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…     

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.     

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.     

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…     

Metal distributions and their fluxes at the coastal boundary of a semi-enclosed ria

Water column samples have been collected in the outer channel of the Ferrol Ria (NW Spain) during four occasions over a tidal cycle. The objective was to study the exchange of dissolved and particulate Cd, Cu, Pb and Zn and particulate Al, Fe and Si between the ria and the adjacent coastal waters. This study provides the first extensive dataset on dissolved and particulate metal concentrations in the water column of a Galician ria. Typical concentrations of dissolved Cd (96 ± 31 pM), Cu (8 ± 4 nM), Pb (270 ± 170 pM) and Zn (21 ± 10 nM) were similar than in other European Atlantic shelf and coastal waters. The fraction of metals in the particulate phase followed the trend: Pb > Cu Zn > Cd. The outgoing water from the ria was enriched in dissolved and particulate Cu, Pb and Zn compared with incoming waters, whereas Cd concentrations were similar for both waters. The suspended particulate matter was composed of a mixture of marine and continental material. The latter end-member was found to arise from the metal-rich ria bed sediments, which is diluted by the dominant metal-poor marine end-member. The net output flux of Cu from the channel is balanced by the freshwater inputs to the ria, and the net Zn flux gave a positive output to coastal waters. For Pb, the net flux to the coastal waters is less than that input from the rivers, as a result of its particle reactivity and deposition in sediments. On the contrary, a net input flux of dissolved Cd from coastal waters was observed, highlighting the oceanic source of this metal in the Galician rias. Results from the budget calculations are in agreement with the differential geochemical behavior of these elements in coastal waters.     

Trace metals in seawater and copepods in the ocean outfall area off the northern Taiwan coast

The distribution, partitioning and concentrations of trace metals (Cd, Cr, Cu, Fe, Mn, Pb and Zn) in seawater, including dissolved and particulate phases, and in copepods in the ocean outfall area off the northern coast of Taiwan were investigated. Normalization of metal concentrations to the background metal concentration to yield relative enrichment factors (EF), which were used to evaluate the contamination of dissolved and particulate trace metals in seawater around the ocean outfall. The EF results indicated that the outfall area was significantly contaminated by dissolved Fe and Zn, and by particulate Fe, Cr, Cu, Pb and Zn. In addition, most trace metals were chiefly in the particulate phase. The average percentage of total metal concentrations (dissolved plus particulate phases) bound by suspended particulate matter followed the sequence Al(95%) = Mn(95%) > Pb(88%) > Cu(86%) > Fe(72%) > Zn(32%) > Cr(17.5%) > Cd(3.4%). Therefore, metal contamination is better evaluated in solid phase than in the dissolved phase. The concentration ranges of trace metals in the copepods, Temora turbinata, Oncaea venusta and Euchaeta rimana, near the outfall were: Cd, 0.23-1.81 microg g(-1); Cr, 16.5-195 microg g(-1); Cu, 14-160 microg g(-1); Fe, 256-7255 microg g(-1); Mn, 5.5-80.8 microg g(-1); Pb, 2.6-56.2 microg g(-1); Zn, 132-3891 microg g(-1); and Al, 0.21-1.13%. Aluminum, and probably Fe, seemed to be the major elements in copepods. The concentrations of trace metals in copepods, especially Temora turbinata, near the outfall were generally higher than those obtained in the background station. The mean increase in bioconcentration factor of metals in copepods ranged from 4 to 7 and followed the sequence Al(6.4) > Cu(6.2) > Fe(6.0) > Zn(5.7) > Pb(5.6) > Cr(5.5) > Cd(5.1) > Mn(4.7). Therefore, marine copepods in the waters of northern Taiwan can accumulate trace metals over background concentrations and act as contamination indicators.     

