Remobilisation of 109Cd, 65Zn and 54Mn from freshwater-labelled river sediments when mixed with seawater

A major fraction of trace metals transported by rivers is associated with sediments, especially during flooding, when erosion and resuspension increase sediment loads. Upon contact with seawater in estuaries, changes in ionic strength and pH may remobilise trace metals from sediment surfaces into more bioavailable forms. The objective of the present work was to investigate time-dependent interactions between trace metals and freshwater sediments and their potential remobilisation upon contact with seawater. Two river sediments (one organic and one inorganic) were labelled with 109Cd2+, 65Zn2+ and 54Mn2+ radioactive tracers for periods up to 6 months. Sorption of tracers occurred rapidly (> or = 80% sorption, < 1 h), followed by a slower approach to pseudoequilibrium. Kd(6 months) were estimated as 460, 480 and 2200 ml/g (inorganic sediment) compared to 5300, 4000 and 1200 ml/g (organic sediment) for 109Cd, 65Zn and 54Mn, respectively. Remobilisation of tracers from labelled sediments was studied using sequential extractions. Artificial seawater extracts simulated an estuarine environment. Subsequent extractions provided information about more strongly sorbed tracer fractions within sediments. Remobilisation of 109Cd by seawater was significant (> 65%) and least affected by sediment type or freshwater labelling time. Redistribution of Cd to strongly bound phases was minimal (4% and 1% of 109Cd in strongly oxidisable fractions). Seawater remobilisation of 65Zn was significantly greater from the organic sediment (54%) compared to the inorganic sediment (8%), where a large fraction of 65Zn (14%) became irreversibly bound. Similarly, more 54Mn was remobilised by seawater from the organic sediment than the inorganic sediment (66% and 3% remobilised, respectively), i.e., 54Mn became more strongly bound in the inorganic sediment. A simple three-box model, based on first-order differential equations, was used to describe the interaction between tracers in spiked freshwater and two operationally defined sediment fractions ("seawater exchangeable" and "seawater unexchangeable") up to 6 months of freshwater labelling. Model simulations were fitted to experiment data and apparent rate constants were calculated using numerical optimisation methods. Sorption ratios from modelling data (i.e., k1/k2) were greater for organic compared to inorganic sediments, while fixation ratios were higher in inorganic sediments. In conclusion, trace metals can be remobilised from sediments on contact with seawater in estuaries. High organic content in sediments increased initial sorption of tracers but inhibited redistribution to more strongly bound fractions over time, resulting in greater remobilisation of tracers when in contact with seawater.     

Fractionation studies and bioaccumulation of sediment-bound heavy metals in Kolleru lake by edible fish

Kolleru lake is the largest fresh water lake in the districts of East and West Godavari of Andhra Pradesh, India. Many anthropogenic sources contribute to the heavy metal pollution in the lake and the bioaccumulation of heavy metals in fish helps in assessing the aquatic pollution. Total contents and fractionation of selected heavy metals, viz., Zn, Cu, Cd, Pb, Cr, Ni and Co were measured in sediment sample and three edible fish. The investigation aimed at revealing differences in the accumulation pattern of heavy metals in fish inhabiting sediments characterized by varying metal bioavailability. The metal concentrations were found to be greater than the background concentrations of sediments indicating the anthropogenic origin of metals. Good recovery values were obtained for metal contents in sediments and fish. Large fractions of Zn, Cd and Cu were associated with mobile fraction of sediment and showed greater bioaccumulation in fish whereas Ni and Co were least mobilisable. The results clearly indicate that the fish of Kolleru lake are contaminated with metals and not advisable for human consumption.     

Pollution load of Pb,Zn, and Cd and mineralogy of the recent sediments of Jordan River/Jordan

The present geochemical analyses of Zn, Pb and Cd in eighteen subsurface sediment samples collected from two locations along the Jordan River show that Cd is anthropogenically enriched in these sediments. In the sediment column, the concentration of Zn, Pb and Cd decreases clearly with depth in the first location of the upper reach, due to the high rate of sedimentation in this location; whereas the enrichment of elements of the lower reach increases gradually towards the old sediments. The Anthropogenic factor of the studied metals lies in the sequence of Pb>Cd>Zn.     

