海洋胶体与痕量金属的相互作用

痕量金属的胶体结合态是海洋中金属的一种相当普遍的存在形式。胶体与痕量金属之间的相互作用影响着痕量金属在海水中的形态、迁移、生物可利用性及其归宿。总结了海洋胶体态金属的存在及其显著性,概述了胶体对金属在河口混合过程中行为的影响,并简要讨论了胶体在海水中痕量金属的固液相分配中的作用。     

海洋蓝细菌生物固氮的研究进展

海洋生物固氮是海洋中氮循环的重要过程，其对海洋吸收CO2有着重要的影响。海洋固氮蓝细菌的种类和数量也有待进一步探明。现今的研究已表明，蓝细菌对海洋的氮平衡和生物生产有着重要的贡献。从海洋生物固氮的研究现状和研究方法着手，阐述了海洋生物固氮的意义，并重点对影响海洋生物固氮的因素、海洋蓝细菌生物固氮的生物化学和分子生物学机制等研究方面做了细致的综述，在此基础上提出了海洋生物固氮方面有待深入研究的科学问题，旨在为海洋生物固氮及氮的生物地球化学研究提供基础资料。     

镉稳定同位素研究进展

Cd具有挥发性和亲硫性,在海洋环境中Cd为微量营养元素,而在生态环境及农业土壤环境中Cd为有毒元素.因此,镉同位素被应用于海洋科学、地球科学、环境科学及农业科学研究,并展现出巨大的应用潜力.本文总结了近年来富含有机质的环境样品、植物样品和生物样品的消解方法,以及Cd分离纯化及双稀释剂校正方法的研究进展.采用微波、高压灰...     

Nature and dynamics of phosphorus-containing components of marine dissolved and particulate organic matter

The molecular sources, dynamics and analytical characterizations of the phosphorus (P) containing components of marine dissolved and particulate organic matter (OM) are reviewed. Using a combination of ¹³C and ³¹P nuclear magnetic resonance spectroscopy on samples collected from a depth profile (20-4000 m) at Station Aloha in the North Pacific subtropical gyre, the biomolecular associations of P functional groups in marine OM are identified. Compositional differences between ultrafiltered dissolved organic matter (UDOM; 1-100 nm size fraction) and ultrafiltered particulate organic matter (UPOM; 0.1-60 μm size fraction) as reflected by NMR and elemental analyses indicate that UDOM does not originate from simple solubilization of UPOM, and the aggregation of UDOM is not the primary source of UPOM. Regression analyses indicated a large fraction of the P in UDOM is associated with carbohydrates and amino acids, but not with lipids. Similar analyses for UPOM indicated that P is associated with carbohydrates, amino acids and lipids. The P functional groups also appear to be balanced in their distribution among molecular classes, because they remain in relatively constant proportion throughout the ocean.     

海相优质烃源岩发育的主要影响因素及沉积环境

对海洋生物、现代海洋沉积和古代海相地层中有机质含量分布特征和实验室模拟实验的结果表明,水体中高生物生产率是海相环境形成富有机质沉积的关键因素;沉积和早期成岩作用期间水体的相对还原环境是有机质富集保存的有利条件;海底深部流体的活动是造成富有机质沉积的不可忽视的因素;沉积速率是影响海相沉积有机质富集的主要因素。现有研究表明,在海相盆地中最有利形成优质烃源岩的沉积环境主要有欠补偿浅水—深水盆地、台缘斜坡、半闭塞—闭塞欠补偿海湾和蒸发潟湖。     

古海洋生产力指标研究进展

寻求反映古海洋生产力变化的指标是古海洋学研究的重要内容。生物沉积物、营养元素、微量元素和同位素、古生物资料等与古海洋生产力具有一定的关系,常用于古海洋生产力的重建工作:(1)生物沉积物主要包括有机碳、生物碳酸盐和生物硅质沉积等,其埋藏速率在很大程度上受到古海洋生产力的控制,常常用作古海洋生产力的替代性指标;(2)在地质时间尺度上,古海洋生产力主要受到大洋中营养元素可利用程度的控制,因此营养元素的相关记录可以提供古海洋生产力状况的重要信息;(3)海洋中某些微量元素的地球化学行为或者与有机质的改造有关,或者受到氧化还原条件变化的控制,或者受到某种浮游生物的生长的影响,从而能够直接或者间接地指示古海洋生产力的变化;(4)海相碳酸盐和有机质的碳同位素记录,海相有机物的氮同位素比值也用以再造古生产率等古海洋学参数;(5)可以利用对微体化石丰度值及其组合反映古生产力的变化。     