Outflow of trace metals into the Laptev Sea by the Lena River

Freshwater concentrations confirm the pristine character of the Lena River environment as already pointed-out in a previous study with a limited set of data (Martin et al., 1993). Total dissolved concentrations of the freshwater are 13.8 ± 1.6 nM, Cu, 4.4 ± 0.1 nM, Ni, 0.054 ± 0.047 nM, Cd, 642 ± 208 nM, Fe, 0.2–0.3 nM Pb and 1.2 ± 1.0 nM, Zn. For Zn and Pb, a simple mixing of the Lena River waters with the Arctic waters is observed. Relationships with salinity suggest that for Cu, Ni and Cd, there is a mobilization of the dissolved fraction from the suspended matter, with an increase of the dissolved concentration of 1.5, 3 and 6 times, respectively. For Fe, the total dissolved concentrations follow an exponential decrease in the mixing zone and 80% of the total “dissolved” Fe is removed from the solution. For Cu, Ni, Cd and Fe, the riverine end-members are 20 nM, 12 nM, 0.3 nM and 47 nM, respectively. When considering the input of total dissolved metals to the Arctic Ocean, the fraction attributed to the freshwaters from the Arctic rivers appears to be small (4% of the input of dissolved metal to the Arctic Ocean for Cd, 27% for Cu, 11 % for Ni and 2% for Zn). Metal concentrations in the Laptev Sea and Arctic Ocean are very similar, indicating a generally homogeneous distribution in the areas sampled.     

Simulating a heavy metal spill under estuarine conditions: Effects on the clam Scrobicularia plana

We describe the effect of heavy metals Zn, Cd, Pb and Cu on the induction of methallothioneins on the clam Scrobicularia plana along a salinity gradient simulated under laboratory conditions. The clams were exposed to constant heavy metal concentrations in a dynamic estuary simulator during a 15-day assay to investigate possible induction of metal-binding proteins in them. The concentration of heavy metals in water was analysed. Clams were analysed for methallothionein concentrations. The speciation of Zn, Cd, Pb and Cu along the salinity gradient was modelled. Zn showed the highest concentrations and its prevalent species was the free ion. Intersite differences have been observed in methallothionein concentration and related to the salinity gradient. It seems that synthesis of methallothioneins is the result of physiological forces acting in concert with the changes in the chemical speciation of metals, owing to the trace metals uptake is controlled by means of an interaction of physiology and physicochemistry.     

四种金属离子对中国对虾无节幼体生长的毒性影响

对虾工厂化育苗在我国沿海已经普及,对虾人工养殖也在沿海地区蓬勃发展,到1992年养殖面积已达200多万亩,人工育苗场全国约有上千个。养殖对虾已成为我国水产业中规模最大、经济效益最高的水产品。但近几年来沿海地区的工业飞速发展,沿岸海水均受到了不同程度的污染,各对虾育苗场卵孵化率普遍下降。今年我国养殖对虾又出现了大面积暴发性死亡,原因是复杂的,但作者认为,治虾病之本应是治水质。众所周知,一切生物的幼体阶段都是最敏感的时期,海水中的金属离子对对虾幼体生长的影响已有报道(吴彰宽等,1988; Lawrence et al.,1981),但其实验环境、方法及条件各有不同。作者于1992年5月至1993年4月在海阳育苗场作了现场实验,本文根据实验结果分析和研究了Zn、Cd、Pb、Cu金属离子对中国对虾受精卵及无节幼体生物毒性的影响;不同pH值海水加入不同浓度的混合金属离子,对无节幼体生长的毒性影响;不同盐度的海水加入不同浓度的混合金属离子对无节幼体生长毒性的影响。     

Behavior of Cu, Ni and Cd during nutrient depletion in a spring bloom in Funka Bay

