Trace element diagenesis in pyrite-rich sediments of the Achterwasser lagoon, SW Baltic Sea

The early diagenesis of trace elements (V, Cr, Co, Cu, Zn, As, Cd, Ba, U) in anoxic sediments of the Achterwasser, a shallow lagoon in the non-tidal Oder estuary in the Baltic Sea, was investigated in the context of pyrite formation. The dissolved major redox parameters show a two-tier distribution with transient signals in the occasionally re-suspended fluid mud layer (FM) and a permanently established diagenetic sequence in the sediment below. Intense microbial respiration leads to rapid depletion of O₂ within the uppermost mm of the FM. The reduction zones of Mn, Fe and sulfate overlap in the FM and in the permanently anoxic sediment section which appears to be a typical feature of estuarine sediments, under low-sulfate conditions. Degrees of pyritization (DOP) range from 50% in the FM to remarkably high values > 90% at 50 cm depth. Pyrite formation at the sediment surface is attributed to the reaction of Fe-monosulfides with intermediate sulfur species via the polysulfide pathway. By contrast, intense pyritization in the permanently anoxic sediment below is attributed to mineral growth via adsorption of aqueous Fe-sulfide complexes onto pyrite crystals which had originally formed in the surface layer.The studied trace elements show differential behavior patterns which are closely coupled to the diagenetic processes described above: (i) Zn, Cu and Cd are liberated from organic matter in the thin oxic layer of the sediment and diffuse both upwards across the sediment/water boundary and downwards to be trapped as monosulfides, (ii) V, Cr, Co and As are released during reductive dissolution of Mn- and Fe-oxyhydroxides, (iii) U removal from pore water occurs concomitantly to Fe reduction in the FM and is attributed to reduction of U(VI) to U(IV), (iv) the Ba distribution is controlled by reductive dissolution of authigenic barite in the sulfate reduction zone coupled with upward diffusion and re-precipitation. The incorporation of trace elements into pyrite is most intense for Co, Mn and As, intermediate for Cu and Cr and little to negligible for U, Zn, Cd, V and Ba. The observed trend is largely in agreement with previous studies and may be explained with differing rates for ligand exchange. Slow and fast ligand exchange and thus precipitation kinetics are also displayed by downcore increasing (Mn, Cr, Co and As) or constantly low (Zn, Cu, Cd) pore water concentrations. The downward increasing degrees of trace metal pyritization (DTMP) for Co, Cu, Zn and As are, in analogy to pyrite growth, assigned to adsorption of sulfide complexes or As oxyanions onto preexisting pyrite minerals.     

Metal binding by humic acids in recent sediments from the SW Iberian coastal area

The concentrations of Cu, Zn, Cr, Ni, Pb, As, Mn and Co were determined by Inductively Coupled Plasma–Mass Spectrometry both in recent sediments from different locations of the Huelva littoral (SW Iberian Peninsula) and in their humic acid (HA) fractions in order to evaluate distribution and binding capacity of those trace elements to HAs. In addition, elemental composition (C, N, S) and δ¹³C values were determined to appraise the sources of organic matter in the area. This study involved the comparison of selected samples taken from different environments including the estuary of the Guadiana River, the main fluvial system of the region, the Tinto and Odiel estuary system and the proximal shelf. Significant positive correlations were found among Cu, Zn, As and Pb in bulk sediments, suggesting a common origin of all of those elements: the mining activities and pyrite deposits located hinterland. On the other hand, results for Cr, Co and Ni pointed to the basic rocks from the low basin of the Guadiana River as their main source. Elemental (C, N) and isotopic (δ¹³C) composition of sediments indicated a significant contribution of autochthonous plankton in coastal shelf sediments, whereas estuarine and riverine sediments showed a major contribution of terrestrial biomass. Geochemical values for their corresponding HAs suggested a greater terrestrial contribution in the sedimentary OM of the coastal shelf sediments than in bulk sediments, which evidenced the influence of coastal currents and sediment fluxes. Humic acids sequester considerable amounts of Cu and Zn contributing to reduce the bioavailability of these contaminants.     

不同成因的海洋铁锰氧化物沉积物中稀土元素的地球化学特征

测试了具代表性的成岩型结核和水成型结壳的稀土元素,以研究稀土元素在这两种成因的海洋铁锰氧化物沉积物的特征及其与成因的关系。稀土元素特征表明稀土元素没有参与成岩型结核的成岩作用。即没有加入到1nm水锰矿中去,而是加入到无定形铁的氧化物、氢氧化物中去。同样,稀土元素也没有直接参与水成结壳的水成作用,即没有加入到锰、铁的氧化物、氢氧化物中去,而是与钙、磷相关。推测在很大程度上是先沉淀在钙、磷相中然后才加入到水成结壳中。稀土元素在这两种类型的沉积物的分布与其成因密切相关。     

东太平洋多金属结核中铁、锰元素的分形演化及其意义

运用分形理论,通过建立不同的相空间,计算了东太平洋多金属结核中的铁、锰元素的时间序列在各相空间中的关联分维,并与其在沉积物岩心中的关联分维进行了对比.通过研究发现,多金属结核中铁、锰元素和沉积物中Fe₂O₃及MnO在分形演化过程中均存在分维吸引子,认为沉积物中的Fe₂O₃和MnO可以用3个变量来描述,它们可能代表了火山、生物和陆地的三种来源,而描述结核中的铁、锰元素却需要14个变量,反映多金属结核中铁、锰元素的来源和/或赋存非常复杂,至少有14个因素在起作用,可能暗示了结核在形成过程中存在复杂的生物化学作用,为多金属结核的生物成因提供了间接的数学证据,同时也合理解释了结核生长结构所具有的自相似韵律现象.     