武汉地区湖泊沉积物重金属的分布及潜在生态效应评价

对武汉地区6个湖泊沉积物重金属元素Hg、Cd、Cu、Pb、Zn、As、Cr、Ni的空间分布特征及其潜在生态效应进行研究。调查区的湖泊底泥重金属含量表现出市区内湖泊沉积物的重金属含量普遍高于郊区湖泊,其中墨水湖中重金属含量最高;湖泊沉积物柱重金属元素垂向分布表现为城区受到一定程度污染的湖泊某些元素表现出表层沉积物显著高于底部沉积物含量的特征,而郊区湖泊除Cd外其它元素垂向含量变化不大,说明郊区湖泊受到人为影响较小。利用潜在生态危害指数法对湖泊沉积物进行生态危害评价,显示武汉地区湖泊元素生态危害排序为：Cd>Hg>As>Cu>Pb>Zn;墨水湖沉积物重金属潜在生态危害相对最高,其次是金银湖;其它湖泊重金属生态危害都比较轻,总体而言武汉湖泊重金属生态危害还是较小的。但参照国外沉积物基准的生态数据库阈值,市区受到人为污染较严重的湖泊沉积物可能会对生物产生负面影响。     

Correlations between speciation of Cd,Cu, Pb And Zn in sediment and their concentrations in total soft tissue of green-lipped mussel Perna viridis from the west coast of Peninsular Malaysia

Total concentrations and speciation of cadmium (Cd), copper (Cu), lead (Pb) and zinc (Zn) in surface sediment samples were correlated with the respective metal measured in the total soft tissue of the green-lipped mussel Perna viridis, collected from water off the west coast of Peninsular Malaysia. The aim of this study is to relate the possible differences in the accumulation patterns of the heavy metals in P. viridis to those in the surface sediment. The sequential extraction technique was employed to fractionate the sediment into 'freely leachable and exchangeable' (EFLE), 'acid-reducible,' 'oxidisable-organic' and 'resistant' fractions. The results showed that significant (P<.05) correlations were observed between Cd in P. viridis and Cd in the sediment (EFLE fraction and total Cd), Cu in P viridis and Cu in the sediment (EFLE and 'acid-reducible' fractions and total Cu) and Pb in P viridis and Pb in the sediment ('oxidisable-organic' fraction and total Pb). No significant correlation (P > .05) was found between Zn in P viridis and all the sediment geochemical fractions of Zn and total Zn in the sediment. This indicated that Zn was possibly regulated from the soft tissue of P. viridis. The present results supported the use of P viridis as a suitable biomonitoring agent for Cd, Cu and Pb.     

Geochemistry and bioavailability of metals in sediments from northern San Francisco Bay

In this study, metals (Be, Cr, Mn, Fe, Ni, Cu, Zn, Ag, Cd, Pb and Hg) in the fine-grained fraction (<63 microm) from 12 sites at different locations in northern San Francisco Bay over a year period from March 2000 to March 2001 were analyzed after acid extraction. The results showed that metal concentrations in the sediments varied from site to site, whereas some of them were found elevated with respect to the sediment of Tomales Bay, CA, which has little contamination history, indicating an enrichment of the metals in the sediment samples analyzed. Sediment toxicity and bioaccumulation evaluation by a clam species, Macoma nasuta, exposed to the sediment samples collected from the six sampling sites was carried out. The results showed that the sediment samples tested significantly reduced clam survival. Toxicity of the sediments to the clam was, in part, related to elevated metal concentrations in the sediments. In order to examine geochemistry of the metals and to understand potential correlations between metal concentrations and geochemical matrix elements of the sediments, bioavailability and toxicity of the metals, detailed analysis of metal concentrations associated with total organic carbon and the Fe-oxy-hydroxides in the sediment samples was performed. The analysis showed that sediment geochemistry appeared to influence metal bioavailability and may have important impacts on the toxicity of these metals to the clam.     

