Behaviour of colloidal trace metals (Cu, Pb and Cd) in estuarine waters: An approach using frontal ultrafiltration (UF) and stripping chronopotentiometric methods (SCP)

The frontal cascade ultrafiltration (UF) technique in conjunction with stripping chronopotentiometry (SCP) has been evaluated for determining the colloidal distribution of Cu, Pb and Cd in estuarine waters. Metallic concentrations in seven size fractions (0.45 μm–0.22 μm; 0.22 μm–300 kDa; 300–50 kDa; 50–30 kDa; 30–10 kDa; 10–5 kDa; <5 kDa) were determined with the aim to investigate their changes along the salinity gradient of the Penzé system (NW France). These data, completed by analysis of the total dissolved metals at 10 stations over the whole freshwater–seawater mixing zone, provided some insights in the removal and addition processes that affect Cu, Pb and Cd in estuaries.     

Distribution of trace metals in anchialine caves of Adriatic Sea,Croatia

This study presents results of the first comprehensive research on ecotoxic trace metals (Cd, Pb, Cu and Zn) in aquatic anchialine ecosystems. Data show the influence of hydrological and geological characteristics on trace metals in highly stratified anchialine water columns.     

南海表层水中的溶解态Cu,Pb, Zn,Cd

于1998年“南海海洋环境调查”外业工作期间在南海的各个站位,按照严格的防沾污措施采集了106个表层海水样品.采用溶剂萃取-石墨炉原子吸收法对样品中的痕量重金属Cu,Pb,Zn,Cd含量进行了分析测试.测得各重金属的平均值如下:Cu 0.100 μg/dm3,Pb 0.060μg/dm3,Zn 0.086 μg/dm3,Cd 0.007μg/dm3,接近世界大洋水的浓度水平.各重金属的空间分布呈现出海区周边含量高于中央,浓度有自近岸向远海逐渐减小的趋势.相关分析的结果表明各重金属夏季相关性优于冬季,Cu与Cd存在良好的正相关关系,并且首次在南海表层水发现Cu,Cd与营养盐的相关关系.将重金属浓度值作数理统计分析,得到它们在南海的基线值.     

Techniques for determination of trace metals in small samples of size-fractionated particulate matter: phytoplankton metals off central California

The oceanic biogeochemical cycles of many trace elements are dominated by their association with the growth, death, consumption and sinking of phytoplankton. The trace element content of marine phytoplankton reflects nutritional status, species composition, surface area to volume ratios, and interactions with bioactive and toxic elements in the ambient seawater. Despite the ecological and environmental importance of trace element assimilation by autotrophs, there are few modern measurements of trace elements in phytoplankton assemblages from the natural environment. Here we introduce a new method for collection and analysis of size-fractionated particulate samples from practical seawater volumes. We pay particular attention to accurate determination of trace element filter blanks which are typically the limiting factor for analysis of such samples. Metals were determined at very low detection limits by high resolution inductively coupled plasma mass spectrometry (HR-ICP-MS) for 11 elements (Ag, Al, Cd, Co, Cr, Cu, Fe, Mn, U, Zn and P, which is used as a biomass normalizer) in three types of polymer filters (0.45, 5.0, and 53 μm pore size) and a quartz fiber filter (0.8 μm pore size). To place these new determinations in a practical context, results are presented for a vertical profile of samples filtered from 1–4 l of coastal seawater (0.3–1.0 mg total solid dry weight) at a station off central California. The results demonstrate that the blanks of the evaluated filter types, precleaned appropriately, are sufficiently low to allow accurate determination of the trace metal content of three size-classes of phytoplankton. At the Pacific station, measured phytoplankton Zn content (as Zn/P) agrees with values predicted from single-species culture studies growing at seawater Zn concentrations expected for coastal waters. The new method has utility as a generally applicable and simple size fractionation technique, and allows determination of natural and pollutant elements in small samples of phytoplankton and particles in coastal, estuarine and offshore marine regimes.     

