The chemical changes of DOM from black waters to coastal marine waters by HPLC combined with ultrahigh resolution mass spectrometry

How dissolved organic matter (DOM) undergoes chemical changes during its transit from river to ocean remains a challenge due to its complex structure. In this study, DOM along a river transect from black waters to marine waters is characterized using an offline combination of reversed-phase high performance liquid chromatography (RP-HPLC) coupled to electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS), as well as tandem ESI-FTICR-MS. In addition, a water extract from degraded wood that mainly consists of lignins is used for comparison to the DOM from this transect. The HPLC chromatograms of all DOM samples and the wood extract show two major well-separated components; one is hydrophilic and the other is hydrophobic, based on their elution order from the C₁₈ column. From the FTICR-MS analysis of the HPLC fractions, the hydrophilic components mainly contain low molecular weight compounds (less than 400 Da), while the hydrophobic fractions contain the vast majority of compounds of the bulk C₁₈ extracted DOM. The wood extract and the DOM samples from the transect of black waters to coastal marine waters show strikingly similar HPLC chromatograms, and the FTICR-MS analysis further indicates that a large fraction of molecular formulas from these samples are the same, existing as lignin-like compounds. Tandem mass spectrometry experiments show that several representative molecules from the lignin-like compounds have similar functional group losses and fragmentation patterns, consistent with modified lignin structural entities in the wood extract and these DOM samples. Taken together, these data suggest that lignin-derived compounds may survive the transit from the river to the coastal ocean and can accumulate there because of their refractory nature.     

Particulate peptidoglycan in seawater determined by the silkworm larvae plasma (SLP) assay

Peptidoglycan (PG) is a biopolymer found exclusively in the cell wall of bacteria. Recent chemical analysis of particulate organic matter suggests that a major amount of the muramic acid, an amino sugar present only in PG, could not be accounted for in terms of bacterial cells (Benner and Kaiser, 2003); however, data on particulate PG is quite sparse. In the present study, conducted in 1996, the PG was examined at 5 sampling sites in the northwestern Pacific Ocean, and in natural seawater cultures. Particulate PG, which was concentrated using a 96-well filtration plate equipped with Durapore filters (pore size, 0.22 μm), was measured by the silkworm larvae plasma (SLP) assay. The PG concentration generally decreased with depth and correlated significantly with bacterial abundance throughout the entire water column. However, the ratio of particulate PG to bacterial abundance varied with depth. The average ratio was 0.61 ± 0.53 (average ± SD, n = 40) between 50 and 2000 m, which agreed with the bacterial cellular PG content from 0.63 to 1.1 fg cell⁻¹ obtained in seawater cultures. On the other hand, the ratios of PG to bacteria from the surface to 50 m (3.7 ± 2.6, n = 29) and below 2,000 m (2.1 ± 1.7, n = 7) were significantly higher than that between 50 and 2,000 m. These results may suggest that, in the surface and deep layers, a significant fraction of particulate PG was present in bacterial detritus, whereas this fraction was reduced in the middle layer.     

Zinc speciation in the Northeastern Atlantic Ocean

Measurements of zinc and zinc complexation by natural organic ligands in the northeastern part of the Atlantic Ocean were made using cathodic stripping voltammetry with ligand competition. Total zinc concentrations ranged from 0.3 nM in surface waters to 2 nM at 2000 m for open-ocean waters, whilst nearer the English coast, zinc concentrations reached 1.5 nM in the upper water column. In open-ocean waters zinc speciation was dominated by complexation to a natural organic ligand with conditional stability constant (log K_ZnL′) ranging between 10.0 and 10.5 and with ligand concentrations ranging between 0.4 and 2.5 nM. The ligand was found to be uniformly distributed throughout the water column even though zinc concentrations increased with depth. Organic ligand concentrations measured in this study are similar to those published for the North Pacific. However the log K_ZnL′ values for the North Atlantic are almost and order of magnitude lower than those reported by Bruland [Bruland, K.W., 1989. Complexation of zinc by natural organic-ligands in the central North Pacific. Limnol. Oceanogr., 34, 269–285.] using anodic stripping voltammetry for the North Pacific. Free zinc ion concentrations were low in open-ocean waters (6–20 pM) but are not low enough to limit growth of a typical oceanic species of phytoplankton.     

Quantum yield for the photochemical production of dissolved inorganic carbon in seawater

The direct photooxidation of coloured dissolved organic matter (CDOM) to dissolved inorganic carbon (DIC) may provide a significant sink for organic carbon in the ocean. To calculate the rate of this reaction on a global scale, it is essential to know its quantum yield, or photochemical efficiency. We have determined quantum yield spectra, φ(λ), (moles DIC/mole photons absorbed) for 14 samples of seawater from environments ranging from a turbid, eutrophic bay to the Gulf Stream. The spectra vary among locations, but can be represented quite well by three pooled spectra for zones defined by location and salinity: inshore φ(λ)=e^{−(6.66+0.0285(λ−290))}; coastal φ(λ)=e^{−(6.36+0.0140(λ−290))}; and open ocean φ(λ)=e^{−(5.53+0.00914(λ−290))}. Production efficiency increases offshore, which suggests that the most highly absorbing and quickly faded terrestrial chromophores are not those directly responsible for DIC photoproduction.     

