黄河水中无机固体粒子与4种重金属液-固界面的交换作用

于 1 996年 5— 1 2月在实验室用离子交换法对黄河干流内蒙古清水河县喇嘛湾断面黄河水中无机固体粒子与Cu2 、Pb2 、Zn2 、Cd2 的液 -固界面作用进行了研究 ,得出离子交换率E %与pH的关系 ,找出了 4种重金属离子的pH突跃范围和最大离子交换率。结果表明 ,在黄河水中 4种重金属离子主要以羟基络合物的形式M(OH) 与无机固体粒子进行一价阳离子交换。随金属离子浓度增加E %降低 ,4种重金属离子与转型沙的交换率大于未转型沙。     

Partitioning of trace metals released from polluted marine aerosols in coastal seawater

Mobilization and transfer of atmospherically transported metals to major suspended particulate matter components in seawater have been studied in a multichamber leaching experiment. Data on the meteorological air mass history, enrichment factors and sequential extraction analysis indicate that the highly polluted marine aerosol samples collected on Helgoland are of anthropogenic origin. A significant fraction of the total cadmium (81%), zinc (58%), copper (41%), and lead (40%) was released in seawater within 1 h. When exposed to the aerosol and artificial suspended particulate matter components for another 100 h, a portion of the released metals ranging from 10 to 60% was readsorbed. Zinc and lead were scavenged by iron/manganese oxides or readsorbed by the aerosol particulates. Of the total scavenged copper portion 67% was bound to phytoplankton cell walls which evidences an ecological impact of the polluted marine aerosols even in the coastal environment.     

海洋沉积物的顺序淋滤萃取分析研究现状与发展趋势

在过去几十年里,为了探索海洋沉积物中元素的赋存形态,发展了很多分离沉积物中不同元素结合态的淋滤萃取方法。这些方法对于了解沉积物中微量元素的来源、迁移、分散、活动、生物化学及物理化学行为等特征具有重要的意义,并且在海洋地球化学和海洋环境污染研究中已得到广泛应用。本文综合论述了海洋沉积物的顺序淋滤萃取分析方法的研究进展,介绍了两种影响较大的方法,对其选用的萃取试剂以及分析流程进行了详细讨论,并比较了方法的优点和不足。     

浙江三门湾表层沉积物重金属含量分布、赋存形态及生态风险评价

以三门湾表层沉积物为研究对象,对5种重金属(Zn、Cr、Cd、Cu、Pb)的含量分布、赋存形态进行分析,并运用潜在生态危害指数法、Risk Assessment Code(RAC)法、次生相与原生相比值法对重金属生态风险进行了评价。结果表明:三门湾表层沉积物重金属的含量分布整体表现为湾内高于湾外海域,人类活动是主要影响因素。运用BCR法对沉积物中重金属进行分级提取,结果显示 Zn、Cd、Cr、Cu均以残渣态为主要赋存形态(Zn:79.20%~84.25%、Cr:93.24%~96.16%、Cd:34.71%~57.58%、Cu:66.06%~79.51%),而Pb以可还原态为主(56.58%~76.44%)。评价结果中,潜在生态危害指数法和次生相与原生相比值法均显示湾内的重金属污染比湾外严重,而RAC法指出Pb污染为湾外高于湾内海域;潜在生态危害指数法和RAC均指出Cd是主要污染元素;在次生相与原生相比值法中Pb则是主要危害元素,Cd次之。     

Forms of metals in the littoral sediments in Kandalaksha Bay of the White Sea in the Russian Arctic

According to the results of the comparative study performed of the littoral sediments sampled in small inlets of Kandalaksha Bay (the White Sea in the Russian Arctic), the metals (Fe, Mn, Cu, Zn, Pb, Cr, and Li) occur mainly in a biogeochemical-stable mineral-incorporated form, which comprises 77–99% of the total metal content. The ratio of the liable form, which is easily extracted by a weak acid, is on average 3.2% for the total Fe, 2.0% for Mn, 1.7% for Cr, 5.6% for Pb, 5.8% for Zn, 6.5% for Cu, and is negligible for Li. The concentrations of the most studied trace metals are below the threshold level according to the environmental quality guidelines (the sediment analysis). The ratio of the metal forms evidences the natural origin of the elevated concentrations of both Zn and Cr in the sediments.     

烟台近岸典型生态区沉积物重金属形态分布及其污染状况

运用Tessier连续提取法,对烟台海岸带3个典型生态敏感区表层沉积物重金属Cr、Cu、Cd、Pb、Zn、Ni的形态分布和污染状况进行了分析研究。结果表明,研究区域中河口区与排污口区重金属Cr、Cu、Cd、Zn和Ni的含量较高,尤其是Cd污染严重。养殖区基本符合海洋沉积物质量第1类标准;重金属Cr、Cu、Pb、Zn和N...     