海相碳酸盐岩优质烃源岩发育的主要影响因素

我国近3×106km2的海相碳酸盐岩分布区长期被认为是潜在的油气勘探区,近年来虽然我国在海相碳酸盐岩地层的油气勘探有了一些突破,但与广泛分布的海相碳酸盐岩区相比,取得的成果还不令人满意。其关键问题是海相碳酸盐岩沉积盆地优质烃源岩发育相带不明,控制优质烃源岩发育的主要因素不清。本文根据海洋生物、现代海洋沉积和古代海相地层中有机质含量分布特征和实验室模拟实验结果,提出影响海相沉积有机质富集的主要因素有:沉积物形成时水体中生物生产率、沉积速率、沉积阶段及早期成岩作用阶段的氧化还原环境、海底深部流体作用等。其中,水体中高生物生产率是海相环境形成富有机质沉积的关键因素,沉积阶段和早期成岩作用阶段水体的相对还原环境有利于有机质富集保存,海底深部流体的活动是形成富集有机质沉积的不可忽视的因素。沉积速率是影响海相沉积有机质富集的主要因素,适当的沉积速率是海相沉积富集的有利条件。     

Sedimentary pyrite formation: An update

Sedimentary pyrite formation during early diagenesis is a major process for controlling the oxygen level of the atmosphere and the sulfate concentration in seawater over geologic time. The amount of pyrite that may form in a sediment is limited by the rates of supply of decomposable organic matter, dissolved sulfate, and reactive detrital iron minerals. Organic matter appears to be the major control on pyrite formation in normal (non-euxinic) terrigenous marine sediments where dissolved sulfate and iron minerals are abundant. By contrast, pyrite formation in non-marine, freshwater sediments is severely limited by low concentrations of sulfate and this characteristic can be used to distinguish ancient organic-rich fresh water shales from marine shales. Under marine euxinic conditions sufficient H₂S is produced that the dominant control on pyrite formation is the availability of reactive iron minerals.Calculations, based on a sulfur isotope model, indicate that over Phanerozoic time the worldwide average organic carbon-to-pyrite sulfur ratio of sedimentary rocks has varied considerably. High $\text{C}\text{S}$ ratios during Permo-Carboniferous time can be explained by a shift of major organic deposition from the oceans to the land which resulted in the formation of vast coal swamps at that time. Low $\text{C}\text{S}$ ratios, compared to today, during the early Paleozoic can be explained in terms of a greater abundance of euxinic basins combined with deposition of a more reactive type of organic matter in the remaining oxygenated portions of the ocean. The latter could have been due to lower oceanic oxygen levels and/or a lack of transportation of refractory terrestrial organic matter to the marine environment due to the absence of vascular land plants at that time.     

Amino Sugars and Their Indicating Role in the Cycling of Organic Matter in Marine Environment

As a kind of marine organic matter with important geochemical characteristics, amino sugars can effectively reflect the source, diagenetic state and mineralization process of organic matter by their concentration and composition in marine environment. This article systematically concluded the research progresses of amino sugars from the aspects of their source, composition and distribution characteristics in marine environment, and the role as a biomarker indicating source and diagenetic state of marine organic matter. The result showed that the macromolecular morphology, the oxygen and nutrient level and the sedimentary environment could affect the reactivity of amino sugars. The higher ratios of glucosamine to galactosamine (GlcN/GalN) and the Total Hydrolysable Amino Acids to Total Hydrolysable Amino Sugars (THAA/THAS) can reflect the fresh planktonic organic matter source and the lower ratios can reflect the conversion from planktonic to bacterial organic matter. The carbon and nitrogen normalized yield of total hydrolysable amino sugars, however, could give contradictory results depending on the relative contribution of the source and degradation degree of organic matter. Muramic acid is suitable to estimate the contribution of relatively fresh bacteria organic matter to particulate and sediment organic matter, but it is not suitable for applying in the dissolved organic matter because of its very low concentration leading from its rapid recycle. It is critical to enhance the research on the contribution of different microorganisms to amino sugars and differentiate the influence of organic matter source and degradation on amino sugars in marine environment. The research on the conversion and fate of amino sugars in marine environment is also needed.     

