Sediment Parameters of Northwest Black Sea Shelf and Slope: Implications for Transport of Heavy Metals and Radionuclides

In June 1990, sediment cores were obtained from several locations in the Northwest Black Sea shelf and slope by a joint US/USSR scientific team aboard the survey vessel R/V VODYANITSKY. the goal of this investigation was to determine the distribution and levels of radioactivity resulting from the Chernobyl 1986 nuclear accident. the sediment was characterized for texture, mineral composition, redox state, heavy metals, and radionuclides. Correlations emerging from these data reveal paths of dispersal and transport of materials from river sources to deposition sites on the shelf and slope. Kaolinite in the clay mineral suite clearly reflects a dispersal pattern originating in the Danube River and progressing in an easterly direction across the shelf. Sand-size gypsum and the elemental heavy metals Zn, Cu, Cr, and Pb (probable industrial source) as well as the elements Al and Mg (probable terrigenous source) also show a dispersal pattern from the Danube station location in an easterly direction across the shelf. the dispersal direction indicated by these materials is not in conflict with recent existing notions concerning the hydrology of the Northwest Black Sea. Barium anomalies at a midshelf location may be related to operations in the Lebada oil fields situated updrift. Heavy mineral dispersal reflect the Danube and -Crimean Provinces established for the shelf and relate to terrestrial source areas. in addition, the heavy mineral monazite correlates with the radioactive Th 232 found most abundantly in the Crimean Province. Local anomalies of Mn, Fe and U in the sediment at station locations are related to redox (Eh) conditions and other factors. Cs^134/137 data, reported by Curtis and Broadway (1991), correspond to transport and dispersal patterns implicit in the mineralogic, anthropogenic indicators, and sediment characteristics of the study area.     

Partitioning of Cs-137 Between Sediment and Water From the Black Sea

As part of a joint USA/USSR Environmental Agreement to determine the distribution and concentration of Chernobyl radioactivity in the northwest Black Sea area, the sediment from eight stations was collected and analyzed to assess the ability of this material to adsorb radiocaesium. Batch tests were conducted in which Cs-137 tracer was added to mixtures of sediment and bottom water, with contact solutions ranging from 85 Bq ml^-1 to 1,760 Bq ml^-1. This work was done in an argon atmosphere at 9.5°C, which is the average temperature of the sediment. Isotherms were linear for all cores and distribution ratios (R_D) calculated from the slopes of the isotherms ranged from 660 to 1,660 ml g^-1. These isotherms fit a simplified Freundlich isotherm. Correlations of R_D to a number of sediment parameters describing texture and mineralogy were determined. A close relationship was observed between R_D for caesium and the percentage of illite contained in the samples.     

Partitioning of Cs-137 Between Sediment and Water From the Black Sea

Abstract

As part of a joint USA/USSR Environmental Agreement to determine the distribution and concentration of Chernobyl radioactivity in the northwest Black Sea area, the sediment from eight stations was collected and analyzed to assess the ability of this material to adsorb radiocaesium. Batch tests were conducted in which Cs-137 tracer was added to mixtures of sediment and bottom water, with contact solutions ranging from 85 Bq ml^?1 to 1,760 Bq ml^?1. This work was done in an argon atmosphere at 9.5°C, which is the average temperature of the sediment. Isotherms were linear for all cores and distribution ratios (R_D) calculated from the slopes of the isotherms ranged from 660 to 1,660 ml g^?1. These isotherms fit a simplified Freundlich isotherm. Correlations of R_D to a number of sediment parameters describing texture and mineralogy were determined. A close relationship was observed between R_D for caesium and the percentage of illite contained in the samples.     

