Dissolved inorganic carbon (DIC) and its carbon isotopic composition in sediment pore waters from the Shenhu area,northern South China Sea

The Shenhu area is one of the most favorable places for the occurrence of gas hydrates in the northern continental slope of the South China Sea. Pore water samples were collected in two piston cores (SH-A and SH-B) from this area, and the concentrations of sulfate and dissolved inorganic carbon (DIC) and its carbon isotopic composition were measured. The data revealed large DIC variations and very negative δ ¹³C-DIC values. Two reaction zones, 0–3 mbsf and below 3 mbsf, are identified in the sediment system. At site SH-A, the upper zone (0–3 mbsf) shows relatively constant sulfate and DIC concentrations and δ ¹³C-DIC values, possibly due to bioturbation and fluid advection. The lower zone (below 3 mbsf) displays good linear gradients for sulfate and DIC concentrations, and δ ¹³C-DIC values. At site SH-B, both zones show linear gradients, but the decreasing gradients for δ ¹³C-DIC and SO₄ ²⁻ in the lower zone below 3 mbsf are greater than those from the upper zone, 0–3 mbsf. The calculated sulfate-methane interface (SMI) depths of the two cores are 10.0 m and 11.1 m, respectively. The depth profiles of both DIC and δ ¹³C-DIC showed similar characteristics as those in other gas hydrate locations in the world oceans, such as the Blake Ridge. Overall, our results indicate an anaerobic methane oxidation (AMO) process in the sediments with large methane flux from depth in the studied area, which might be linked to the formation of gas hydrates in this area.     

贵州夜郎湖表层水体地球化学昼夜变化及其影响因素

为探究岩溶水库水文地球化学行为过程,对贵州普定夜郎湖表层水体进行了为期3 d的高分辨率昼夜监测。结果表明：1）多变的天气和水文条件叠加导致水体离子指标昼夜变化不显著,规律性较差。而水温、DO、pH值、SpC、SIc、pCO₂等常规理化指标受水温变化和生物作用表现出明显的昼夜波动。2）利用亨利常数和主成分分析,得到温度变化、生物作用、人类活动、水库的蓄水与放水对夜郎湖水库水文地球化学特征变化的贡献率分别为21.66%、17.28%、14.08%和10.22%,说明作用于水库水文地球化学行为的因子具有多元性。3）δ ¹⁸O表现出与DO一致的波动趋势,即白天上升,晚上下降,反映在短时间尺度上,氢氧稳定同位素变化受控于生物过程（主要是呼吸作用过程）;而对比水库水体和大气降水的d-excess（d值）发现,水库水体的d值（8.21‰）显著偏低于当地大气降水的d值（9.64‰）,说明在长时间尺度上,主要受蒸发效应引起的不平衡分馏影响。     

臭氧及臭氧类高级氧化技术降解甲基对硫磷的效能

文章研究了臭氧及臭氧类高级氧化技术(AOPs-O3)在不同pH条件下降解甲基对硫磷(MP)的效能。结果表明,在pH 3~10的条件下(反应过程控制pH),单独臭氧化5min即可完全降解MP,但不同pH下化学耗氧量(COD)和有机磷的释放率差异明显。在pH为3.3,7.5和9.4的条件下单独臭氧30min后COD的去除率分别为55.17%,89.64%和93.10%,有机磷的释放率分别为16.33%,95.00%和99.99%。考虑酸性条件下可以规避碳酸盐的负面影响(特别是高浓度废水),利用O3/H2O2/Ti(IV)在pH 3.3条件下处理MP溶液,COD去除率和有机磷释放率分别达到89.64%和81.57%。相对法计算求得MP与O3和羟基自由基(·OH)的速率常数分别为31.98L·(mol·s)-1和7.488×109 L·(mol·s)-1。活性污泥法的测试结果表明,MP经O3/Ti(IV)/H2O2(pH=3.3)和O3(pH=9.4)可提升含MP废水的可生化性,但与培养液体系相比仍具有一定的毒性。     