Dissolved Cu, Pb, Zn and Cd in the South China Sea surface waters

The understanding of the distribution of trace heavy metals in the world ocean has greatlyimProved in the past decades. But most of the data are of vertical profiles of certain stations(Bruland, l980; Paul et al., l992; RObert et al., l990) and large--scale study of temporaland spatial variability of trace heaVy metals in the ocean is rather few. In fact, affected by ver-tical mixing by upwelling or convection, biogenic removal, atmospheric fallout and continentalinput frorn rivers, the dist…     

Distribution and contamination of trace metals in surface sediments of the East China Sea

The distributions, contamination status and annual sedimentation flux of trace metals in surface sediments of the East China Sea (ECS) were studied. Higher concentrations of the studied metals were generally found in the inner shelf and the concentrations decreased seaward. The sequences of the enrichment factor (EF) of the studied metals are Cu > Mn > Ni > Zn > Pb > Fe. The values of EF suggest that the metals contamination in the middle and outer shelves of the ECS is still minor. The annual sedimentation fluxes of trace metals in the ECS were: Fe, 3.48 × 10⁷ t/y; Mn, 9.07 × 10⁵ t/y; Zn, 1.08 × 10⁵ t/y; Ni, 4.48 × 10⁴ t/y; Pb, 4.32 × 10⁴ t/y and Cu, 3.1 × 10⁴ t/y, respectively. Approximately 55–70% and 10–17% of the sedimentation fluxes of trace metals were deposited in the inner shelf and the Changjiang estuarine zone.     

Improved dithiocarbamate/oxine solvent extraction method for the preconcentration of trace metals from seawater using metal exchange back-extraction

A rapid single extraction procedure using dithiocarbamate complexing agent, a di-isobutyl ketone (DIBK) organic phase and Hg exchange back-extraction is described for the simultaneous quantitative preconcentration of Cd, Co, Cu, Fe, Ni, Pb and Zn in seawater. An 8-hydroxyquinoline (oxine) extraction technique is also presented for the subsequent determination of Mn using the same reagents and operating system. The proposed method gave quantitative spike recoveries for all metals and was in excellent agreement with the certified results for CASS-3 marine reference seawater. Blanks and detection limits are in the low ppt range. The method gives a preconcentration factor of 72 for an 80-ml sample, facilitating the analysis of pristine seawater samples.     

夏季外海水入侵对大亚湾浮游植物群落结构的影响

夏季大亚湾存在由粤东沿岸上升流所引起的外海水入侵现象,且入侵强度存在年际差异,作者利用大亚湾2004～2017年历年夏季航次调查数据,将弱入侵年份与强入侵年份进行对比分析,以探讨外海水入侵对大亚湾浮游植物群落结构的影响。结果显示,当外海水入侵由弱变强时,湾内水体理化特征发现显著变化,水体由高温低盐转变为低温高盐,N、P等营养盐含量出现下降。海水理化性质的改变导致了浮游植物群落结构的变化,硅藻、甲藻种类数以及浮游植物Shannon-wiener指数均出现升高;浮游植物总丰度和硅藻丰度下降,甲藻丰度变化不明显;常见浮游植物种类伪菱形藻属(Pseudo-nitzschiasp.)、角毛藻属(Chaetocerossp.)和叉角藻(Ceratiumfurca)丰度出现下降,而中肋骨条藻(Skeletonemacostatum)和菱形海线藻(Thalassionemanitzschioides)丰度出现升高;优势种由单一硅藻种类向硅藻和甲藻共为优势转变。此外,外海水入侵还会通过改变海水理化因子的空间分布以及湾内上层水体流向来影响浮游植物群落结构的空间分布。     

Nitrogen and phosphorus species in the coastal and shelf waters of Southeastern North Carolina, Mid-Atlantic U.S. coast