鄱阳湖主要入湖口重金属的分布及潜在风险评价

于2011年5月在鄱阳湖的主要入湖口采集了水样和表层沉积物,测定并分析了其中Cu、Zn、Pb、Cd 4种重金属元素的含量和分布。同时采用地积累指数法、潜在生态危害指数法和生态毒性效应等评价方法对沉积物中重金属的污染状况进行了分析评价。结果显示：鄱阳湖主要入湖口水体重金属Cu、Zn、Pb、Cd含量均符合国家渔业水质标准要求,除修河的Pb和信江、饶河入湖口的Cd含量属于国家地表水Ⅱ类水质外,其它所有样地的4种重金属含量均低于国家地表水I类标准限值。沉积物中4种重金属含量均超过鄱阳湖相应背景值且呈积累富集的趋势,其中信江入湖口、饶河入湖口以及三江口已受到重金属的严重污染,潜在生态危害均为中等,而污染最轻的区域为南主湖区。揭示重金属污染程度顺序为Cu＞Zn＞Pb＞Cd;单个重金属潜在生态风险顺序为Cd＞Cu＞Pb＞Zn。进一步的生态毒性效应评价结果表明,虽然鄱阳湖主要入湖口沉积物已经受到重金属污染,但对多数底栖生物未产生明显毒害     

滴水湖沉积物中重金属污染特征与评价

分析滴水湖及其周边沉积物中Hg、As、Cu、Cd、Pb、Zn和Cr等7种重金属含量特征,并用地累积指数法、潜在生态风险指数法和主成分分析法对沉积物中的重金属污染状况进行了评价和分析。结果表明,滴水湖沉积物中As和Pb低于上海市潮滩背景值,Hg、Cd、Zn和Cr均高于潮滩背景值,50%样点的Cu高于潮滩背景值;地累积指数法评价结果表明滴水湖沉积物中Cr的平均污染水平为偏中污染,Hg、Cd和Zn为轻度污染,As、Cu和Pb为清洁水平;潜在生态风险指数法评价结果表明滴水湖沉积物重金属为中等生态风险,Hg和Cd是潜在生态风险的主要贡献元素;主成分分析结果表明,滴水湖沉积物中Hg、Cu、Cd、Pb、Zn和Cr主要来自于人为源,As主要来自底质滩涂     

玄武湖沉积物中重金属的垂直分布

选取中国典型城市内湖--南京玄武湖为研究对象,采用目前运用较为广泛的欧洲标准测试分析委员会(now the Standards,Measurements and Testing Programme)推荐的BCR连续提取法对沉积物中Pb、Cd、Ni、Zn、Cr和Mo 6种重金属形态在垂向上的分布进行测定,并对其潜在迁移风险进行讨论。结果表明：玄武湖沉积物中6种重金属总量由大到小的顺序为：Zn＞Cr＞Mo＞Ni＞Pb＞Cd,含量分别为14880~24412、11255~13578、5519~7730、4142~4981、857~2005和129~173 mg/kg,除Pb外均高于南京土壤环境背景值。在50 cm的柱状沉积物样品中,Pb与Cd主要以可氧化态和残渣态存在,Mo、Ni、Zn和Cr主要以残渣态为主要的存在形态。6种重金属的总量与不同形态在垂向上的分布因金属种类不同有所差异。玄武湖沉积物中含有丰富的有机质(80%~110%),且pH值为偏酸性至近中性(582~713),沉积物中的重金属具有较高的潜在迁移风险,在城市湖泊污染治理中应予以足够的重视     

玄武湖沉积物中重金属污染的潜在生物毒性风险评价

采用ICP－MS仪测定了玄武湖沉积物中Zn、Cd、Ni的含量,并应用沉积物质量基准法(SQGs)和地累积指数法（Igeo）对重金属的潜在生物毒性进行分析。结果表明：玄武湖沉积物中Zn、Cd和Ni的含量分别为7526~17911、517~898和4776~14728 mg/kg,分别是为南京土壤环境背景值的108~291、5170~8980和133~411倍,表明Zn的污染程度较轻,Cd和Ni的污染较重,且人为活动对重金属含量有重要影响。沉积物中重金属的分布具有明显的区域特征,Zn、Cd、Ni浓度的最大均值均出现于东南湖(SE L)的沉积物中。利用地累积指数法和生物数据库基准对玄武湖表层沉积物进行生物毒性风险评价得出的结论与此相似,潜在生物毒性风险的顺序依次为Cd＞Ni＞Zn。从采样点的布设来看,东南湖的潜在生物毒性风险最严重。     

Effects of cadmium and zinc on larval growth and survival in the ground beetle,Pterostichus oblongopunctatus

