Dissolved trace metals in the Western Mediterranean Sea: total concentration and fraction isolated by C18 Sep-Pak technique

An investigation of trace metal distributions in the Western Mediterranean Sea was carried out during the RRS Discovery cruise (July 1993) in which a transect from the Strait of Gibraltar to the Strait of Sicily was conducted. Organically complexed dissolved trace metals and their total concentrations were measured to investigate the end-members and to predict the environmental capacity of the Mediterranean for potential toxic metals. The distribution of trace metals can be accounted for by the mixing of several end-members and by some atmospheric inputs to the surface water. For Pb and Fe, the effects of the atmospheric inputs are more pronounced than for the other metals. Due to the rapid exchange of water masses, the Western Mediterranean may have the ability to assimilate the increased external inputs for some trace metals such as Cu, Cd, Ni and Zn. But the external inputs for Pb and Fe exceed the removal capacity of the Western Mediterranean and these elements may accumulate in the water column of the western basin. The C18 Sep-Pak technique and direct determination by DPASV were used to determine the amount of trace metal–organic complexes. The C18 Sep-Pak column isolates only a small fraction of trace metals except for Cu. The maximum hydrophobic fractions for the studied trace metals, except for Cd and Pb, which are not detectable, were found in the subsurface layer at all stations. This maximum may well be linked to picoplankton activity and the picoplankton, prochlorophytes may have an important role in the speciation of dissolved Cu as well as Synechococcus. These organic ligands for Cu were produced at the maximum of biological activity in the Western Mediterranean basin and seem to be accumulated at halocline level by Mediterranean hydrodynamic characteristics. However, direct determination by DPASV showed that the major part of Cu, Cd and Pb, complexed by organic materials, was not isolated by C18 Sep-Pak technique.     

九龙江口生物可利用磷的行为与入海通量

于1995年3、5月在九龙江口进行两个航次的现场调查,研究不同形态磷的河口行为,并估算生物可利用磷的入海通量。结果表明,在S＜20区域内,溶解活性磷（DRP）的行为受控于“缓冲机制”,其含量在8～10μg／dm3水平上下波动。颗粒磷中MgCl2。可提取磷（MgCl2-P）含量随盐度增大而增大,并与叶绿素a以及悬浮物中Fe、Mn、Al含量呈正相关关系。NaOH／NaCl可提取磷（NaOH／NaCl－P）随盐度增大按指数关系下降,其含量与悬浮物中Fe、Mn、Al含量呈正相关关系。HCl可提取磷（HCl－P）在河口区的行为表现为保守混合。九龙江口生物可利用磷入海通量约517t／a,其中潜在生物可利用磷（PBAP）的贡献为溶解活性磷（DRP）的3倍。     

北部湾沉积物中重金属元素的地球化学特征及物源初探

本文根据北部湾沉积物岩心样调查结果计算了铜、铅、锌、镉、汞、砷等重金属元素的背景值,并分析了其与南海陆架区和南海全海域沉积物背景值、广西土壤背景值之间的差异.对北部湾表层沉积物中重金属含量及近10 a的变化趋势以及岩心样中重金属元素含量近百年以来的变化趋势综合分析结果表明:北部湾近岸海域沉积物中铜、砷、汞、镉重金属元素含量总体呈增长趋势,北部湾中部海域沉积物中重金属元素含量的年际变化有升有降,至湾口处沉积物中重金属元素的含量基本不变.综合评价结果表明,北部湾近岸沉积物中砷、汞、镉等重金属元素的地球化学特征明显受到广西人类活动的影响.北部湾沉积物中的重金属元素主要来源于人类活动影响下的广西沿岸陆源输入,经由琼州海峡的外部海域物质输入也有贡献.     

金属大气腐蚀实验方法进展与研究动态

金属材料及其制品与所处的自然环境间因环境因素的作用而引起材料变质或破坏称为金属材料的大气腐蚀。金属材料的大气腐蚀机制主要是材料受大气中所含的水分、氧气和腐蚀性介质的联合作用而引起的破坏。按腐蚀反应可分为化学腐蚀和电化学腐蚀两种，在干燥无水分的大气环境中发生的腐蚀属化学腐蚀，其它情况下均属于电化学腐蚀，但它又别于全浸在电解液中的电化学腐蚀，它是在电解液薄膜下的电化学腐蚀，水膜的厚度及干湿交变频率、氧的扩散速度等因素，都影响着大气腐蚀的过程与速度。     

