Metal pollution of estuarine sediments caused by leaching of acid sulphate soils

This study tracks changes in metal distribution in estuarine sediments as a result of leakage from acid sulphate (AS) soil landscapes in the Boreal Zone (Finland). The main objective was to identify the impact of these nasty soils on sediment geochemistry in a biologically sensitive and shallow brackish-water estuary. In order to do this four sediment cores were sampled in a profile extending seawards from the mouth of the Vörå River, which is one of the most heavily AS soil-impacted rivers in Finland and Europe. Two of the cores were rather deep (2.5 m and 4.0 m) and the others were shallow (0.4 m and 0.8 m). The results showed that an appreciable amount of aluminium (Al), cobalt (Co), cadmium (Cd), copper (Cu), manganese (Mn), nickel (Ni) and zinc (Zn) were elevated in the surface and sub-surface of the sampled bottom sediments compared to the deeper sediment background levels. These metals are all known to be abundantly leached from the AS soils. At the site approximately 4 km away from the river mouth, the concentrations of Cd, Co, Mn, Ni and Zn were elevated 5–100 times as compared to the background levels and showed an intriguing cyclic pattern, most likely reflecting seasonal leaching dynamics in the AS soil landscapes. In contrast, metals that are not abundantly leached from AS soils, i.e. chromium (Cr), iron (Fe) and vanadium (V) had consistently low concentrations throughout all sediment cores. The elevated metal concentrations in the top layers of the sediments in the estuary are alarming. The continuous land uplift of the region combined with the episodic rapid declines in pH may result in short and long term extensive release of metals. This, in turn, may have significant effects on the trace-metal contents in the Gulf of Bothnia and the entire Baltic Sea.     

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...     

Accumulation of Phosphorus and Heavy Metals in the Peel-Harvey Estuary in Western Australia: Results of a Preliminary Study

Concentrations of P and of heavy metals (Zn, Cd, Pb, Cu) were determined in sediment cores from the Peel-Harvey Estuary in Western Australia. Two cores were extracted, each representing one of the two basins of the estuary. Sediments were dated by surplus²¹⁰Pb, by¹³⁷Cs and by changes in the Fe/S ratio. Increasing exports of P from the mainly agricultural catchments have resulted in more than a doubling of both total P and acid extractable inorganic P in sediments of the estuary. Accumulation of P in the estuary is less than expected for complete retention of inputs of P from the major tributaries. Historical data show that since 1950 average concentrations of dissolved inorganic P have approximately doubled in the Peel Inlet and increased by times seven in the Harvey Estuary. Increases in concentrations in surface sediments of acid extractable Zn, Cd, Pb and Cu are noticeable in the Peel Inlet, and of Zn and Cd in the Harvey Estuary. The greatest increase, relative to background, is shown by Zn. Concentrations of extractable Zn and Cd in surface sediments are similar to those estimated from average concentrations in the water column for equilibrium adsorption to organic matter in sediments. Extractable Pb is greater than estimated for equilibrium adsorption to sediments. Extractable Cu is of the order of what can be expected for equilibrium adsorption to sediments in the Peel Inlet, but is less than expected in the Harvey Estuary.     

Distribution of metal concentrations in sediments of the coastal zone of the Gulf of Riga and open part of the Baltic Sea

The comparison of spatial and temporal distribution of Hg, Cd, Pb, Cu, Ni, Zn, Mn and Fe concentrations in sediments from the Gulf of Riga and open Baltic Sea along the coastal zone is presented for the first time. There were considerable differences in Pb, Zn, Mn and Fe levels in sediment at various stations of the Gulf of Riga. A significant difference of Cd, Pb, Cu, Ni, Zn levels was found in sediments of various stations in the open Baltic coast. The amount of Cd, Pb, Cu, Ni, Zn and Fe levels also differed significantly in the sediments of the Gulf of Riga in different years. A considerable yearly difference in amount of Hg, Cd, Pb, Cu, Ni and Mn levels was found in sediments in the open Baltic coast. The essential highest values of Pb and Zn in coastal sediments of the open Baltic Sea are stated in comparison with the Gulf of Riga. The concentrations of other metals have only a tendency to be higher in coastal sediments of the open Baltic Sea in comparison with the Gulf of Riga. Natural and anthropogenic factors were proved to play an important role in determining resultant metals concentrations in the regions.     