Characterization of a major refractory component of marine dissolved organic matter

Refractory carboxyl-rich alicyclic molecules (CRAM) are characterized in marine dissolved organic matter (DOM) using nuclear magnetic resonance spectroscopy and ultrahigh resolution mass spectrometry. CRAM are distributed throughout the water column and are the most abundant components of deep ocean DOM ever characterized. CRAM are comprised of a complex mixture of carboxylated and fused alicyclic structures with a carboxyl-C:aliphatic-C ratio of 1:2 to 1:7. CRAM are expected to constitute a strong ligand for metal binding, and multiple coordination across cations could promote aggregation and marine gel formation thereby affecting CRAM reactivity and the bioavailability of nutrients and trace metals. It appears CRAM are ultimately derived from biomolecules with structural similarities to sterols and hopanoids. The occurrence of CRAM in freshwater and terrestrial environments seems likely, considering the global distribution of biomolecules and the similarities of biogeochemical processes among environments.     

粘土矿物保存海洋沉积有机质研究进展及其碳循环意义

海洋沉积物吸附有机质的量和有机质循环周期与粘土矿物类型和吸附方式密切相关,并在全球碳循环中扮演着不同的角色。粘土吸附有机质有物理吸附和化学吸附之分,前者主要存在于粘土的微孔隙中,参与年、十年或百年尺度的循环;后者主要存在于粘土矿物层间和外表面,稳定性较好,有机质易于保存,可参与百万年或更长时间的循环,这种不同时间尺度内的碳循环,将会改写海洋沉积物有机碳“源”、“汇”的关系。不同类型粘土矿物的性质存在差异,决定了吸附有机质量的多寡,蒙脱石的吸附量远大于伊利石的吸附量,这可能是造成全球不同海域中有机碳“源”、“汇”变化的原因。海洋沉积物处于水圈、生物圈和岩石圈的交汇地带,有机碳的差异和变化,都会对全球碳循环及气候变化产生重要的影响。     

The composition of ferromanganese nodules of the Chukchi and East Siberian seas

Ferromanganese nodules from the floors of the Chukchi and East Siberian seas were examined by means of analytical electron microscopy and plasmic and chemical analysis. It was found that the nodules consisted of aggregates of colloform and poorly crystallized matter of globular and irregular shapes, in which the minerals of iron and manganese were mainly presented by hematite, vernadite, and asbolane. The samples from the Chukchi Sea contained single micrograins of native gold. The tested nodules were comparable to oceanic ones in iron content. The contents of manganese, ore elements, and most of microelements are well below those of the ocean. The comparison of the composition of bottom sediments and considered nodules showed that the latter were enriched during their formation by factors of 100–200 in manganese, of 10–18 in cobalt, and of 4–8 in iron, nickel, and zinc. However, the process of diagenetic accumulation of metals by nodules in the marine environment is less effective than in the open ocean with the sediments of higher con-tent of mobile element forms and of higher exposure time compared to marine sediments.     