The concentrations of Cu, Ni and Cd were determined in Funka Bay during a spring phytoplankton bloom, consisting of diatoms. Just after the bloom, both dissolved Cd and nutrients were removed in the euphotic zone. However, the removal ratio of Cd to phosphate was very different from that in seawater. The removal of Cd took place at a Cd/phosphate ratio of 0.07×10⁻³, which was lower than in seawater before the bloom (0.25×10⁻³), leading to an increase in this ratio in seawater exceeding 0.7×10⁻³ at the end of the bloom. Elevated concentrations of Cd and phosphate were observed in the deeper layer after the bloom due to the decomposition of detrital materials produced in the bloom. The ratio of Cd/phosphate in the regeneration step was 0.24×10⁻³ which was different from the removal ratio of 0.07×10⁻³. These observations suggest that the high Cd/phosphate ratio in the regeneration would reflect a relatively high regeneration rate of Cd than that of phosphate. No significant decrease in Cu and Ni concentrations was observed during the development of the bloom, suggesting that biological removal of these metals was not so significant during the spring bloom. The concentrations of Cd, Cu and silicate in surface waters increased after the bloom with decreasing salinity due to the influence of a spring thaw.     

Mobilization of metals from riverine suspended matter in seawater

Suspended matter from rivers in the Russian Far East was leached by seawater to assess the extent of Zn, Cd, Pb, and Cu release from the land-derived solids to estuarine and coastal waters. The concentration of solids in the leaching experiments was 0.25 g/l. The suspended matter used varied in metal content from background levels to heavily contaminated.The concentration of Zn, Cd, Pb, and Cu in the leaching solution after 1, 4, 24, 48, and 96 h was determined by anodic stripping voltammetry. Measurable Cd was transferred from river suspended matter to seawater with both background and elevated Cd concentrations, though the amount of Cd released was different. The increase in Zn and Pb in solution was observed only at the enriched concentration of metals in the suspended solids. The Cu transfer into solution was more pronounced from material with elevated Cu concentration, but the amount of degradable organic matter in the solid phase was more important.The losses of metals from the riverine solids varied from 60% to 80% of total concentration for Cd to negligible for Pb, independent of contamination. The Zn loss depended on the initial concentration in the solids and decreased from 11–16% for the heavily contaminated suspended matter to 3–8% for the moderately enriched ones and to negligible for the pristine solids. Cu loss varied from 1% to 30% of total content, with no clear dependence on concentration in the suspended matter.The significance of additional input of dissolved metals to estuarine and coastal waters from remobilization was assessed by comparison with the initial concentration of dissolved metals in river water. Such experiments could be used to assess the water quality impact of atmospheric fallout of contaminated solids and storm drainage from the urbanized areas, in addition to river suspended matter studies.     

Simulating a heavy metal spill under estuarine conditions: effects on the clam Scrobicularia plana

We describe the effect of heavy metals Zn, Cd, Pb and Cu on the induction of methallothioneins on the clam Scrobicularia plana along a salinity gradient simulated under laboratory conditions. The clams were exposed to constant heavy metal concentrations in a dynamic estuary simulator during a 15-day assay to investigate possible induction of metal-binding proteins in them. The concentration of heavy metals in water was analysed. Clams were analysed for methallothionein concentrations. The speciation of Zn, Cd, Pb and Cu along the salinity gradient was modelled. Zn showed the highest concentrations and its prevalent species was the free ion. Intersite differences have been observed in methallothionein concentration and related to the salinity gradient. It seems that synthesis of methallothioneins is the result of physiological forces acting in concert with the changes in the chemical speciation of metals, owing to the trace metals uptake is controlled by means of an interaction of physiology and physicochemistry.     

Some peculiarities of the trace-metal distribution in Baltic waters and sediments

Between 1980 and 1984 extensive studies were carried out in the Baltic Sea on trace metals (Cd, Co, Cu, Fe, Hg, Mn, Ni, Pb and Zn) in water, suspended matter and sediments. The results enabled the influence of different factors on metal distribution patterns to be considered. The vertical profiles of dissolved and particulate metals in waters of the central deep basins reflect influences caused by oxygen deficiency and anoxic conditions in near-bottom water layers. Peculiarities at Station BY15 in the Gotland Deep included high dissolved Fe, Mn and Co concentrations and remarkable enrichment of Zn (0.64%), Cd (51 μg g⁻¹) and Cu (0.15%) in particulate matter from the anoxic zone. Manganese-rich particles were accumulated above this layer.In fine-grained soft sediments below anoxic deep waters, maximum contents of Cd, Cu and Zn were observed, relative to other coring sites, between Bothnian Bay and Lübeck Bight. The Hg content in sediments probably reflects the joint flocculation with organic matter. Land-based sources seem to play the leading part for maximum lead contents.     