Spatial Variations of Heavy Metals in the East China Sea Continental Shelf Surface Sediments

Surface sediments collected from continental shelf of the East China Sea were analyzed for heavy metals (iron, manganese, copper, zinc, lead, cadmium), carbonate, organic carbon contents, and grain sizes. the range of concentrations observed were iron: 0.3-1.3 wt%, manganese: 2.3-14 μmole/g, copper: 7.1-184 μmole/g, zinc: 0.16-0.77μmiole/g, lead: 15-98 μmole/g, cadmium: 0.17-3.9 μmole/g, carbonate: 3.6-87 wt%, sand: 10-100%, silt: 0-70% and clay: 0-50%.

A zonal distribution pattern of the heavy metals was found in the East China Sea Continental shelf sediments. High concentrations of most heavy metals, organic carbon and fine-grained sediments were observed in the inner shelf zone, especially those near the discharge of the Yangtze River. Concentrations of these heavy metals decreased from the inner shelf to the shelf break region. High concentrations of metals were also found in sediments near Taiwan. Iron concentrations decreased north-east of the central shelf region. High concentrations of cadmium were found in the shelf break region where biogenic carbonate is predominant. This study showed that biogenic carbonate in the East China Sea shelf break region and the terrigenous sediments from the Yangtze River and island of Taiwan were the major sources of heavy metals. Heavy metal concentrations were strongly influenced by the content of the coarse-grained quartz sand present in the sediments.     

Spatial Variations of Heavy Metals in the East China Sea Continental Shelf Surface Sediments

Surface sediments collected from continental shelf of the East China Sea were analyzed for heavy metals (iron, manganese, copper, zinc, lead, cadmium), carbonate, organic carbon contents, and grain sizes. the range of concentrations observed were iron: 0.3-1.3 wt%, manganese: 2.3-14 μmole/g, copper: 7.1-184 μmole/g, zinc: 0.16-0.77μmiole/g, lead: 15-98 μmole/g, cadmium: 0.17-3.9 μmole/g, carbonate: 3.6-87 wt%, sand: 10-100%, silt: 0-70% and clay: 0-50%.

A zonal distribution pattern of the heavy metals was found in the East China Sea Continental shelf sediments. High concentrations of most heavy metals, organic carbon and fine-grained sediments were observed in the inner shelf zone, especially those near the discharge of the Yangtze River. Concentrations of these heavy metals decreased from the inner shelf to the shelf break region. High concentrations of metals were also found in sediments near Taiwan. Iron concentrations decreased north-east of the central shelf region. High concentrations of cadmium were found in the shelf break region where biogenic carbonate is predominant. This study showed that biogenic carbonate in the East China Sea shelf break region and the terrigenous sediments from the Yangtze River and island of Taiwan were the major sources of heavy metals. Heavy metal concentrations were strongly influenced by the content of the coarse-grained quartz sand present in the sediments.     

Preliminary Caesium Data From A Cooperative Us/Ussr Monitoring Survey for Chernobyl Radioactivity in the Black Sea

In June 1990, scientists from the US Environmental Protection Agency's (EPA) Office of Radiation Programs (ORP), and the Woods Hole Oceanographic Institution (WHOI), travelled to Sevastopol in the Soviet Union to work with radioecologists and marine scientists from the USSR Institute of Biology of the Southern Seas (IBSS). the purpose of this cooperative programme was to conduct a monitoring survey for radioactivity in the northwestern Black Sea. Samples of sediment, surface and in-situ water, and biota were collected from fourteen stations for post-survey radionuclide analyses to determine levels of radioactivity in the Black Sea environment resulting from the Chernobyl nuclear power plant explosion and subsequent transport of radioactivity via the Dnepr and Danube rivers. This paper presents the preliminary data for caesium-137 and caesium-134 in sediment samples analyzed by the EPA/ORP. Caesium-137 was measured at four shallow (20–114 m) stations on the shelf near the mouth of the Dnepr and Danube Rivers, but was not detected in sediments from comparable depths at stations further off shore or in slope sediments at depths of 510–1288 meters. Caesium-134 was detected only in sediments from the shallow-water station nearest to the Danube River.     