胶州湾沉积物重金属形态不同浸取方法的比较与污染讯息指示作用初探

海洋沉积物中重金属的活性形态对于指示沉积物污染状况具有重要作用;为探寻简洁且能够有效提取重金属活性形态的浸提方法;实验研究了0.1 mol/L和1 mol/L盐酸的单级提取和欧共体标准局（European Community Bureau of Reference）提出的BCR分级提取法对胶州湾表层沉积物中重金属（Cr、Cu、Ni、Pb、Zn）和Al、Fe、Mn的浸取效果。结果显示;3种提取方法提取的金属含量呈显著正相关关系;两种浓度的稀盐酸对BCR方法中的酸可提取态和可还原态金属均具有较好浸提效果;但对可氧化态金属浸提能力相对较弱。不同提取方法的人为信号指数（ASI）计算结果表明;BCR浸取法提取结果的金属ASI值最大;表明其对沉积物中金属活性形态提取效率较高;1 mol/L HCl提取结果的金属ASI值最低;可能是较高浓度强酸使沉积物较大颗粒内层中“惰性”金属被浸取出来;“增加”了金属活性组分的污染讯息信号;对沉积物中Cu、Pb和Zn而言;0.1 mol/L HCl提取结果的ASI值与BCR方法接近。经过Al归一化后;0.1 mol/L HCl浸提的重金属含量的空间分布与胶州湾的实际污染状况相吻合;表明0.1 mol/L的HCl在一定程度上能够代替复杂的BCR浸取法;此方法可简化重金属活性形态的提取步骤;适合大范围沉积物重金属污染评价。     

Speciation, distribution, and potential ecological risk assessment of heavy metals in Xiamen Bay surface sediment

Based on the survey of surface sediment in Xiamen Bay in October 2011, the speciation, distribution, and potential ecological risk assessment of heavy metals （Cu, Pb, Zn, Cd, and Cr） in this area were studied us-ing the sequential extraction method and ecological risk assessment method. The results indicated：（1） the total concentrations of these heavy metals were influenced by runoff, industrial wastewater, and sewage, and were all higher in the coastal area than the offshore area while the highest area of Pb was a little far-ther away from the coastal water due to atmosphere deposition;（2） sequential extractions suggested that Cu was mainly composed with residual and Fe/Mn-oxide bound fractions, Pb was bound to Fe/Mn-oxide, Zn and Cr were dominated by residual, and Cd bound to exchangeable and carbonate fractions; （3） the order of migration and transformation sequence was Cd＆gt;Pb＆gt;Cu＆gt;Zn＆gt;Cr and the degree of pollution was Cd＆gt;Pb＆gt;Cu＆gt;Zn＆gt;Cr;and （4） the ratios of the secondary and primary phases showed that Zn and Cr were both clean, Cu may be polluted, Pb was moderately polluted, while Cd was heavily polluted.     

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.     

基于Landsat-8 OLI影像的南沙群岛岛礁遥感调查研究

海洋沉积物中重金属的活性形态对于指示沉积物污染状况具有重要作用;为探寻简洁且能够有效提取重金属活性形态的浸提方法;实验研究了0.1 mol/L和1 mol/L盐酸的单级提取和欧共体标准局（European Community Bureau of Reference）提出的BCR分级提取法对胶州湾表层沉积物中重金属（Cr、Cu、Ni、Pb、Zn）和Al、Fe、Mn的浸取效果。结果显示;3种提取方法提取的金属含量呈显著正相关关系;两种浓度的稀盐酸对BCR方法中的酸可提取态和可还原态金属均具有较好浸提效果;但对可氧化态金属浸提能力相对较弱。不同提取方法的人为信号指数（ASI）计算结果表明;BCR浸取法提取结果的金属ASI值最大;表明其对沉积物中金属活性形态提取效率较高;1 mol/L HCl提取结果的金属ASI值最低;可能是较高浓度强酸使沉积物较大颗粒内层中“惰性”金属被浸取出来;“增加”了金属活性组分的污染讯息信号;对沉积物中Cu、Pb和Zn而言;0.1 mol/L HCl提取结果的ASI值与BCR方法接近。经过Al归一化后;0.1 mol/L HCl浸提的重金属含量的空间分布与胶州湾的实际污染状况相吻合;表明0.1 mol/L的HCl在一定程度上能够代替复杂的BCR浸取法;此方法可简化重金属活性形态的提取步骤;适合大范围沉积物重金属污染评价。     