Carabid beetles, like Pterostichus oblongopunctatus, living in metal contaminated areas may be exposed to elevated levels of metals within their diets. However, when compared to other second order consumers, they have one of the lowest observed levels of metals, indicating methods of detoxification to deal with such toxicants. In this study, we investigated if chronic, multigenerational exposure to metals leads to resistance to toxic metal concentrations, and if so, what are the costs associated with them. Adult organisms were collected from two sites, a polluted and a reference site near Olkusz, in southern Poland. These adults were immediately mated, and eggs were collected twice weekly to assess the effects in the larvae of the F(1) generation. Larvae were randomly exposed to one of four artificial mediums: control, 50 mg kg(-1) Cd, 500 mg kg(-1) Zn, and a combined treatment of 50 mg kg(-1) Cd and 500 mg kg(-1) Zn to investigate possible interactions. Individuals were sacrificed at 10, 30, and 40 days. Although metals were not accumulated in larvae (p>0.05), larvae fed the Cd or the Zn treatment grew significantly slower, and had the lowest survival rate (p<0.05) in respect to control. Out of metal treated animals, those on the combined treatment of CdZn grew the quickest and had the highest observed survival (p<0.05). Although previous studies have demonstrated changes in adult population parameters under chronic, multigeneration exposure to toxic metal concentrations, our study did not reveal any changes in the larval stage.     

丹江口水库典型库湾及支流沉积物重金属污染分析及生态风险评价

对丹江口水库上游汉江支流及库湾沉积物中6种重金属元素的污染特征进行分析,采用效应阈值标准(NYSDEC)和Lars Hkanson潜在生态风险指数评价重金属的污染程度和环境风险。研究表明,库湾沉积物与支流沉积物中Ni、Pb含量较为接近;库湾沉积物中Cd、Cr、Cu、Zn含量分别高达186、2712、9991、4783 mg/kg,均超过支流沉积物中相应重金属含量2倍以上。各采样点表层（0~10 cm）沉积物中Pb含量均低于LEL值（最低效应阈值）,Cd、Ni含量均介于LEL值和SEL值（最高效应阈值）之间,而Cr、Cu、Zn含量均有超过SEL值的现象发生。考察沉积物重金属的富集程度发现各采样点表层沉积物中Ni和Pb均未发生富集,而Cd、Cr、Cu和Zn均存在不同程度的富集,其平均富集系数分别为712、180、163和284。根据重金属含量的相关性可知Ni和Pb主要来自于天然地球化学来源,而Cd、Cr、Cu和Zn则主要受人为源影响。以丹江口库区土壤（黄棕壤）中重金属背景值为参比,发现表层沉积物总体处于高生态风险,且以Cd生态风险为主;参与评价的5种重金属潜在生态风险程度顺序为Cd＞Cu＞Cr＞Zn＞Pb     

Heavy metals in organisms and sediments from Turkish Coast of the Black Sea, 1997-1998

During the period 1997-1998, macroalgae, sea snail, mussel, fish and sediment samples were collected at different stations of the Turkish Black Sea coast in order to establish the concentration of selected heavy metals. Heavy metals analyzed were Cd, Co, Cr, Ni, Zn, Fe, Mn, Pb and Cu. The results showed that the Turkish Black Sea coast is facing heavy metal pollution. The metal concentrations in macroalgae, sea snail, mussel and sediment samples are very high. However, Cd, Pb and Cu concentrations in anchovy fish decreased, while Co, Fe, Zn, Cr, Mn and Ni contents had changed when compared previous data. The metal levels in macroalgae did not follow the same pattern as concentrations in sediments at the same station. On the other hand, concentrations of Cd, Co, Cr, Zn, Fe, Mn and Cu in sea snail, mussel and fish samples were related to sediment data in the examined stations.     

An assessment of toxicity in profundal lake sediment due to deposition of heavy metals and persistent organic pollutants from the atmosphere

A Tier I Sediment Ecological Risk Assessment of profundal lake sediment contaminated by diffuse pollution of heavy metals and POPs deposited from the atmosphere was completed. The concentrations of seven heavy metals and four groups of POPs (OCs, PCBs, PAHs, PBDEs) were determined in the profundal sediment of ten lakes in the United Kingdom and two sediment toxicity tests completed (chironomid survival and emergence and cladoceran survival and reproduction). The results showed that around half the lakes are at least moderately contaminated by Pb, Zn, Cd, As and PAHs deposited from the atmosphere and the toxicity quotient suggests that the contaminants of concern are Pb, As and PAHs, and not the other metals nor OCs and PCBs. There was toxicity in the sediment of four of the lakes. The Probable Effect Concentration Quotient values indicated that metals in the sediments of Scoat Tarn, Agden Reservoir and Llyn Llagi were likely to be responsible for the laboratory toxicity found in these lakes, with PAHs also contributing in Agden Reservoir.     