The diversity of small-scale wetlands, high salinity tidal creeks, salt marshes, estuaries, and a wide and shallow shelf with the Gulf Stream close to the break makes the coastal zone of south-eastern North Carolina (U.S.) a natural laboratory for the study of the cycling of nitrogen (N) and phosphorus (P) in coastal and shelf waters. We assessed the summer concentrations, forms, and ratios for each N (total dissolved N, nitrate + nitrite, ammonium and dissolved organic N) and P (total dissolved P, o-phosphate and dissolved organic P) pool as these nutrients travel from tidal creeks, salt marshes and two large estuaries to Long and Onslow Bays. Additionally, we measured ancillary physical (temperature, salinity and turbidity) and chemical (dissolved oxygen, chlorophyll a and pH) water properties. Highest concentrations of all individual N and P compounds were found in the upper parts of each tributary and were attributed to loads from agricultural and urban sources to the coastal watersheds, continuing downstream to receiving estuaries. In all areas, dissolved organic N and P species were predominant constituents of the total dissolved N and P pools (64–97% and 56–93%, respectively). The lower parts of estuaries and surface shelf waters were characterized by oceanic surface values, indicating removal of N and P downstream in all tributaries. The different watershed and hydrological characteristics also determined the different speciation of N and P pools in each estuary. Despite a high level of anthropogenic pressure on the uppermost coastal waters, there is self-regulation in this coastal ecosystem with respect to human perturbations; i.e. significant amounts of the N and P load are retained within estuarine and nearshore waters without reaching the shelf.     

Comparison of high spatial resolution trace metal distributions with model simulations for surface waters of the Gulf of Cadiz

A multidisciplinary study in the Gulf of Cadiz is revisited, using additional diagnostic modelling tools. The dissolved trace metal (Cu, Ni, Zn, Co) distributions in the Gulf of Cadiz are analysed using modelled tracer evolutions, field observations and the concept of tracer ages. This study shows that a significant part of the observed metal distributions can be explained by the metal inputs of three river systems (Guadiana, Rio Tinto and Odiel, Guadalquivir) discharging into the Gulf of Cadiz, while the remainder of the signal is most likely associated with the benthic metal remobilisation along the shelf of this coastal region.     

Geochemical and hydrodynamic constraints on the distribution of trace metal concentrations in the lagoon of Nouméa, New Caledonia

Seawater samples were collected in the lagoon of Nouméa (southwest New Caledonia) along two transects from eutrophic coastal bays to the oligotrophic barrier reef. Land-based emissions to the lagoon were measured with dissolved and particulate concentrations of chromium (Cr) and nickel (Ni), used as tracers of both terrigenous and industrial (Ni ore treatment) activities, as well as dissolved and particulate concentrations of zinc (Zn), used as a tracer of urban effluents. The spatial variability of metal concentrations was related to geochemical and hydrodynamic conditions, i.e., respectively: (1) natural and anthropogenic emission sources, and chemical processes occurring in the water column; and (2) water residence times. The parameter used to describe the residence time of water masses was the local e-flushing time, i.e. the time required for a tracer mass contained within a given station to be reduced by a factor 1/e. High metal concentrations were found in coastal areas (up to 9000 ng dissolved Ni L⁻¹), and steeply decreased with distance from the coast (down to 101 ng dissolved Ni L⁻¹ near the barrier reef) to reach levels similar to those found in remote Pacific waters, suggesting a rapid renewal of waters close to the barrier. Distributions of metals in the lagoon are controlled upstream by land-based emission sources and later chemical processes. Then hydrodynamics constrain metal distributions, as shown by the observed relationship between local e-flushing times and the spatial variability of metal concentrations. In addition, a change in the direction of prevailing winds yielded a decrease of dissolved metal concentrations at the same site by a factor of 2.5 (Cr and Ni) and 2.9 (Zn). It is suggested that the residence time is a key parameter in the control of elemental concentrations in the lagoon waters, as much as land-based emission sources.     