胶州湾沉积物中有机硫来源及成因机制的研究

有机硫是海洋沉积物中重要的硫形态,其中成岩有机硫对有机质保存和微量元素形态具有重要影响。利用化学提取及硫稳定同位素研究了胶州湾沉积物中碱可提取的腐殖酸硫(HA-S)、富里酸硫(FA-S)以及铬不可还原有机硫(non-CROS)的垂直分布、来源及形成机制。结果表明,non-CROS、HA-S以及FA-S的含量范围分别为19.1~52.6、3.35~7.82和27.3~38.6μmol/g,均处于其他许多近海沉积物中含量的低值区,且3者均为海洋生物有机硫和成岩有机硫的混合物。HA-S和nonCROS以海洋生物有机硫为主,其份数分别为65%~68%和67%~77%,而FA-S则以成岩有机硫为主(54%~73%)。相对于生物有机硫,成岩有机硫更易被碱和酸性Cr(Ⅱ)溶液提取,因此腐殖质硫和non-CROS都不能全面反映沉积物中有机硫的组成和来源。黄铁矿和腐殖质中成岩有机硫含量随深度的同步增加表明黄铁矿形成并未明显地竞争性抑制有机质硫化。     

商业平板式超滤膜包完整性检验：对海洋胶体生物地球化学研究的启示

The performance and integrity of a cassette cross-flow ultrafilter(Pellicon 2, Millipore) are examined with a suite of macromolecules of different molecular masses. The retention coefficient during the cross-flow ultrafiltration experiments increases with increasing molecular mass and reaches 90% with 10 kDa dextran in both milli-Q water and ultrafiltered seawater media. Based on a 90% retention coefficient, the molecular mass cut-off for the ultrafiltration membrane is defined at 10 kDa, which is ten times(1 kDa) that rated by the manufacturer. To further validate the accuracy of the laboratory calibration, the samples from the lower Zhujiang River and the Jiulong River Estuary are ultrafiltered with the cassette ultrafiltration membrane and the colloidal organic carbon abundances in these samples are quantified with the ultrafiltration permeation model based on time series permeation subsamples. The colloidal organic carbon abundances are 5.8%–21.1% in the Jiulong River Estuary and 5.6%–11.0% in the lower Zhujiang River. These are consistent with the reported values for both estuaries as well as with the colloidal organic carbon abundances in marine environments over the coastal and open oceans with 10 kDa cut-off membranes. Therefore, these field data support the laboratory calibration result and indicate the validity of the experimental and quantification procedure adopted. The discrepancy between the nominal molecular mass cut-off and the actual pore size of the ultrafiltration membrane should be of great concern for research in colloidal and nanoparticle biogeochemistry. Careful examination of the membrane integrity should be taken during ultrafiltration experiments in order to avoid misleading molecular mass cut-off information.     

水下荧光光谱探测装置控制系统的设计与实现

海水中有色可溶性有机物(CDOM,Chromophoric Dissolved Organic Matter,常称之为黄色物质)是影响海洋水色的三大成分之一,海水中CDOM的研究具有重要的意义。本文针对CDOM水下原位探测激光诱导荧光光谱探测装置开发了一套控制系统,该控制系统分为水上甲板控制和水下数据采集两部分,水上甲板控制部分通过8芯电缆与水下数据采集部分实现供电及通信,水下数据采集部分以PC104嵌入式工控机为核心,控制整体采集部分的工作,甲板控制部分通过远程控制软件来操控PC104以实现水下数据的采集和存储。实验室环境测试及近海现场实验表明,该系统能够可靠完成水下荧光光谱装置的控制和数据的采集及通信需求,实现海水中有色可溶性有机物的水下原位探测。     

基于分段副产物瞬时选择性的反应器网络综合

针对第三类反应体系的反应器网络综合问题,提出将串联反应以反应物到目的产物的反应步数为依据的新分段策略。通过比较不分段目的产物、不分段目的产物和中间产品、分段副产物和分段目的产物这四种不同的瞬时选择性,提出以分段副产物瞬时选择性为参数,以其对关键组分浓度或转化率的导数为依据选择各阶段最合适的反应器,以目的产物总选择性最大为目标采用遗传算法优化反应器网络。通过三个实例验证了本文所建立方法在解决复杂反应反应器网络综合问题的有效性,且本方法同样适用于简单反应体系。     

Aliphatic biomarker signatures of early Oligocene-early Miocene source rocks in the central Qiongdongnan Basin: Source analyses of organic matter

The geochemical signatures of fifty-four rock samples and three supplementary drill stem test(DST) oils from the Yacheng-Sanya formations in the central Qiongdongnan Basin(CQB) were analysed. Reconstruction of the early Oligocene-early Miocene(36–16 Ma) palaeovegetation and source analyses of organic matter(OM) were conducted using aliphatic biomarkers in ancient sediments and DST oils. Both the interpreted aquatic and terrigenous OM contributed to the CQB source rocks(SRs) but had varying relat...     

The application of isotopic and biogeochemical markers to the study of the biochemistry of organic matter in a macrotidal estuary, the Loire, France

The biogeochemistry of organic matter in a macrotidal estuary, the Loire, France, has been studied for two years during different seasons. Both particulate matter and sediment have been sampled in the riverine zone, in the maximum turbidity zone and in the ocean near the river mouth. Two techniques have been used: carbon isotopic ratio determination and analysis of lipid-marker signatures in the n-alkane, n-alkene and fatty acid series. For the period corresponding to the output of the maximum turbidity zone in the ocean, the complete change of organic matter, continental in nature in the inner estuary, pure marine in the outer estuary is well illustrated by the decrease of δ¹³C values and of carbon preference index of n-alkanes. Input sources of organic matter by continental plants, plankton and micro-organisms are discussed from biogeochemical-marker analyses data along with the processes of accumulation of particles and their evolution with the season. Some criteria for evidencing the nature of various organic-matter pools are assessed and compared in different chemical-marker series as follows: high molecular weight n-alkanes and fatty acids, perylene for continental imprints, polyunsaturated 18-, 20- and 22-carbon fatty acids, n-C₁₇, n-alkenes and squalene for algae imprints, branched iso and anteiso fatty acids, Δ11-C_18:1 for microbial imprints.