Physical resuspension and vertical mixing of sediments on a high energy continental margin (Sydney, Australia)

Four sediment cores from the continental margin adjacent to Sydney were analyzed for 210Pb, 137Cs, trace metals (Ag, Cd, Co, Cu, Mn, Ni, Pb, Zn), iron, dry bulk density, mud and moisture content. The concentrations of trace metals in the total sediment are low at all sites, although slightly elevated concentrations of Ag, Cu, Pb and Zn are present in the fine fraction of sediment (< 62.5 microns) near a major ocean outfall. Concentrations of trace metals in the fine fraction of sediment are similar in the upper 10-15 cm, indicating strong vertical mixing of the sediments, whereas an upward coarsening grain size in the upper 1-3 cm of sediment supports physical resuspension during storms. Sediment accumulation rates on the middle shelf adjacent to Sydney were estimated from downcore profiles of 210Pb and 137Cs and range between 0.2 and 0.4 cm yr-1. Although the mass fluxes of Cu, Pb and Zn within a distance of 2 km from the outfall (up to 36.1, 30.8 and 86.2 micrograms cm-2 yr-1, respectively) are greater than 20 km north of the outfall (< 23.5 micrograms cm-2 yr-1), the low concentrations of trace metals in sediments near the outfall support an efficient dispersal of anthropogenic contaminants on this continental margin.     

Speciation of elements in sediment samples collected at lakes Volvi and Koronia, N. Greece

A five-step sequential extraction procedure was applied for the determination of the distribution of seven elements (Cd, Pb, Cr, Cu, Mn, Zn, Fe) in sediment samples collected at two lakes, Volvi and Koronia, located in N. Greece. Samples were taken in two seasons, and the average concentration of the elements was calculated. The accuracy evaluated by comparing total trace metal concentrations with the sum of the five individual fractions proved to be satisfactory. Based on the results determined at one sampling point in Koronia and two sampling points along the lake Volvi, it seems that the two lakes have not yet been polluted. There were no significant changes in the individual seasonal concentrations of elements in this monitoring period. Cd, Pb, Cu and Cr are associated with the oxidizable, carbonates and residual fractions. Zn and Fe are associated with residual and reducible fractions. The metals that we most easily extracted in the samples analysed in both lakes are Pb, Cr, Cd, Cu and also Mn in the case of Koronia lake.     

Partitioning of metals in sediments from the Odiel River (Spain)

The Odiel River runs through an area known as the Iberian pyrite belt in the province of Huelva in the southwestern corner of the Iberian Peninsula. Its waters are acidic and contain large amounts of heavy metals from erosion and mining activity. In addition, the Odiel River estuary is one of the most industrialized areas in southern Spain and, consequently, receives the discharge of industrial and urban waste. Seventeen sediment samples from the Odiel and its main tributaries were analyzed for this study. The chemical partitioning of metals (Cu, Zn, Cd, Pb, Fe, Ni, Cr and Co) in each sample was determined in four fractions (acid-soluble, reducible, oxidizable and residual). The total content of each of the metals was also determined. The results showed high concentrations of Fe, Cu, Zn, Pb and Cd, undoubtedly as a result of contamination from the mining and industrial activity mentioned above. However, the concentrations of the other metals analyzed were low since there are no sources of pollution by them in the Odiel River. Based on the chemical distribution of metals, we found that Cd, Zn and Cu are the most mobile metals (i.e., metals that can pass easily into the water under changing environmental conditions). Cd is the metal that showed the highest percentages in the acid-soluble fraction (the most labile) and the lowest in the residual fraction. However, Pb, Fe, Cr and Ni are present in the greatest percentages in the residual fraction, which implies that these metals are strongly linked to the sediments.     