Contrasting behaviour of trace metals in the Scheldt estuary in 1978 compared to recent years

Dissolved and particulate trace metals (Cu, Cd, Pb, Zn, Ni, Fe and Mn) measured at six stations along the Scheldt estuary in October/November 1978 are compared with more recent data. Based on Ca content in the suspended matter, three distinct geochemical regions could be distinguished: the upper estuary (salinity 1–7) dominated by fluvial mud, mid-estuary (salinity 7–17) where the composition of the suspended matter remained relatively constant, and the lower estuary where marine mud prevailed. Re-suspension of sediments is the major factor controlling the composition of the particles in the upstream region. Anoxic conditions prevailed in the upper part of the estuary extending to a salinity of 15 in 1978, while at present the seaward boundary of the anoxic water body is located at less saline waters. Furthermore, the present-day metal load is much lower than in 1978. As a consequence of the changed situation, maxima in dissolved concentrations of redox-sensitive metals in the mid/lower estuary have moved as well, which affects the trace metal re-distribution pattern. In the anoxic zone, exchange processes between dissolved and particulate metal fractions were strongly redox regulated, with Fe and Mn as excellent examples. Iron was removed from the dissolved phase in the early stages of mixing resulting in an increase in the suspended particulate matter of the leachable ‘non-residual' Fe fraction from 2 to 3.5%. Due to its slower kinetics, removal of Mn from solution occurred in mid-estuary where oxygen concentrations increased. Cu, Cd and Zn on the contrary were mobilised from the suspended particles during estuarine mixing. External inputs of Pb, and to a lesser extent of Cu, in the lower estuary resulted in the increase of their particulate and the dissolved concentrations. Calculated K_d (distribution coefficient) values were used to assess the redistribution between the dissolved and particulate phase of the investigated metals. Due to the existence of the anoxic water body in the upper estuary, the importance of redox processes in determining the K_d values could be demonstrated. The sequence of K_d values in the upper estuary (Fe, Cd, Zn, Pb > Cu > Ni, Mn) is significantly different from that in the lower estuary (Fe > Mn > Pb, Ni, Zn, Cu, Cd). Thus, in such a dynamic estuary single metal-specific K_d values cannot be used to describe redistribution processes.     

The biogeochemistry of some heavy metals and metalloids in the Ob River estuary-Kara Sea section

The biogeochemical behavior of the group of heavy metals and metalloids in the water (including their dissolved and suspended particulate forms), bottom sediments, and zoobenthos was studied in the Ob River estuary-Kara Sea section on the basis of the data obtained during cruise 54 of the R/V Akademik Mstislav Keldysh in September–October 2007. The changes in the ratios of the dissolved and suspended particulate forms of Fe, Mn, Zn, Cu, Pb, Cd, and As were shown, as well as the growth of the fraction of adsorbed forms in the near-bottom suspended particulate matter under the mixing of the riverine and marine waters. The features of the metals’ accumulation in the typical benthic organisms of the Ob River estuary and the Kara Sea were revealed, and their concentrating factors were calculated based on the specific conditions of the environment. It was shown that the shells of the bivalves possessing a higher biomass compared to the other groups of organisms in the Ob River estuary play an important role in the deposition of heavy metals. The mollusks of the Ob River estuary accumulate Cd and Pb at the background level, whereas the Cu and Zn contents appear to be over the background level.     