Comparative study of digestion methods EPA 3050B (HNO₃--H₂O₂--HCl) and ISO 11466.3 (aqua regia) for Cu, Ni and Pb contamination assessment in marine sediments

Knowing the metal extraction capacity of a digestion method is crucial for a better environmental interpretation of metal concentrations determined in sediments. One of the main problems at the present is the lack of harmonization of information obtained by two of the most popular sediment partial digestion methods: ISO 11466.3 (aqua regia) and EPA 3050B (HNO?--H?O?--HCl). In the present work, the amount of Cu, Ni and Pb leached by using both methods was compared with the total content of those elements in marine sediments collected, as an example, from the Cienfuegos Bay, Cuba. Similar amounts of Cu were extracted by both methods; while leaching of Ni and Pb were different. Generally, the EPA method extracted more Ni than the ISO method. In contrast, Pb was extracted in a larger amount by the ISO method. Some explanations are given for the observed results. X-ray Diffraction, X-ray Fluorescence, Particle Induced X-ray Emission Spectrometry and Energy Dispersive X-ray coupled to Scanning Electron Microscopy were employed for this purpose. On the other hand, none of the methods studied extracted simultaneously the fraction of all the metals, probably provided by human activity (Theoretical Anthropogenic Fraction) in both sediments studied. The use of ISO 11466.3 or EPA 3050B is recommended since the analytical performance parameters of both, in combination with Flame Atomic Absorption Spectrometry, are adequate. For a better environmental interpretation of the analytical results, information on the extraction efficiency of the selected method for specific elements and sediments under study should also be provided, together with the determined concentrations.     

An evaluation of metal bioaccessibility in estuarine sediments using the commercially available protein, bovine serum albumin

The bioaccessibility of metals (Al, Ca, Fe, Mn, Ag, Cd, Co, Cu, Ni, Pb, Sn, Zn) in oxic estuarine sediments has been evaluated using solutions of a commercially available protein (bovine serum albumin; BSA) that mimic the chemical conditions encountered in the gut environment of many deposit-feeding organisms. Over a 20 h incubation period with 5 g L^− 1 BSA, metal mobilisation was generally biphasic in that a relatively short period of rapid release was succeeded by more gradual release or approach to equilibrium, although in some cases metal readsorption was evident during the time-courses. Availability to BSA, defined as metal released after 20 h relative to metal extracted by boiling aqua regia, was greatest for Cd, Ni, Ca and Zn and lowest for Fe and Mn, and correlated well with, but was an order of magnitude lower than, metal digested by acidified hydrogen peroxide. Time-courses conducted in the absence of the protein revealed that significant quantities of Ca and Mn were water-soluble, reflecting the partial dissolution of carbonates and hydrous Mn oxides, respectively. Additional experiments indicated a net increase in metal release with increasing BSA concentration and, with the exception of Ca and Mn, a substantial increase in metal mobilisation after sediment organic matter had been digested by peroxidation. These observations suggest that, apart from Ca and Mn, metal release proceeds via complexation with component amino acids of the protein, denudation of organic host phases, and exposure of inorganic, metal-bearing minerals. Accordingly, the bioaccessibility of a metal is predicted to be dependent on its (i) affinity for proteinaceous ligands, (ii) association with components of digestible sediment organic matter, and (iii) degree of binding at relatively weak sites on sediment phases that are exposed or modified by the action of proteins and other chemical constituents of the gut environment.     

Distribution of As, Cr and V species in the Po-Adriatic mixing area, (Italy)

The distribution of dissolved and participate concentrations of As, Cr and V was investigated in the mixing area of the Po river in five surveys over the period March 1992-March 1995. The data obtained indicate noticeable contamination of coastal waters of the northern Adriatic with Cr but not As or V. Total dissolved concentrations for As and V were comparable with oceanic levels but were higher by a factor of 4 for Cr. These results suggest either low anthropogenic inputs of As and V, from terrigenous and atmospheric sources, or efficient removal mechanisms. The investigated metals had low reactivity during freshwater-seawater mixing and the distribution of concentrations in the dissolved and solid phases suggests that the dilution process is the main factor controlling the transport of these metals to the sea in low-to-medium solid transport conditions. Further investigations are required to elucidate the behavior of these metals during high solid transport conditions. Significant changes in the speciation of As occurred during the transition between the two end-member matrices. In the coastal waters of the northern Adriatic, the arsenite fraction in winter, and the arsenite and dimethylarsinate fractions in summer increased with respect to riverine waters. Changes in the speciation of chromium were minor, but also showed a small increase in reduced species in marine waters.     