我国领海基线向陆一侧“内水”的涵义

我国的《领海及毗连区法》第2条规定:"领海基线向陆地一侧的水域为中华人民共和国的内水"。我国的《海域使用管理法》第2条规定:"本法所称内水,是指中华人民共和国领海基线向陆地一侧至海岸线的海域"。"两法"对"内水"的定义有水域和海域之分,因此容易引起解读上的分歧或执法上的模糊。分歧之一是,根据《海域使用管理法》,从领海基线向陆地一侧至海岸线部分,是否包括河口、海湾、滩涂等"内水";分歧之二是,根据《领海及毗连区法》,是否认定一部分"内水"即内海是由直线基线法所致。为什么"两法"对"内水"有水域和海域两种不同的定义?其一,"两法"针对的客体不同,《领海及毗连区法》针对的客体是国际或国外,该法的主体是国家主权;《海域使用管理法》针对的客体是国内海域,该法的主体是国内海域的使用管理。《联合国海洋法公约》(以下称《公约》)规定"领海基线向陆一面的水域构成国家‘内水’的一部分",那么另一部分"内水"就是正常基线向陆一侧的水域,包括江、河、海湾等,它完全置于国家领土主权之下。其二,用专业术语上的海岸线替代《海域使用管理法》中的海岸线会出现矛盾。专业术语上同指水陆分界线的有海岸线和"干出线"两种。前者是涨潮时离岸最近的线,后者是退潮时离岸最远的线,依据《公约》规定:"测算领海宽度的正常基线是沿海国官方承认的大比例尺海图所标明的沿岸低潮线,即退潮时海水离岸最远的那条线",所以低潮线更加符合《公约》和《海域使用管理法》中海岸线的定义,怎样理解海岸线才不会出现矛盾呢?本文认为,完全意义上的海岸线是大潮高潮线与低潮线之间的一条带状面,这个面有时被水淹没,有时出露,且宽窄不等,陡缓不一。当解读了《公约》的有关条款后,就不难理解领海基线向陆地一侧至海岸线的水域中有盐度为0.05~30和30~36范围的"内水"存在,盐度范围为0.05~30的"内水"是指按正常基线法划定领海基线而出现的"内水",包括水域和海域;盐度范围为30~36的"内水"是指按正常基线与按直线基线法划定的领海基线之间出现的"内水",即内海。它们在法律层面上有主从之分,不能混淆。     

灰色聚类法评价长江口、杭州湾海域表层海水中的重金属污染程度

通过2007年秋季航次我国近海海洋环境的综合调查,研究了长江口与杭州湾海域表层海水中重金属汞、砷、铜、铅、锌、镉、总铬的含量与分布,利用灰色聚类法对海水中的重金属元素进行评价。参照《国家海水水质标准GB3097-1997》,通过灰类白化权函数确定海水水质分级界限及各参评指标对不同等级的聚类权,构建了海水中重金属的灰色聚类法综合评价模型。该模型能够较客观、合理地评价海水中的重金属。评价结果表明,长江口与杭州湾海域表层海水中的重金属总体情况良好,但是汞、铅含量偏高,尤其是汞。长江口外以北、杭州湾北岸口外及舟山群岛邻近海域的海水水质相对较差,陆源排污为主要影响因子。     

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.     

南沙群岛海域海水中胶体铜、锌、铅

对海水中元素基本形态的区分通常是采用0.45μm孔径的滤膜过滤分离,但海水中那些并非溶解态的胶体粒子具有较大的变形性[1],并具有较小的粒度,在过滤时,基本上都进入了滤液而被算作溶解形态,这使得深入理解元素在海水中的形态分布及其海洋生态效应受到限制[2].     

Trace metal fronts in Scottish coastal waters

Dissolved cadmium and copper concentrations have been determined in 76 surface water samples in coastal and ocean waters around Scotland by anodic stripping voltammetry (ASV). A trace metal/salinity ‘front’ is observed to the west, north and north-east of Scotland separating high salinity ocean water (>35 × 10⁻³) with low concentrations of dissolved Cd and Cu from lower salinity (<35 × 10⁻³) coastal water containing higher concentrations of Cd and Cu. Mean Cd concentrations in ocean and coastal waters are 7 ng dm⁻³ (0·06 n ) and 11 ng dm⁻³ (0·10 n ) respectively; for Cu the respective levels are 60 ng dm⁻³ (0·95 n ) and 170 ng dm⁻³ (2·68 n ). The observed distribution is attributed principally to freshwater runoff and the advection of contaminated Irish Sea water into the study area.     