柴达木盆地昆特依盐湖的地球化学演化与古气候变化

１９９０年用铀系年代学及古地磁对昆特依盐湖沉积物进行年代测定，探讨该湖区地球化学演化与古气候变化关系。结果表明，该区最老的盐层形成于早更新世晚期（大于７３０ｋａ），大量的盐类沉积则始于３００ｋａ左右；盐湖沉积物中元素含量变化主要受古盐度、矿物、类质同象和吸附控制；沉积物水溶Ｆ／Ｃｌ比值与古盐度成反比关系；该湖２０００ｋａ以来的古环境演变：盐层形成于干冷、偏酸性的氧化环境，泥岩层形成于湿暖、偏碱性的     

南太平洋富稀土海区海水中的溶解态稀土元素空间分布特征研究

深海富稀土沉积物因其资源潜力巨大,近年来备受关注。一般认为,沉积物中稀土元素和钇（总称REY）的主要来源为上覆海水,但针对富稀土海区上覆海水中REY的研究较少。本研究针对南太平洋富稀土海区采集的3个站位的全水深海水样品,测试出了15种溶解态REY,并对比了邻近海域已发表的数据,分析了该海区REY的空间分布特征。研究区表层水中溶解态REY浓度主要受风尘输入影响,而中层和深层水体中溶解态REY浓度主要受水团控制。经过澳大利亚后太古代页岩（PAAS）和北太平洋深层水（NPDW）归一化后的配分模式可确定REY间的分馏特征,分辨出不同水团。与其他大洋中报道的REY数据比较发现,表层水中REY浓度受风尘和河流输入影响导致差别较大,中层水中REY浓度与印度洋较为接近,深层水中REY浓度与不同大洋的水团年龄表现为正相关趋势,即REY浓度由小到大依次为大西洋、印度洋、南太平洋、北太平洋。     

湖相介形类壳体微量元素在古环境重建中的应用

湖相介形类壳体微量元素（本文主要指Mg和Sr）是重建古环境的重要指标之一,可以定性或定量地反映湖水信息。自20世纪80年开始应用以来,经过30余年的发展取得了很大进展。在古环境重建过程中主要存在两类影响因素：（1）其宿生水体中M/Ca比值（M主要指Mg和Sr）的影响因素：季节变化、微环境差异和湖泊演化过程,这类因素通过对宿生水体中M/Ca比值来影响介形虫壳体中的M/Ca比值,进而造成古环境重建结果的误差增大或可靠性降低;（2）介形类壳体微量元素分配系数的影响因素：宿生水体中M/Ca比值、温度、碱度等,这类因素能够直接影响介形类壳体分泌、钙化的生命-化学过程的因素,是定量重建的重要影响因素。加强现代介形类生活习性和微量元素组成变化过程的研究可以消除或减小以上影响因素对古环境重建的影响,提高介形类壳体化石中微量元素组成在古环境重建研究中的精度和可靠性。     

基于ANUSPLIN的京津冀区域逐日气温格点数据集建立方法研究

为建立一个高精度、高空间分辨率的逐日气温格点数据集,满足公共气象服务对于精确信息及实时信息的需要,利用2018年6—8月京津冀区域以及临近省区共3 974个国家级及区域气象观测站质控后的逐日气温资料,采用ANUSPLIN软件对逐日气温数据进行空间内插,得到了京津冀区域逐日气温格点数据集(0.01°×0.01°),并分别利用反距离权重插值法、普通克里金插值法、样条函数法对逐日气温数据进行空间插值,采用相关系数(Corr)、平均绝对误差(MAE)、平均相对误差(MRE)等作为评估指标来检验插值精度。结果表明:1) ANUSPLIN软件满足了空间插值对精度及曲面平滑度的要求,能直观体现京津冀区域气温由北向南递增的空间分布特征; 2) 4种插值方法中,基于ANUSPLIN软件的插值结果最优,相关系数平均达0.97,其样本误差在1℃之内占比为90.59%,MAE为0.46℃,MRE为1.81%; 3)插值误差较大的区域位于冀北高原、燕山丘陵及太行山脉一带,高海拔、低站点密度等是造成插值误差的主要原因。基于ANUSPLIN插值方法建立的逐日气温格点数据集具有分辨率高、空间插值误差小的优势,ANUSPLIN对气温的空间分布具有较好的预测能力。     

Binogeochemical process of major elements in sinking particulate of Nansha coral reef lagoons,South

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西菲律宾海沉积物铁族元素地球化学

本文对取自西菲律宾海区的三个柱状沉积物岩芯的铁族元素地球化学行为进行了系统的研究。从元素的含量及剖面变化、元素的相关性及组合特征,铁族元素与主元素的关系以及元素的赋存状态等方面探讨了物质来源、沉积作用和古气候,并据此进行了地层划分。沉积物有4种来源:海底火山源、生物源、自生源和陆源。海底火山物质提供了较多的铁族元素,相形之下,自生沉积作用较弱。元素地层学研究表明,在全新世温暖期和晚更新世寒冷期铁族元素表现出不同的地球化学行为,尤以Mn和亲生物(Ca)元素对气候的反映灵敏。WP_2孔和WP_(40)孔铁族元素特征相似,与WP_1孔差别较大。