体重和温度对华贵栉孔扇贝(Chlamys nobilis)耗氧率和排氨率的影响

采用室内实验生态学方法对华贵栉孔扇贝的耗氧率和排氨率进行了研究。旨在为华贵栉孔扇贝养殖容量的调查及生态生理的研究提供参考,并可为海洋生态系统动力学和贝类能量学研究提供科学依据。实验结果表明,在实验温度(13—33℃)范围内,华贵栉孔扇贝的耗氧率(OR)和排氨率(NR)与体重(W)都呈负相关,可以用Y=aW-b表示。华贵栉孔扇贝的耗氧率和温度的关系可以表示为OR=-c+b1T-b2T2。在13—28℃温度范围内,华贵栉孔扇贝的耗氧率随温度的升高而增加,28℃时,耗氧率达到最大值,温度升高到33℃时,耗氧率反而下降。而排氨率与温度的关系可以表示为1NR=c1edT,在实验温度范围内,排氨率随温度的升高则呈持续升高趋势。华贵栉孔扇贝呼吸和排泄Q10值范围分别为0.466—2.471和1.129—2.437。在23—28℃温度范围内,不同规格华贵栉孔扇贝的耗氧率和排氨率的比值(原子数O:N)较高。方差分析表明,体重、温度及二者的交互作用对华贵栉孔扇贝的耗氧率和排氨率均有极显著的影响(P0.01)。华贵栉孔扇贝的日常代谢明显高于标准代谢,耗氧率和排氨率平均值分别提高29.9%和69.4%。     

帕劳群岛附近海域延绳钓渔场大眼金枪鱼(Thunnus obesus)的环境偏好

2005年8—12月,利用金枪鱼延绳钓渔船对帕劳群岛附近海域进行调查,研究大眼金枪鱼的环境偏好。所获数据包括:①温度、盐度、溶解氧垂直分布,测定的钓钩深度;②作业参数;③渔场气象数据;④渔获统计数据。分析方法和步骤为:①应用逐步回归的方法,建立钓钩预测深度计算模型;②根据温度、盐度、溶解氧垂直分布曲线、预测深度、取样数据,利用统计和聚类分析的方法分析大眼金枪鱼的环境偏好。结果表明:①在帕劳群岛附近海域,大眼金枪鱼偏好的水层为180.0—219.9m、水温范围为11.0—12.9℃、盐度范围为34.50—34.99、溶解氧范围为3.00—3.99mg/L;②一般情况下,水温及其体温的变化决定成熟大眼金枪鱼的活动水层,其偏好的水温为10.0—14.0℃;③大眼金枪鱼的适盐性较广;④溶解氧高于门限值(0.8mg/L)时,大眼金枪鱼的分布由其它环境因子决定。     

Kinetic and equilibrium studies of copper-dissolved organic matter complexation in water column of the stratified Krka River estuary (Croatia)

An interaction of dissolved natural organic matter (DNOM) with copper ions in the water column of the stratified Krka River estuary (Croatia) was studied. The experimental methodology was based on the differential pulse anodic stripping voltammetric (DPASV) determination of labile copper species by titrating the sample using increments of copper additions uniformly distributed on the logarithmic scale. A classical at-equilibrium approach (determination of copper complexing capacity, CuCC) and a kinetic approach (tracing of equilibrium reconstitution) of copper complexation were considered and compared. A model of discrete distribution of organic ligands forming inert copper complexes was applied. For both approaches, a home-written fitting program was used for the determination of apparent stability constants (K_i^equ), total ligands concentration (L_iT) and association/dissociation rate constants (k_i¹,k_i^- 1).A non-conservative behaviour of dissolved organic matter (DOC) and total copper concentration in a water column was registered. An enhanced biological activity at the freshwater–seawater interface (FSI) triggered an increase of total copper concentration and total ligand concentration in this water layer. The copper complexation in fresh water of Krka River was characterised by one type of binding ligands, while in most of the estuarine and marine samples two classes of ligands were identified. The distribution of apparent stability constants (log K₁^equ: 11.2–13.0, log K₂^equ:8.8–10.0) showed increasing trend towards higher salinities, indicating stronger copper complexation by autochthonous seawater organic matter.Copper complexation parameters (ligand concentrations and apparent stability constants) obtained by at-equilibrium model are in very good accordance with those of kinetic model. Calculated association rate constants (k₁¹:6.1–20 × 10³ (M s)^− 1, k₂¹: 1.3–6.3 × 10³ (M s)^− 1) indicate that copper complexation by DNOM takes place relatively slowly. The time needed to achieve a new pseudo-equilibrium induced by an increase of copper concentration (which is common for Krka River estuary during summer period due to the nautical traffic), is estimated to be from 2 to 4 h.It is found that in such oligotrophic environment (dissolved organic carbon content under 83 µM_C, i.e. 1 mg_CL^− 1) an increase of the total copper concentration above 12 nM could enhance a free copper concentration exceeding the level considered as potentially toxic for microorganisms (10 pM).     