Preliminary Caesium Data From A Cooperative Us/Ussr Monitoring Survey for Chernobyl Radioactivity in the Black Sea

In June 1990, scientists from the US Environmental Protection Agency's (EPA) Office of Radiation Programs (ORP), and the Woods Hole Oceanographic Institution (WHOI), travelled to Sevastopol in the Soviet Union to work with radioecologists and marine scientists from the USSR Institute of Biology of the Southern Seas (IBSS). the purpose of this cooperative programme was to conduct a monitoring survey for radioactivity in the northwestern Black Sea. Samples of sediment, surface and in-situ water, and biota were collected from fourteen stations for post-survey radionuclide analyses to determine levels of radioactivity in the Black Sea environment resulting from the Chernobyl nuclear power plant explosion and subsequent transport of radioactivity via the Dnepr and Danube rivers. This paper presents the preliminary data for caesium-137 and caesium-134 in sediment samples analyzed by the EPA/ORP. Caesium-137 was measured at four shallow (20-114 m) stations on the shelf near the mouth of the Dnepr and Danube Rivers, but was not detected in sediments from comparable depths at stations further off shore or in slope sediments at depths of 510-1288 meters. Caesium-134 was detected only in sediments from the shallow-water station nearest to the Danube River.     

Heavy metal accumulation in algae and sediments of the Black Sea coast of Turkey

The paper reports heavy metal accumulation in algae collected at four stations and in sediments at three stations on the Black Sea coast of Turkey. The metals analysed are Cd, Co, Cr, Cu, Fe, Pb, Sb and Zn. The metal content of algae increased generally (with some exceptions) from 1991 till 1993 in ?ile and Sinop. In the sediments Sb in ?ile, As in Riva, Fe, Zn in Sinop are high. According to these findings the metal pollution increased in Turkish area of the Black Sea during the years investigated.     

Sources and Distribution of Heavy Metals in East China Sea Surface Sediments

Box cores and surficial sediments collected from the shelf, slope and Okinawa Trough of the East China Sea were analyzed for loss on ignition, and concentration and speciation of Al, Fe, Mn, Pb, Cd, Cu and Zn. in general, concentrations of these metals are higher in the inner shelf and lower in the midshelf, but the highest LOI, Cd and Mn levels are found in the Okinawa Trough. Spatial distributions of these metals in surficial sediments indicate that the Yangtze River is the major source for materials deposited in the inner shelf. the results of a six-stage sequential leaching experiment indicate that the fluvial input includes natural (e.g., Al and Fe) and anthropogenic (e.g., Pb) materials. the depletion concentration of these metals in the midshelf sediments reflects the dominance (∼ 70%) of coarse, relict sand, while the enrichments in the inner shelf and the Okinawa Trough sediments are due to the fine grained, organic-rich sediments. the speciation of Mn in the sediments of the Okinawa Trough indicates that its distribution is diagentically or hydrothermally controlled.     

Sources and Distribution of Heavy Metals in East China Sea Surface Sediments

Box cores and surficial sediments collected from the shelf, slope and Okinawa Trough of the East China Sea were analyzed for loss on ignition, and concentration and speciation of Al, Fe, Mn, Pb, Cd, Cu and Zn. in general, concentrations of these metals are higher in the inner shelf and lower in the midshelf, but the highest LOI, Cd and Mn levels are found in the Okinawa Trough. Spatial distributions of these metals in surficial sediments indicate that the Yangtze River is the major source for materials deposited in the inner shelf. the results of a six-stage sequential leaching experiment indicate that the fluvial input includes natural (e.g., Al and Fe) and anthropogenic (e.g., Pb) materials. the depletion concentration of these metals in the midshelf sediments reflects the dominance (～ 70%) of coarse, relict sand, while the enrichments in the inner shelf and the Okinawa Trough sediments are due to the fine grained, organic-rich sediments. the speciation of Mn in the sediments of the Okinawa Trough indicates that its distribution is diagentically or hydrothermally controlled.     