The utility of near infrared spectroscopy for age estimation of deepwater sharks

Reliable age information is vital for effective fisheries management, yet age determinations are absent for many deepwater sharks as they cannot be aged using traditional methods of growth bands counts. An alternative approach to ageing using near infrared spectroscopy (NIRS) was investigated using dorsal fin spines, vertebrae and fin clips of three species of deepwater sharks. Ages were successfully estimated for the two dogfish, Squalus megalops and Squalus montalbani, and NIRS spectra were correlated with body size in the catshark, Asymbolus pallidus. Correlations between estimated-ages of the dogfish dorsal fin spines and their NIRS spectra were good, with S. megalops R²=0.82 and S. montalbani R²=0.73. NIRS spectra from S. megalops vertebrae and fin clips that have no visible growth bands were correlated with estimated-ages, with R²=0.89 and 0.76, respectively. NIRS has the capacity to non-lethally estimate ages from fin spines and fin clips, and thus could significantly reduce the numbers of sharks that need to be lethally sampled for ageing studies. The detection of ageing materials by NIRS in poorly calcified deepwater shark vertebrae could potentially enable ageing of this group of sharks that are vulnerable to exploitation.     

A spectral model for the sea-state with explicit forcing terms

A spectral ocean wave model with explicit representations of the identified physical source terms is described. The model has the ability to represent the evolution of the wave spectrum effectively without the need for a very short integration timestep. This is achieved by incorporating a simple parameterisation for the weakly nonlinear wave-wave interactions and using a predictor step to estimate the integral parameters which govern the form of this function. The model was tested over a number of ideal situations and conformed well to the data. It also performed comparably to the third-generation WAM model. In field trials the model was driven by winds derived from numerical weather prediction model initialisations via a diagnostic marine boundary layer model. The wave estimates were compared with data from a Waverider buoy at a site exposed to the Southern Oceans. Significant wave heights were modelled well with a root-mean-square error of 0·9m and a scatter index of 0·24. Frequency characteristics produced poorer results but similar to other operational models, i.e. frequency was over-estimated. Comparisons with significant wave heights from the GEOSAT radar altimeter gave a spatial measure of the model's performance which was similar to the temporal measure from the Waverider buoy data.     

The measurement of the volatile organic fraction of the TOC in seawater

A method based on a dynamic head-space extraction and high-temperature oxidation of the trapped organic matter is described for the determination of the volatile organic carbon (VOC) concentration in seawater. The VOC concentrations in various geographic regions have been measured and calculated as a fraction of the total organic carbon (VOC/TOC). The VOC concentrations ranged from 15–60 μg C/liter in most oceanic areas. This volatile component was found to be a small fraction (1.5–6%) of the TOC. The VOC concentrations are highest in coastal regions and in the surface zone while the VOC/TOC ratio is relatively constant with depth and location. The volatile organic components may be important to the cycling of organic matter in sea water and the dynamics of this role have been postulated.     

The hydrophobic fraction of organic matter in the Krka River Estuary

Surface active substances have been studied in the Krka River Estuary using an a.c. polarography method and various fractionation procedures. Total surface substances (SA_T) were separated into (particulate) heterodispersed and dissolved fractions by filtration. The dissolved fraction was separated into hydrophobic basic and neutral components, hydrophobic acid and hydrophilic components by sorption on to XAD-8 resin.The content and the composition of SA_T varied seasonally, depending on the biological activities taking place in the Krka River Estuary. The accumulation of SA_T, with hydrophobic properties, occurred at the fresh/saline water interface along the vertical profile. Daily changes in the form of the surface active substances along the vertical profile were observed. The formation of the heterodispersed fraction, especially observable in the upper freshwater layer and at the halocline, resulted in the change of physico-chemical properties of surface active substances. Organic matter appeared mainly in a dissolved form in the deeper saline water layer, showing negligible oscillations.The electrochemical characterization of the fractionated SA_T indicated that strong hydrophobicity of the surface active substances under natural pH conditions could be attributed to the significant contribution of the heterodispersed fraction of the organic material, which is the most reactive part of the surface active substances in the Krka River Estuary.The dissolved fraction of the surface active substances, prevailing in the deeper saline water layer, exhibited either hydrophilic or conditionally hydrophobic properties, depending on pH and ionic strength of the medium.     