陆架边缘海环境下金属元素与有机质富集关系探讨

陆架边缘海是“河口—陆架”体系重要的碳汇,黏土矿物作为主要载体将有机质与金属元素吸附于表面或层间,通常表现为粒度、有机质和金属元素含量之间高度正相关。本文通过分析南黄海中部沉积物粒度、总有机碳、主微量元素,探讨三者之间分布特征和相互关系,进一步开展金属元素、有机质与黏土矿物吸附模拟实验,结果表明,酸性条件（pH=4）下适量的金属离子（Zn2+、Ni2+、Pb2+）明显促进伊利石对腐殖酸（有机质主要组成部分）吸附,腐殖酸吸附量达到20.06 mg/g,其中金属离子加入使腐殖酸吸附量提高6.25%;同时碱性条件（pH=8）下金属离子也能够促进伊利石对腐殖酸吸附,腐殖酸吸附量达到15.7 mg/g,金属离子加入使腐殖酸吸附量提高38.9%。金属离子的阳离子键桥作用促进伊利石吸附腐殖酸,且酸性环境下腐殖酸的吸附量高于碱性环境。证实了陆架边缘海背下金属元素的参与对黏土矿物吸附腐殖酸具有明显促进作用,有利于在全球碳循环过程形成边缘海“碳库”,同时海洋酸化可能造成海洋溶解有机质降低和重金属离子浓度升高,对陆架边缘海海洋生态系统平衡构成威胁。     

From land to sea: provenance,composition, and preservation of organic matter in a marine sediment record from the North-East Greenland shelf spanning the Younger Dryas–Holocene

The organic matter content of marine sediments is often used to infer past changes in ocean conditions. However, the organic carbon pool preserved in coastal sediments is a complex mixture derived from different sources and may not reflect in situ processes. In this study, we combine taxonomic identification of reworked palynomorphs with pyrolysis organic geochemistry and reflected-light organic petrographic microscopy to investigate the provenance, composition and preservation of organic matter in a marine sediment core retrieved from the NE Greenland shelf. Our study reveals continuous yet variable input of land-derived organic carbon to the marine environment throughout the late Younger Dryas–Holocene, with the highest input of inert carbon in the late Younger Dryas. Although the sediments contain some recent marine palynomorphs, there is no other evidence of fresh marine organic carbon. In contrast, our results indicate that these shelf sediments represent a significant sink of recycled organic carbon. The results of pyrolysis geochemistry revealed that ~90% of the total organic carbon in the sediments is inert. The organic petrography analyses revealed that >70–84% of the organic carbon in the sediment core is terrigenous. Reworked dinoflagellate cysts showed a continuous provenance of Cretaceous land-derived material, most likely from the nearby Clavering Island. Our study points to the importance of constraining the organic matter origin, composition and preservation in marine sediments to achieve more accurate palaeoenvironmental reconstructions based on organic proxies.     

以Al/Ti比值为地球化学示踪剂反演海洋古生产力的研究进展

地球化学家通常用Al对其它重金属进行归一化以校正沉积物来源、粒度、矿物组成等方面的影响,因此现代海洋沉积物样品中Al、Ti含量的结果主要用于定量描述陆源输送的贡献。近期研究结果发现,在受陆源物质输送影响较小,沉降颗粒主要以生源颗粒物为主的赤道大洋区,沉积物中出现明显的“过剩铝”信号,“过剩铝”约占沉积物中总铝含量的50％。因此,用沉积物中Al的含量来估算陆源碎屑的比例会导致过高的结果,建议用Ti、Sc作为参比元素校正陆源物质的影响。沉积物中的Al/Ti比值可用来示踪水体中颗粒物的沉降通量和初级生产的改变。综述了近期以Al/Ti比值这种新的地球化学示踪剂反演古生产力的最新研究进展,提出了在我国陆架边缘海开展此项工作可能存在的问题与挑战。     

Effect of organic matter and selected heavy metals on sorption of acenaphthene,fluorene and fluoranthene onto various clays and clay minerals

The effects of organic matter (80% humic and 15% fulvic acid) and coexistence of heavy metals (Ni, Pb and Zn) on sorption of three polycyclic aromatic hydrocarbons (PAHs)—acenaphthene, fluorene and fluoranthene—were examined for kaolinite, 60% kaolinite?+?40% sand, and 43% kaolinite?+?42% sand?+?15% bentonite. In total 108 batch sorption tests of PAHs were conducted for three types of clay mineral mixtures in six possible combinations of soil organic matter and heavy metal contents from no heavy metals and organic matter added to maximum organic matter added with spiked heavy metals. Results showed that the existence of metals increased the sorption of PAHs onto kaolinite from 4.7% for acenaphthene to 17.9% for fluoranthene. Organic matter in a kaolinite-sand-bentonite matrix could increase PAH sorption by up to 140% for fluoranthene. In all cases, increases were greater for fluoranthene, a larger PAH molecule. Heavy metals coexisting with organic matter led to enhanced sorption of PAHs compared to clay minerals without organic matter. Synergistic effects of organic matter and heavy metals on PAH sorption increments in the mixtures studied were such that the overall sorption could be 10–41% higher than that based on summation of the separate effects of metals and organics.     