Levels of heavy metals in blue whiting caught from the eastern Black Sea area of Turkey

This paper presents data on the concentrations of 5 metals, copper (Cu), cadmium (Cd), iron (Fe), zinc (Zn) and lead (Pb) in Blue Whiting sampled from the Eastern Black Sea coast of Turkey. The highest metal concentrations of Cu, Cd, Fe, Zn and Pb were recorded in Blue Whiting with the values of 2.71, 0.601, 14.137, 15.322 and 1.078 μg g^‐1 dry weight, respectively. On average the metal concentrations in Blue Whiting followed the order of Zn > Fe > Cu > Pb > Cd. Temporal differences of concentrations of these metals were significant (p < 0.05). Spatial fluctuations of Cu, Cd, Fe, Zn and Pb concentrations in Blue Whiting were also significant (p < 0.01). It was found that the concentrations of Cu, Cd, Fe, Zn and Pb in the muscle in Blue Whiting were below the limit of Public Health Regulation in Turkey.     

Behaviour of trace metals in surface sediments of the Black Sea

Early diagenetic processes control the behavior, and more specifically the dissolved‐solid phase distribution of heavy metals in sediments. The depth distribution of Co, Mn, Cu, Zn, Ni, and Fe in sediment were determined in box cores from the Black Sea. The sequential analyses results of these metals indicate contrasting behavior of Mn and Co during early diagenesis, consistent with their respective chemistries and particle‐associations. The profiles of extractable trace metals in the cores are clearly related to sediment type or depositional environment. Topmost sections of the profiles for these elements are generally similar, i.e. rapid decrease in concentration below the sediment surface.     

Heavy Metals in Sediments and Oysters From Bluefields Bay, Nicaragua

The distribution of trace metals (Co, Cu, Fe, Mn, Ni, Pb and Zn) was investigated during a year (1994-95) in surface and core sediment samples and in the oyster (Crassotrea rhizophorae) from Bluefields Bay, Nicaragua. the aim was to assess the arthropogenic impact of potential pollutant sources, mainly Bluefields City, since domestic waste waters are discharged directly or by infiltration to the bay. Lyophilised samples were submitted to different acid digestion methods and analysed by flame atomic absorption spectrophotometry. the results showed highest contents for copper, lead and zinc near Bluefields City, with an increase in the affected area in the rainy season that is generated by greater city run off. Metal contents in oysters do not show the same distribution pattern than in sediments and were similar to those from other areas without reflecting pollution levels.     

Heavy metals availability (Fe, Mn, Zn, Cu and Cr) in Aden Gulf sediments under aerobic and anaerobic conditions

The present study aims to analyse the chemical speciation of heavy metals in relation to aerobic and anaerobic conditions. Two sediment samples (from the Gulf of Aden, Yemen) were incubated under flooded conditions. In particular, the chemical forms of Fe, Mn, Zn, Cu and Cr under the experimental conditions were studied using a sequential chemical extraction method. The pH and Eh of the suspension were measured as critical parameters controlling the fate of the metals in the environment. The results showed that the metals concentration in the different forms varied with time incubation and affected by the variation of redox potential and pH value. Also, the changes in both redox potential (Eh) and pH values had evident effects on heavy metals transformation. It is obvious that the highest redox potential affected the amount of iron and manganese in the oxides form. When the redox potential decreased to-133 and-170 mV, it caused a significant transformation of the Fe-Mn oxide form to the water-soluble and exchangeable fractions. Under anaerobic conditions, the relative percentage of all five metals including the summation of four fractions (the water-soluble and exchangeable, carbonate, oxides and organic fractions) constituted 45-60% of the total amount of iron, 33-50% for manganese, 33-63% for Zn, 63-74% for Cu and 19-43% for Cr. Both zinc and copper among water-soluble and exchangeable fraction were high at the end of incubation period, this accompanied by a significant decrease in the content of the organically bound fraction. In general, the reducing conditions were more favorable for metal bound to water soluble and exchangeable fraction.     