The use of a consequential perspective to upgrade the utility of Life Cycle Assessment for fishery managers and policy makers

Attributional LCA, which monitors specific production systems in steady state conditions, is increasingly used in fisheries to assess the environmental profile of fleets and seafood supply chains. However, this approach is not pertinent to assess the environmental consequences of (large scale) policies. In contrast, consequential LCA (CLCA) has been successfully implemented in other sectors to assess the expected changes in environmental impacts of a given production system and other (marginal) production systems that may be affected in response to changes driven by policy or strategic decisions. CLCA commonly combines LCA with economic models to simulate the interactions occurring between the analysed systems. However, the use of these models may not be the most appropriate approach to follow for fisheries. Hence, it seems feasible that CLCA should be combined with stock prediction tools rather than with economic models, to determine how changes in stock sizes and quota restrictions may cause variations in the environmental impact of fishing fleets.     

Development of passive sampling devices for bioavailable contaminants of current and emerging concern: Waitemata Harbour case study

Bioavailable contaminant concentrations are an important component in assessing environmental effects as they directly affect ecosystem health. Shellfish contaminant monitoring programmes have traditionally filled this requirement but are being phased out in some jurisdictions. Passive sampling devices (PSDs) have the potential to replace shellfish monitoring; however, there are still knowledge gaps to address before this can occur. This study assessed the suitability of three different PSDs in providing the required information to replace shellfish monitoring. PSDs were deployed at three historic mussel monitoring sites with different levels of urban influence in the Waitemata Harbour, Auckland, New Zealand. Contaminants of interest were urban heavy metals, plus current and emerging organic contaminants. PSDs provided extremely low detection limits and, for some contaminants, very strong correlations to shellfish. PSDs can currently complement shellfish in monitoring, but it is premature to make conclusions as to the suitability of PSDs in replacing shellfish monitoring until more information is available.     

The oxygen isotopic composition of the fraction less than 2 microns (clay fraction) in Recent sediments from western Europe

The oxygen isotopic composition of the clay fraction in Recent argillaceous sediments in western Europe shows regional differences, the δ¹⁸_SMOW values varying between + 15.8 and + 21.7‰. This phenomenon is used for sediment-transport studies. In the Rhine-Meuse estuary a landward transport of marine sediments is observed. The clay fraction of the sediments in the Wadden Sea is only for a minor part derived from the rivers Rhine and Meuse.     

The geochemistry of trace metals in the Brazos River estuary

A seasonal study of trace metal behavior and transport in the Brazos River estuary was conducted in the winter, spring and fall of 1981. Surface water was analyzed for total dissolved Pb, Cu, Mn and Fe, and particulate Cd, Pb, Cu, Mn and Fe. Ancillary data included river discharge, total suspended matter, pH, major ions, nutrients, dissolved and particulate organic carbon and humic acid.The major ions were generally conservative across the river water-seawater mixing zone; however, a significant input of alkalinity and Ca was measured in the spring, attributable to cation exchange on clays and sediment diagenetic processes. Distinct concentration maxima were found in the 3–10‰ chlorinity range for dissolved Pb (0·06–0·9 nm), Cu (6–42 nm), Mn (2–290 nm) and Fe (5–80 nm). Particulate metal concentrations showed significant seasonal and spatial variations: Cd, 0·09–0·57 ppm; Pb, 15–43 ppm; Cu, 12–32 ppm; Mn, 250–1990 ppm and Fe 0·5–5·4%. Reducing conditions leading to diagenetic remobilization in estuarine sediments are proposed to be an important source of dissolved metals for estuarine water. Calculations of dissolved riverine metal transport to the ocean that include estuarine metal input are as much as 40 times greater than when estuarine processes are ignored.     

论法制化海洋行政管理

海洋有着丰富的自然资源,是人类生存与发展的希望所在。21世纪是海洋世纪,向海洋进军,开发利用海洋资源,造福人类,这是21世纪人类实践活动的主题之一。在海洋实践活动中,如何更好地管理海洋,实现海洋经济价值的最大化,笔者认为,依法管海、依法治海和依法用海是我国海洋管理的基本手段和发展趋势。为了推动我国法制化建设的进程,本文仅就海洋管理的法制化问题谈几点看法。     

Production of bioavailable and refractory dissolved organic matter by coastal heterotrophic microbial populations