Winkler's method overestimates dissolved oxygen in seawater: Iodate interference and its oceanographic implications

Dissolved oxygen in seawater has been determined by using the Winkler's reaction scheme for decades. An interference in this reaction scheme that has been heretofore overlooked is the presence of naturally occurring iodate in seawater. Each mole of iodate can result in an apparent presence of 1.5 mol of dissolved oxygen. At the concentrations of iodate in the surface and deep open ocean, it can lead to an overestimation of 0.52 ± 0.15 and 0.63 ± 0.05 μmol kg^− 1 of oxygen in these waters respectively. In coastal and inshore waters, the effect is less predictable as the concentration of iodate is more variable. The solubility of oxygen in seawater was likely overestimated in data sources that were based on the Winkler's reaction scheme for the determination of oxygen. The solubility equation of García and Gordon [Garcia H.E., Gordon, L.I., 1992. Oxygen solubility in seawater: Better fitting equations. Limnol. Oceanogr. 37, 1307–1312] derived from the results of Benson and Krause [Benson, F.B., Krause, D. Jr., 1984. The concentration and isotopic fractionation of oxygen dissolved in freshwater and seawater in equilibrium with the atmosphere. Limnol. Oceanogr. 29, 620–632] is free from this source of error and is recommended for general use. By neglecting the presence of iodate, the average global super-saturation of oxygen in the surface oceans and the corresponding efflux of oxygen to the atmosphere both have been overestimated by about 8%. Regionally, in areas where the degree of super-saturation or under-saturation of oxygen in the surface water is small, such as in the tropical oceans, the net air–sea exchange flux can be grossly under- or overestimated. Even the estimated direction of the exchange can be reversed. Furthermore, the presence of iodate can lead to an overestimation of the saturation anomaly of oxygen in the upper ocean attributed to biological production by 0.23 ± 0.07%. AOU may have been underestimated by 0.52 ± 0.15 and 0.63 ± 0.05 μmol kg^− 1 in the surface mixed layer and deep water, while preformed phosphate and preformed nitrate may have been overestimated by 0.004 ± 0.001 and 0.06 ± 0.02 μmol kg^− 1 in the surface mixed layer, and 0.005 ± 0.0004 and 0.073 ± 0.006 μmol kg^− 1 in the deep water. These are small but not negligible corrections, especially in areas where the values of these parameters are small. At the increasing level of sophistication in the interpretation of oxygen data, this source of error should now be taken into account. Nevertheless, in order to avoid confusion, an internationally accepted standard needs to be adopted before these corrections can be applied.     

Oxidation of copper(I) in seawater at nanomolar levels

The oxidation and reduction of nanomolar levels of copper in air-saturated seawater and NaCl solutions has been measured as a function of pH (7.17–8.49), temperature (5–35 °C) and ionic strength (0.1–0.7 M). The oxidation rates were fitted to an equation valid at different pH and ionic strength conditions in sodium chloride and seawater solutions:

The reduction of Cu(II) was studied in both media for different initial concentrations of copper(II). When the initial Cu(II) concentration was 200 nM, the copper(I) productions were 20% and 9% for NaCl and seawater, respectively. The effect of speciation of copper(I) reduced from Cu(II) on the rates was studied. The Cu(I) speciation is dominated by the CuCl₂⁻ species. On the other hand, the neutral chloride CuCl species dominates the Cu(I) oxidation in the range of 0.1 M to 0.7 M chloride concentrations.     

Similarity of electrophoretic dissolved protein spectra from coastal to pelagic seawaters

Dissolved proteins in seawater samples collected from a coastal area of Tokyo Bay, Sagami Bay and a location off the Kuroshio Current were investigated by one-dimensional sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) and high resolution two-dimensional electrophoresis (2-DE). Four to nine protein bands were detected in SDS-PAGE in the apparent molecular weight (MW) range from 12 kilo Dalton (kDa) to 49 kDa. The 2-DE technique distinguished 10 to 46 protein spots exhibiting isoelectric point (pI)/MW ranging 4.3–9.2/12–63 kDa. The elecrophoretic patterns were similar between the coastal and pelagic samples, as well as previously reported patterns from various pelagic areas. The close similarity of electrophoretic mobility on both SDS-PAGE and 2-DE gels indicates the compositional homogeneity of dissolved proteins in seawater throughout a broad range of marine environments. Proteinaceous dissolved organic matter (DOM) that was unresolved and smeared staining characteristics on both SDS-PAGE and 2-DE gels was first observed in Tokyo Bay waters in the present study and its possible sources are discussed. Although the two protein species, 48 kDa and 39 kDa proteins, have been identified as homologues of Porin P and low molecular weight-alkaline phosphatase of Pseudomonas aeruginosa PAO1, respectively, four strains of P. aeruginosa and two species of Pseudomonas spp. have been newly identified as the source organisms of these proteins using the N-terminal amino acid sequence data determined in previous studies.