The Influence of Anthropogenic Contamination On Metals Release From Coastal Sediment Suspensions with Aerated Sea Water

The zinc, cadmium, copper and lead release from the uncontaminated and contaminated coastal sediments with aerated sea water was studied. the metals transfer to the dissolved forms was monitored during one-two months by differential pulse anodic voltammetry (DPASV). the sediments with different initial degree of contamination were sampled in the Peter the Great Bay, Sea of Japan around Vladivostok-the biggest city in Russian Far East. Sediment contamination by metals led to increased release to solution of zinc due to sulphide oxidation and cadmium on account of organic matter decomposition. the copper behaviour was complicated by strong binding with organic matter and enhancements of copper release can only be seen in sediment with a low organic matter content. Significant lead transfer to dissolved forms was not observed regardless of sediment contamination. the temperature affected the release of cadmium and copper through enhanced organic matter destruction. the dissolved metal fluxes from the sediment transformation are compared with metal fluxes towards bottom. Such comparisons show that second contamination by dissolved metals of the studied coastal environment may be important for cadmium only.     

The Influence of Anthropogenic Contamination On Metals Release From Coastal Sediment Suspensions with Aerated Sea Water

The zinc, cadmium, copper and lead release from the uncontaminated and contaminated coastal sediments with aerated sea water was studied. the metals transfer to the dissolved forms was monitored during one-two months by differential pulse anodic voltammetry (DPASV). the sediments with different initial degree of contamination were sampled in the Peter the Great Bay, Sea of Japan around Vladivostok-the biggest city in Russian Far East. Sediment contamination by metals led to increased release to solution of zinc due to sulphide oxidation and cadmium on account of organic matter decomposition. the copper behaviour was complicated by strong binding with organic matter and enhancements of copper release can only be seen in sediment with a low organic matter content. Significant lead transfer to dissolved forms was not observed regardless of sediment contamination. the temperature affected the release of cadmium and copper through enhanced organic matter destruction. the dissolved metal fluxes from the sediment transformation are compared with metal fluxes towards bottom. Such comparisons show that second contamination by dissolved metals of the studied coastal environment may be important for cadmium only.     

辽河表层沉积物重金属生态风险与综合毒性表征

采用ICP-MS测定了辽河26个支流表层沉积物间隙水中7种重金属(Pb、Cu、Cr、Zn、Ni、As、Cd)的含量,并应用间隙水毒性基准单位(IWCTU)和Nemeraw指数(NI)对间隙水重金属生态风险进行了评价;同时利用摇蚊幼虫活体生物毒性测试方法评估了辽河流域26个支流表层沉积物的综合毒性。研究结果显示,辽河支流表层沉积物间隙水7种重金属平均含量为:Pb 3.92μg·L-1,Cu 5.73μg·L-1,Cr 7.21μg·L-1,Zn 4.33μg·L-1,Ni 4.48μg·L-1,As 5.89μg·L-1,Cd 0.29μg·L-1,根据IWCTU值和NI值,柴河、养息牧、亮子河、凡河、付家窝堡、接官厅具有潜在的生态风险;综合毒性表征结果表明,柴河、长沟子河、付家窝堡、柳河、一统河、潮沟河表层沉积物对摇蚊幼虫具有较高毒性。结合重金属毒性和综合毒性分析,认为辽河流域支流表层沉积物毒性应该是由复合污染形成,而不仅仅是重金属污染。     

Heavy Metals in the Bed and Suspended Sediments of Anyang River, Korea: Implications for Water Quality