Production of dissolved organic matter (DOM) by heterotrophic microbial communities isolated from Loch Creran (Scotland) was studied in time course incubations in which cells were re-suspended in artificial seawater amended with variable proportions of glucose, ammonium and phosphate. The incubation experiments demonstrated that microheterotrophs released part of the substrate as new DOM, with a production efficiency of 11 ± 1% for DOC, 18 ± 2% for DON and 17 ± 2% for DOP. Estimating the impact of this production in Loch Creran, showed that from 3 ± 1% (DOC) to 72 ± 16% (DOP) of DOM could originate from the heterotrophic microbial community. The produced DOM (PDOM) was both bioavailable (BDOM) and refractory (RDOM). Bioavailability as assessed by the difference between the maximum and the end DOM concentration, was generally higher than found in natural systems, with DOP (73 ± 15%, average ± SD) more bioavailable than DON (70 ± 15%), and DON than DOC (34 ± 13%).The stoichiometry of PDOM was linked to both nutrient uptake and BDOM ratios. Absorption and fluorescence of DOM increased significantly during the incubation time, indicating that microheterotrophs were also a source of coloured DOM (CDOM) and that they produce both bioavailable protein-like and refractory humic-like fluorophores.     

The distribution and geochemistry of some trace metals in the Bermuda coastal environment

Results of the analyses of the water column and sediments of the Bermuda Platform for Cd, Cu, Fe, Mn, Ni, Pb and Zn are presented. The major process controlling the water column concentrations is physical mixing of open ocean waters with inshore waters, which are polluted by a wide range of diffuse inputs. Sedimentation within the inshore waters plays a lesser, but significant, role as do fluxes from the sediments of Fe and Mn and possibly phytoplankton uptake of Zn. Concentrations within the sediments are controlled by the formation of trace metal enriched clay/organic particles in the inshore areas and their subsequent redistribution by sediment resuspension, except for Fe and Mn which are largely associated with clay lattices.     

Baseline establishment for metals in the western Clarion-Clipperton Zone

Resource exploitation in the Clarion-Clipperton Zone (CCZ) is of major research interest worldwide, but its influence on the environment is poorly understood, especially due to the lack of baseline values for metals in the surrounding sediment. This work aimed to establish the baseline values of 17 metals (Ba, Ca, K, Mg, Mn, Na, Ag, As, B, Cd, Co, Cr, Cu, Hg, Ni, Pb, and Zn) using normalization, the cumulative frequency curve method considering a total of 172 samples taken from 8 multitube cores and 1 box sediment core collected in the western CCZ during the COMRA-45 cruise campaign from August to September 2017. The baseline values of the evaluated metals were as follows: 1 932 mg/kg for Ba, 29 512 mg/kg for Ca, 18 150 mg/kg for K, 17 120 mg/kg for Mg, 6 747 mg/kg for Mn, 28 546 mg/kg for Na, 0.571 mg/kg for Ag, 5.00 mg/kg for As, 94.4 mg/kg for B, 0.626 mg/kg for Cd, 104 mg/kg for Co, 76.1 mg/kg for Cr, 370 mg/kg for Cu, 0.028 mg/kg for Hg, 190 mg/kg for Ni, 27.5 mg/kg for Pb and 156 mg/kg for Zn. Our findings would fill the baseline value gap in the study area and further improve accuracy of environmental impact assessments on the impact of resource exploitation.     

The impact of metals on the reproductive mechanisms of the ascidian Ciona intestinalis

Environmental pollution due to anthropogenic activities may exert an adverse impact on the reproductive mechanisms of animals. In particular, environmental chemicals introduced into seawater are able to disrupt the normal development and function of the reproductive system of marine animals. In this study, we have used the whole‐cell voltage clamp technique to examine the effects of four metals – lead, cadmium, mercury, and zinc – on reproductive mechanisms of the marine ascidian Ciona intestinalis (tunicates). In particular, we measured the effect of metals on plasma membrane electrical properties, the steady‐state conductance, the fertilization current in the mature oocyte, and larval development. Results show that oocyte voltage‐gated sodium currents are significantly reduced by all four metals, steady‐state conductance is affected only by zinc, and post‐fertilization contraction is inhibited only by lead. The fertilization current is suppressed in the presence of zinc and mercury. Embryo development up to larval stage is inhibited by zinc and mercury exposure with a reversible effect; however, a long‐term effect on larval morphology was observed. After exposure to cadmium, fertilization occurs but gives rise to abnormal larval development. These findings highlight the point that exposure to metals represents a significant risk factor for the physiology of reproduction of marine species and suggest a possible role of the C. intestinalis as a bioindicator for marine pollution monitoring.     