海口湾海水重金属的行为特征

本文对海口湾溶解态铜、铅、锌、镉进行了测定.铜的变化范围为:0.47～1.16μg/dm3,平均值为0.78μg/dm3;铅的变化范围为:0.94～2.36μg/dm3,平均值为1.36μg/dm3;锌的变化范围为:1.28～4.83μg/dm3,平均值为3.14μg/dm3;镉的变化范围为:0.005～0.072μg/dm3,平均值为0.030μg/dm3,Cu、Zn的溶解态含量在龙昆路生活污水排污沟口、秀英工业排污沟口及海甸溪口的测站相对较高,Pb、Cd溶解态含量较低,湾内各站平面分布较为均匀.它们的溶解态含量垂直变化趋势为:Cu、Pb、Zn底层大于表层,而Cd表层大于底层.对Cu、Pb、Zn、Cd的颗粒态含量也进行了测定,指出海口湾海水中的颗粒物对重金属的净化起一定作用.对铜的溶解态中的强络合态和不稳态铜也进行了研究,强络合态占总溶解态的比例均在85%以上,对生物起毒性作用有关的不稳态铜含量很低,均小于5nmol/dm3,表明目前海口湾海水中的重金属铜不会对生物生长产生影响.     

Isotopic,trace element and nutrient characterization of coastal waters from Ubatuba inner shelf area,south-eastern Brazil

Stable isotopes, tritium, radium isotopes, radon, trace elements and nutrients data were collected during two sampling campaigns in the Ubatuba coastal area (south-eastern Brazil) with the aim of investigating submarine groundwater discharge (SGD) in the region. The isotopic composition (δD, δ¹⁸O, ³H) of submarine waters was characterised by significant variability and heavy isotope enrichment. The stable isotopes and tritium data showed good separation of groundwater and seawater groups. The contribution of groundwater in submarine waters varied from a few % to 17%. Spatial distribution of ²²²Rn activity concentration in surface seawater revealed changes between 50 and 200 Bq m⁻³ which were in opposite relationship with observed salinities. Time series measurements of ²²²Rn activity concentration in Flamengo Bay (from 1 to 5 kBq m⁻³), obtained by in situ underwater gamma-spectrometry showed a negative correlation between the ²²²Rn activity concentration and tide/salinity. This may be caused by sea level changes as tide effects induce variations of hydraulic gradients, which increase ²²²Rn concentration during lower sea level, and opposite, during high tides where the ²²²Rn activity concentration is smaller. The estimated SGD fluxes varied during 22–26 November between 8 and 40 cm d⁻¹, with an average value of 21 cm d⁻¹ (the unit is cm³/cm² per day). The radium isotopes and nutrient data showed scattered distributions with offshore distance and salinity, which implies that in a complex coast with many small bays and islands, the area has been influenced by local currents and groundwater–seawater mixing. SGD in the Ubatuba area is fed by coastal contaminated groundwater and re-circulated seawater (with small admixtures of groundwater), which claims for potential environmental concern with implications on the management of freshwater resources in the region.     

Behavior features of heavy metals in the Haikou Bay waters

INThonUCrIONBecause of the discharge of industrial waste water, waste residue, waste gas and acid rain theheavy metals concentration in river and lake and eventually in seawater have been increasing.Therefore many studies on heavy metals innuencing marine ecological environment have beencarried out (Sun et al., 1990; Sunda and Guillard, 1976; Zhu et al., 1992). After entering intothe sea, heavy metals change, transfer and transform, and these processes have gained attentionfrom marine envi…