The objective of this study is to compare Anyang River bed sediments with water chemical composition and to assess the anthropogenic chemical inputs into the river system. Eight sampling locations were chosen along the river channel. Bed and suspended river sediments and water samples were collected, and analyzed for their chemical and physical composition. Data revealed that trace element concentrations in the river water were generally below world average, except for As, Mn, Ni and Cr. Among the three phases: water, bed and suspended sediment, more than 99% of the trace elements was associated with the bed sediment. Concentrations of trace elements in the sediment were a function a particle size distribution and organic content. The calculated degrees of enrichment based on the least influenced sample (ASD 1) indicated the river sediments were enriched with respect to background. The enrichment factors for Pb, Zn and As were relatively lower than for Cr, Co, Ni and Zn. The difference in the enrichment seems to reflect the human activities influence in the basin, and specially for Cd. Speciation of the elements in the five different chemical forms in the sediment by sequential extraction indicated that the reducible fraction was predominant for Fe, Zinc and Cu showed an irregular variation among the different fractions; whereas, Cd and Pb were more regular. Zinc and Cu highly existed mostly in exchangeable forms. Acid soluble and reducible forms were also important for most metals. The speciation implies that the metals associated with the sediment are subject to release into water bodies as goechemical variables (pH and Eh) change. Currently, the introduced metals are deposited near the source area and are mostly associated with the sediment, implying that the river bed sediment acts mainly as a sink, rather than a pool. The accumulated and enriched toxic trace elements can pose a potential pollution of river water.     

莱州湾表层沉积物中重金属时空分布、污染来源及风险评价

运用污染风险评价标准和方法研究了2010年5月(春)、8月(夏)、10月(秋)和12月(冬)莱州湾表层沉积物中7种重金属污染物的时空分布特征、来源及生态风险。结果表明,表层沉积物中Cr、Zn和Pb含量均呈现春季低于其他季节特征,秋季Hg含量是其他季节的4倍,Cu、As和Pb含量无显著季节差异。表层沉积物中Cr、Cu、Zn、As和Cd最高值出现在莱州湾中部及小清河河口等西部水域,来源呈现受自然作用影响较大的特征;而Hg和Pb最高值出现在龙口和界河河口等东部水域,来源呈现受周边工业污染物的人为排放影响较大的特征。基于地理累积指数、生态效应浓度以及Hakanson潜在生态风险指数的综合评价表明,13%~29%的研究区域的表层沉积物受到轻微程度的Cd、Hg和Pb污染,Cd和Hg高值水域达到中等生态风险程度;Hg和As在65%~68%的研究区域的表层沉积物中达到可能对沉积物底质环境及生物群落产生不利生态影响水平。基于对重金属污染物的评价结果,莱州湾表层沉积物质量较好,局部区域存在Hg、Pb、Cd和As的潜在污染风险。     

A Comparative Study On the Levels of Trace Metals in Some Mediterranean and Red Sea Fishes

Samples of Mugil cephalus, Liza ramada, Siganus luridus, Siganus rivulatus, Epinephelus alexandrinus, Epinephelus areolatus, Epinephelus fasciatus, Epinephelus chlorostigma, Cephalopholis argus and Cephalopholis sonnerati were collected from the Mediterranean and Red Seas and their muscle and bone analyzed by AAS for some trace metals (Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, Pb). the results showed that these metals accumulate in the bones to a greater extent than in the muscle. the highest accumulated element is cobalt (4.7-20.8 times), while the lowest is lead (1.1-2.5 times). the accumulation is more pronounced in Red Sea species than in Mediterranean species. the elevated levels of lead in Mugil cephalus (2.6-3.0 mg kg^-1) and Epinephelus alexandrinus (3.0-3.9 mg kg^-1) were attributed to the intake in food in the polluted environment of Alexandria coastal water. the relationship between body size and concentration of trace metals using a standard linear regression technique gives a significant positive correlation for cobalt, manganese, iron and lead in the muscle, as well as for lead in the bones of Mugil species from the Red Sea, while the Mediterranean species showed little correlation.

There is a tendency for increased concentrations of the essential metals manganese, iron and copper with increasing trophic level of the fish, while the opposite is true for the toxic metals chromium and lead. Our results indicate that there is no risk from toxic metal concentrations in muscle of fish from the Mediterranean and Red Seas consumed by man even in contaminated areas.