鄱阳湖表层沉积物中砷及重金属赋存形态及其潜在生态风险

重金属污染是水体沉积物污染的主要问题之一,研究沉积物中重金属元素的赋存形态,探索水体中重金属的来源,可以为水体重金属污染治理修复提供理论基础。采用BCR三步连续提取法对鄱阳湖枯水期表层沉积物中As和7种重金属元素（Cd、Co、Cr、Cu、Ni、Pb和Zn）的赋存形态进行了研究,并基于重金属风险评价代码（Risk Assessment Code, RAC）方法评估了鄱阳湖表层沉积物中的As和7种重金属元素的潜在生态风险。结果表明,鄱阳湖表层沉积物中As、Co、Cr、Cu、Ni和Zn主要以残渣态的形式存在(6160%~8518%);Pb主要以残渣态（5097%）和铁锰氧化物结合态（4102%）为主要的赋存形态,其可提取态所占比例为4903%,具有较高的二次释放潜力;Cd的赋存形态主要以弱酸提取态（4160%）和铁锰氧化态（2719%）为主,其可提取态所占比例高达7749%,潜在生态风险较大。RAC分析结果表明,鄱阳湖表层沉积物Cd的生态风险整体上位于高风险,需要加强对鄱阳湖Cd污染的关注。所有站点Cr的弱酸提取态所占比例均低于1%,表明鄱阳湖Cr污染的生态风险为无风险,As、Ni和Pb属于低风险,而Cu、Co和Zn位于低风险至中等风险     

Bioavailability of sediment-associated and low-molecular-mass species of radionuclides/trace metals to the mussel Mytilus edulis

Sediments can act as a sink for contaminants in effluents from industrial and nuclear installations or when released from dumped waste. However, contaminated sediments may also act as a potential source of radionuclides and trace metals to the water phase due to remobilisation of metals as dissolved species and resuspension of particles. The marine mussel Mytilus edulis is a filter-feeding organism that via the gills is subjected to contaminants in dissolved form and from contaminants associated to suspended particles via the digestive system. In this paper the bioavailability of sediment-associated and seawater diluted Cs, Co, Cd and Zn radioactive tracers to the filtering bivalve M. edulis has been examined. The mussels were exposed to tracers diluted in ultrafiltered (<10 kDa) seawater (Low Molecular Mass form) or to tracers associated with sediment particles from the Stepovogo Fjord at Novaya Zemlya in short-term uptake experiments, followed by 1-month depuration experiments in flow-through tanks. A toxicokinetic model was fitted to the uptake and depuration data, and the obtained parameters were used to simulate the significance of the two uptake pathways at different suspended sediment loads and sediment-seawater distribution coefficients. The results of the model simulations, assuming steady state conditions, suggest that resuspended particles from contaminated sediments can be a highly significant pathway for mussels in the order ¹⁰⁹Cd ≌ ⁶⁵Zn < ¹³⁴Cs < ⁶⁰Co. The significance increases with higher suspended sediment load and with higher K_d. Furthermore, the experimental depuration data suggest that Cs is retained longer and Co, Cd and Zn shorter by the mussels when associated with ingested sediments, than if the metals are taken up from the low molecular mass (LMM) phase.     

Heavy metals in sediments from Makupa and Port-Reitz Creek systems: Kenyan Coast

Copper, zinc, lead and cadmium heavy metals were determined in sediments from the Kenyan Coast. Sediment samples were obtained from Makupa and Port Reitz Creek systems. The samples were digested using concentrated hydrochloric acid and the metal content determined using Atomic Absorption Spectrophotometer (AAS). The method of analysis was evaluated using Soil-7 certified reference material (International Atomic Energy Agency, IAEA). For comparison, sediment samples were also analysed using Energy Dispersive X-ray fluorescence technique and results obtained show good agreement. Higher metal concentrations were obtained in Makupa Creek sediments (Cu, 102+/-46.0; Zn, 1017+/-840; Pb, 103+/-35.8; Cd, 51.0+/-14.3) as compared to Port Reitz Creek system (Cu, 21.6+/-7.1; Zn, 57.1+/-17.9; Pb, 26.2+/-11.6; Cd, 1.38+/-0.7). There was significant (p=0.05) variation in the elemental concentrations between and within sites. Industrial activities and a nearby municipal dumpsite were associated with the higher elemental concentrations particularly in Makupa Creek.