海洋中氟氯烃的研究进展

研究海洋中的氟氯烃对全球气候变化和海洋环流的研究有重要意义.氟氯烃不仅是温室气体,还破坏大气平流层中的臭氧,也是近代海洋科学研究的有效工具,可以作为化学示踪剂,广泛用于示踪海洋环流、水团运动混合过程、海洋通风过程,测定水团年龄、海水混合和循环速率以及海气交换速率等的研究.对过去几十年海洋中氟氯烃的研究进展进行了评述,介绍了海水中氟氯烃的分布特征与通量研究、氟氯烃在海洋中的应用及分析方法,同时简述了大气中氟氯烃的分布特征.概述了该研究领域有待进一步研究的问题.     

Evidence of Bio-Organic Mineralization

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Metal ion binding to colloids from database to field systems

Nowadays, environmental problems related to soil pollution with heavy metals are numerous, therefore, it is important to understand metals behaviour in aquatic sediments and soils and to estimate their transfer. The fate of metals in the environment is closely related to their interactions with the major reactive compartments (organic matter, iron and manganese oxides, clays). The objective of this work is to develop an approach based on the combination of several models to study metal ion speciation in different environmental systems. Models used to describe the interactions of metals with the main reactive phases in the soil are CD-MUSIC (amorphous and crystallized iron oxides), NICA-Donnan (organic matter and manganese oxides) and cationic ion exchange model (clays). First, this work implies the definition of generic parameters to describe the interactions of the studied metals with iron and manganese oxides and part of this information is missing in the literature. Then, after a validation of the approach by comparison with analytical results, this multi-surface model is applied to test sites corresponding to one soil and two riverine environments.These new models give good predictions of the behaviour of major and trace metal ions even in heterogeneous systems characteristic of natural environment. The measured free metal concentrations in the solution are in agreement with those obtained from model calculations. In the case of the soil test site, the soil solution composition and speciation are predicted using the soil major constituents characteristics.     

Changes in the compound classes of dissolved organic matter along an estuarine transect: A study using FTIR and C NMR

In this work, we use Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance spectroscopy (¹³C NMR) data to quantify the changes of major chemical compound classes (carboxylic acid, amide, ester, aliphatic, aromatic and carbohydrate) in high molecular weight (HMW, >1 kDa) dissolved organic matter (DOM) isolated along a transect through the Elizabeth River/Chesapeake Bay system to the coastal Atlantic Ocean off Virginia, USA. Results show that carboxylic acids and aromatic compounds are lost along the transect, while HMW DOC becomes enriched in carbohydrate moieties that could have a mid-transect source, perhaps the intensive red tide bloom (Choclodinium polykrikoides) which occurred during our sampling period. Taking the second derivative of the FTIR spectra resolved three pools of de-protonated carboxylic acids at our Dismal Swamp site (used to represent terrestrial organic matter in this area): one carboxylic acid pool, complexed with iron, seems to be lost between the Dismal Swamp and river sites; the second appears biogeochemically active throughout the riverine transect, disappearing in the coastal ocean sample; the third seems refractory, with the potential to be transported to and to accumulate within the open ocean. Five-member ring esters (γ-lactones) were the major ester form in the Dismal Swamp; aliphatic and acetate esters were the dominant esters in the estuary/marine DOM. No amide groups were detectable in Dismal Swamp DOM; secondary amides were present at the estuarine/marine sites. Coupling FTIR with ¹³C NMR provides new insights into the biogeochemical roles of carboxylic acid, amide and ester compounds in aquatic ecosystems.