The influence of particle size of the dispersed mineral fraction on the settlement of marine and estuarine muds

Considering the sedimentation behaviour of suspensions, four states of different sediment-water mixtures are usually distinguished, these being (in increasing concentration) dilute suspensions, concentrated suspensions, fluid muds and mud deposits. As the concentration values delimiting these states vary considerably from one cohesive sediment to another, a procedure for their quantitative determination is proposed here. This paper deals mainly with the effects of hindered settling in interacting concentrated suspensions and of sedimentation in fluid muds. In contrast to the settling velocity of individual particles in a dilute suspension, which must be studied statistically as a stochastic variable denoted W, hindered settling and sedimentation velocities can be described by a scalar denoted V, as solids at any particular level of concentrated suspensions and fluid muds settle at the same velocity. On the basis of settlement tests carried out in this study and published data on organic-rich cohesive sediments, a concentration-dependent empirical law for a permeability coefficient (k) has been generated for cohesive sediments, using data from ten estuarine and nine marine environments, based on the one-dimensional Kynch theory of sedimentation. Based on the median diameters of the dispersed mineral fraction, the main provenances of the sediments are: fine to very fine clay from tropical marine/estuarine environments, medium clay to very fine silt from estuaries in western France, and fine to coarse silt from marine (harbour) environments in the Normandy region of France. A general trend for the influence of the grain size of the mineral fraction on the permeability coefficient has been established. It is demonstrated that the concentrations delimiting the different states of sediment-water mixtures can also be related to the grain size of the mineral fraction. Thus, hindered settling and sedimentation processes of muds, similar to the marine and estuarine cohesive sediments considered in this paper, can be studied as generic problems parameterized through a defined median diameter of the dispersed mineral fraction. Results for Loire estuary sediments are presented separately, based on specific tests to analyse the influence of experimental conditions on settlement. Moreover, the concentration values delimiting the different sediment-water mixture states have been largely established for this estuary.     

厦金海域珊瑚体内重金属水平和分布特征

采用电感耦合等离子体质谱仪测定了厦金海域8种珊瑚中Cr、Mn、Co、Ni、Cu、Zn、As、Cd、Sn、Sb、Pb重金属的含量,通过数据处理、主成分分析方法,分析了重金属分布特征和其主要来源。采用单因子污染指数法对珊瑚重金属的污染水平进行了评价。结果表明,其平均浓度水平从大到小依次为:ZnMnSnCrCuAsNiPbSbCdCo。在8种珊瑚中,星柳珊瑚(Astrogrogia sp.)、等柳珊瑚(Paris fruticosa)、Paraplexaura sp.的重金属含量较高,花柳珊瑚(Anthogorgia sp.)和Guaiagorgia anas的含量较低。台湾海域珊瑚中Cu、Zn、Pb、Ni的含量、委内瑞拉海域珊瑚中Zn、Pb、Ni的含量远高于厦金海域珊瑚体内相同重金属含量,大堡礁珊瑚中Cu含量较厦金海域的略高。通过相关性分析发现,Cr、Co、Ni、Zn和Sn的种间差异较为显著。根据主成分分析,厦金海域珊瑚体内重金属元素可能的污染来源有:农业污染、港口生活污水和工业污水的排放、船舶油漆、涂料侵蚀、电镀工业。单因子污染指数法评价结果表明,6种重金属元素中,大佰屿、白哈礁和角屿的主要污染物是Mn。白哈礁、大佰屿站位的珊瑚体内重金属Mn处于重度污染水平,角屿站位的处于中度污染水平。     

新仙女木事件的发生及其全球性意义

综合国内外学者对短时间尺度气候事件的研究成果 ,对新仙女木事件 ( YD)的全球性分布及其界定方法和成因机制进行探讨。揭示了新仙女木期的气候特征和多种不同的气候替代指标 ,表明在太阳辐射 -大气 -冰盖 -陆地 -生物相互作用、多层次反馈的全球气候系统中存在着非线性气候变化 ,且在时间上、地域上存在着明显的差别 (不同步性 )。进一步阐明了 YD事件是全球性气候突变事件 ,是全球气候变暖、海平面上升过程中一次短暂的滞缓或回返 ,支持了 Fairbanks的气候 -海平面变化理论。冰期 -全新世过渡期气候变暖的驱动力是地球轨道参数的变化 ,YD事件作为非轨道事件 ,其驱动力可能归因于全球 CO2 浓度的变化 ,但 CO2 变化的因果关系至今尚无定论。