The pathway and fate of the heavy metal mixture in Xiamen marine experiment enclosures

The pathway and fate of heavy metals were studied in 10m3 enclosures at Xiamen Bay in 1985. The dissolved metals added are removed rather quickly during the first days, and their half-removal times ( t1/2) (d) are as follows: Pb 5. 4-5. 8, Hg 6. 7-14, Zn 11-22, Cu 16 - 29, and Cd 30-89. Zinc is transferred biologically to particles during phytoplankton bloom. The main Fate of added metals after 27 days is as follows; over 80% Cd and 60% Cu remain in dissolved phase, more than 60% Pb and 50% Hg transfer to settling settlement, while Zn is equally distributed in dissolved phase and settling settlement. The wall uptake is less than 2% of the total metals added. Organic materials play an essential role in the partition and the transfer of heavy metals in water column. Terrigenous and autochthonous particles show different affinities to different metals. Most heavy metals associate weakly with zooplankton. The Binding of Cd, Pb, Zn and Cu to the particles shows distinctive features related to the diagenetic     

大辽河口溶解态重金属的变化特征及影响因素研究

分别于2009年7月和2010年4月在大辽河口采集表层水样,测定了水体中溶解态Cu、Pb、Zn、Cd和Cr的含量,并对其分布特征及影响因素进行探讨。结果表明:除2010年4月Cu,及个别站位Pb、Zn含量较高外,表层水重金属含量均达到国家一类海水水质标准。2010年4月表层水中Cu、Pb、Zn、Cr的浓度大于2009年7月,2航次Cu、Cd、Cr的含量由河向海呈逐渐上升趋势,2010年4月Pb、Zn的含量表现为河口段高于口外海滨。重金属的含量和分布主要受径流量、潮汐作用以及风浪扰动的影响。     

福建东山湾海水中溶解态重金属平面分布及影响因素初探

根据2011年5月(春)和8月(夏)福建省东山湾海洋生态环境的调查数据,研究了海水中溶解态重金属(Cu、Pb、Zn、Cd和Cr_(T))的平面分布特征及其影响机制,结果表明:(1)海水中溶解态重金属含量平面分布呈在西南部形成“点源汇集状高值区”且自西向东逐渐递减趋势;除锌元素外,重金属含量季节变化趋势均为夏季>春季。(2)20世纪80年代以来,除海水中Zn含量逐年增加外,Cu、Pb和Cd等污染物含量的变化趋势基本符合倒“U”形环境库兹涅茨曲线。(3)采用数理统计软件分析各溶解态重金属含量之间相关性,春季海水中重金属含量除总铬外,其余4种重金属含量两两呈显著正相关;夏季海水中重金属含量仅Cu-Cd和Cd-Cr_(T)相关性较好。(4)温度、盐度、pH值、化学需氧量、溶解氧、营养盐和生物效应是海水中溶解态重金属含量变化重要的影响因子。     

THE CONCENTRATION AND DISTRIBUTION OF TRACE METALS IN THE SURFACE WATERS OF XIAMEN HARBOR

Dissolved, weakly and strongly bound particulates Cu, Pb, Zn, Cd, Co, Ni and Fe have been measured in the surface water sampled from eleven stations in Xiamen Harbor by clean laboratory methods and GFAAS. The average concentrations found in dissolved fractions are Cu: 0.41±0.12; Pb: 0.014±0.008; Zn: 0.084±0.043; Cd: 0.022±0.004; Co: 0.009±0.004; Ni: 0.15±0.02; and Fe: 0.15± 0.02 μg/kg, which make up 62%, 6%, 12%, 85%, 5%, 25% and <1% of the total metals in the surface water respectively. The results are mucn lower than those reported previously in the coastal waters of China. Industrial sources of trace metal contamination are likely responsible for the distribution of trace metals.     

FORM DISTRIBUTION OF Zn, Cd, Pb AND Cu IN WATERS OF THE NORTHWEST BOHAI GULF

The forms distribution of Zn, Cd, Pb and Cu in waters of the Northwest Bohai Gulf is investigated by inverse polarography of anti-adsorption physically coated mercury film electrode, the higher content of most forms of trace metals is in polluted estuary water, and unstable Zn and Pb are in anomalous distribution. The average concentrations read ΣZn 20.0μg/1 (14.5-36.6 μg/l, ΣCd 0.11pg/1 (0.080-0.14μg/1), ΣPb 1.0μg/1 (0.58-1.6 μg/1), and ΣCu 5.2μg/1) (2.37-8.43 μ/1) respectively.