial zone were widely and extremely polluted by multi-heavy metals as a result of long-term industrial activities.     

Bioaccumulation of cadmium in the ascidian Styela clava (Herdman 1881)

The processes of bioaccumulation and elimination of cadmium by tissues of Styela clava (Herdman 1881) were investigated based on a semi-static two-compartment model. The kinetic parameters (accumulation rate constant k ₁, elimination rate constant k ₂, bioconcentration factor BCF, biological half-life t _1/2 and maximum equilibrium concentration C _Amax) were obtained by non-linear regression. The results showed that S. clava accumulates cadmium from its aquatic environment. BCF decreased with increasing metal concentration in the water, and when the accumulation achieved balance, C _Amax correlated positively with metal concentrations in the water. Concentrations of cadmium in different tissues of S. clava were: gonad > digestive gland ≈ other parts > tunic. The t _1/2 values for cadmium were 15.54-50.40 days in the accumulation process and 11.53-24.55 days in the elimination phase. The high rate of accumulation and elimination of cadmium from the body reveals the potential of the organism to be used as a biomonitor of short-term cadmium fluctuation in marine systems.     

Chitosan oligosaccharide-Ca complex accelerates the depuration of cadmium from Chlamys ferrari

This study investigated the effect of a chitosan oligosaccharide-Ca complex (COS-Ca) on the depuration of cadmium (Cd) from Chlamys ferrari. After exposure to 0.5 mg L-1 CdCl2 for 3 or 7 d, the scallops were treated by COS-Ca prior to determina-tion of Cd, calcium (Ca) and zinc (Zn) contents, Cd distribution in organs, malondialdehyde (MDA) content and antioxidant variables. Results showed that COS-Ca reduced Cd content in the viscera of the scallops, with highest Cd depuration rate (47%) observed on day 3. The COS-Ca concentration substantially affected Cd depuration, and the exposure to 8.75 mg L-1 COS-Ca led to significantly higher Cd depuration rate compared with those of lower COS-Ca concentrations (1.75, 3.5, 5.25, and 7.00 mg L-1). Distribution analysis of Cd in scallop organs indicated that COS-Ca significantly reduced Cd content in the kidney throughout the 5-d experiment, as well as in the gill during the early stage of Cd depuration. In addition, COS-Ca treatment decreased glutathione peroxidase (GSH-Px) activity and MDA content while increasing superoxide dismutase (SOD) and catalase (CAT) activities on different days. Our work suggested COS-Ca complex treatment as an effective method for acceleration of Cd depuration from Cd-contaminated bivalves.