胶州湾及青岛近海表层沉积物重金属赋存形态研究

2008年11月和2010年11月分别在青岛近海6个站位和胶州湾9个站位采集了表层沉积物样品,应用连续提取法分离和测定其主要成分和重金属的赋存形态。结果表明,易还原态的重金属受铁锰氧化物体系显著影响,其中镍的迁移过程基本受控于该体系,有机结合态的铬和钡迁移变化受有机质一定影响,其他形态重金属主要受外源输入影响。Pb和Cr存在显著富集,相对其他金属污染较明显。Pb的生态风险最高。胶州湾东部,尤其是李村河口附近重金属污染程度和不稳定性都最为明显。     

Enzymatic mobilisation of trace metals from estuarine sediment

Proteinase K, a non-specific protease that is representative of enzymes encountered in the digestive environment of deposit-feeding organisms, has been employed to determine the nature and extent of enzymatic mobilisation of trace metals (Al, Fe, Mn, As, Cu, Pb and Zn) from contaminated estuarine sediment. The extent of metal release by the enzyme was critically dependent on whether and how the sample had been dried and, for all metals except Mn, mobilisation was greatest when the sample had not been dried. The fraction of metal available to the enzyme, f_e, defined as the amount of metal released from undried sediment after 4 h incubation relative to the total metal concentration, was less than 1% in all cases. Significantly, however, there was a strong correlation between f_e and published factors defining the enrichment of metals in the gut fluids of the deposit-feeding lugworm, Arenicola marina. This suggests that, at least qualitatively, the mechanics of metal mobilisation in situ are replicated by the commercial enzyme. Thermally denaturing the enzyme resulted in mobilisation that was greater than (As and Cu) or similar to (all other metals) release engendered by the active enzyme, suggesting that the principal mechanism of metal mobilisation is not related to proteolysis but more likely involves complexation or exchange with component amino acids of the enzyme.     

Environmental status of Daya Bay surface sediments inferred from a sequential extraction technique

The chemical partitioning of 12 trace metals (Ba, Cd, Co, Cu, Mn, Mo, Ni, Pb, Sc, Sr, U, Zn) in 9 surface sediments from Daya Bay, northern South China Sea, was studied by a four-step sequential extraction technique to assess their environmental/pollution status. The studied metals take on different fraction composition patterns, and some of them show significant spatial variation especially for Cd. A majority of the studied metals can be considered immobile because of their high percentages in the residual fraction. It seems that the Daya Bay surface sediments have not yet been polluted by the studied heavy metals which are used as parameters to classify marine sediment quality, i.e., Cd, Cu, Ni, Pb and Zn. For all metals except for Pb, the extent of anthropogenic influences on their total concentrations in the Daya Bay surface sediments is generally imperceptible. The metals’ potential risks to the environment were assessed, and the results showed that they have generally no risk or low risk except for Cd, Mn and Sr.     

The incorporation of minor transition metals into marine manganese nodules

The mechanisms of incorporation of minor transition metals into marine manganese nodules are discussed on the basis of differential chemical leaching.A small portion of iron and manganese in deep-sea nodules was dissolved in dilute acetic acid. Hydrogenous cobalt and nickel in nodules were also slightly leached with the acid solution, while 50–60 % of hydrogenous copper and zinc were leached. This difference suggests that the greater parts of hydrogenous cobalt and nickel are present in the lattices of manganese oxide phases, while the major parts of hydrogenous copper and zinc are present in the sorption sites of manganese oxide phases.The enrichment of minor transition metals in manganese nodules may be controlled by their substitution for manganese atoms in manganese oxide lattices after their sorption on manganese oxide phases.     

三亚东部近岸海域表层沉积物重金属元素地球化学特征及环境质量评价

本文对三亚东部近岸海域表层沉积物中7种重金属元素的地球化学特征和空间分布特征进行了研究,并应用地积累指数法和尼梅罗综合指数法对各重金属的污染程度进行了评价。研究发现, 三亚东部近岸海域表层沉积物中重金属含量总体较低,符合《海洋沉积物质量》一类标准,大多数重金属元素含量的空间分布主要受元素的“粒度控制律”制约,其物质来源主要为陆源细粒沉积。地积累指数法和尼梅罗综合指数法的评价结果均表明,研究区表层沉积物的重金属未达到污染程度,属清洁状态,环境质量良好。     

昌黎黄金海岸保护区表层海域沉积物中重金属的赋存形态特征及生态风险评价

为了解昌黎黄金海岸保护区表层海域沉积物中重金属的污染状况,采用欧共体标准物质局(Community Bureau of Reference,简称BCR)提出的三级4步提取法分析了沉积物中Cr、Pb、Cu、Zn、Ni的形态特征,并利用次生相原生相分布比值法(Ratio of secondary phrase and pr...