Heavy metals in sinking particles and bottom sediments from the eastern Turkish coast of the Black Sea

Concentrations of Cd, Cu, Cr, Co, Ni, Zn, Fe, Mn, Pb, As, and Sb were determined in sediment trap and bottom sediment samples collected seasonally from a station on the eastern Turkish coast of the Black Sea. Cd, Pb and Mn concentrations were highest in the sediment trap samples except during the summer period, whereas Co, Ni, Zn and Fe levels were much lower than corresponding levels found in the surface sediments. Cu, Cr, As and Sb levels showed no definite trend with sediment type. In general, with the exception of Cr, relatively lower metal concentrations in the sediment trap material were determined in the summer period. The highest mass flux, 56.5 g m⁻² day⁻¹, was measured during autumn. The highest flux of heavy metals also occurred during autumn and was strongly dependent on particle mass flux. Based on these results, we suggest that the downward vertical transport of particulate heavy metals in this region is related to the high degree of land erosion and the resultant particulate flux dynamics, which occur here. It was noteworthy that the highest concentrations of Cd, Cu, Co, Zn, Fe and Sb in particles were measured during winter a finding which suggests that enhanced fossil fuel combustion, which occurs during this period in adjacent urban and industrial areas plays an important role in the metal composition of sinking particles in nearshore waters.     

Spatial and seasonal variations of the macrobenthic community and metal contamination in the Douro estuary (Portugal)

The macrobenthic community structure and characteristics of sediments were studied in samples collected seasonally at five stations in the lower mesotidal Douro estuary, Portugal. Sediment characterisation included grain size distribution, total-recoverable metals (Al, Fe, Mn, Zn, Cu, Cr, Pb, Ni and Cd), acid-volatile sulphides (AVS) and simultaneously extracted metals (SEM) and total organic matter contents. Spatial variation surpassed temporal variation both in terms of environmental parameters and community structure. Clear anthropogenic contamination in terms of Zn, Cr, Cu and Pb, and a positive SEM-AVS, indicating the potential bioavailability of these metals, were detected on the north bank of the estuary. Multivariate analysis revealed that in addition to natural sediment characteristics, the anthropogenic metal contamination was influencing the macrobenthic community structure. In fact, greater concentrations of Zn, Cr, Cu and Pb were associated with lower number of species and/or diversity. Finally, the dry weight-normalised metal concentrations appeared as a more useful tool than the SEM-AVS model in predicting disturbance of the macrobenthic community in the studied area.     

Input of particulate heavy metals from rivers and associated sedimentary deposits on the Gulf of Lion continental shelf

Fluxes of the heavy metals chromium (Cr), cobalt (Co), nickel (Ni), copper (Cu), lead (Pb), cadmium (Cd) and zinc (Zn) delivered by rivers to the Gulf of Lion (NW Mediterranean Sea) were estimated over a three year study of the River Rhone and its smaller tributaries. Most of the particulate metal fluxes (80–90%) delivered by these rivers occurred within a very short period of time (less than 12%), a typical trend for the Mediterranean environment, where highly contrasting hydrological regimes were observed over the year. Temporal and spatial variations in the fluxes of these particulate metals were driven by the fluxes in both water discharge and suspended particulate matter load. On the shelf, these particulate metal fluxes, largely arising from the Rhone watershed, were two to ten times more important than those resulting from atmospheric deposition. Co, Cr and Ni in the rivers and on the shelf surface sediments were mainly natural and associated with the finest particles. Cd and Phosphorus appeared to be associated with the silt fraction and to be enriched in the prodelta areas. Pb, Zn and Cu were more closely associated with the organic matter content and also showed enrichment in the organic rich prodeltaic sediments. Anthropogenic influences diminished offshore, except for Pb and Zn which could be supplied from the atmosphere by man-made aerosols. Although most of the metals tended to be enriched in the prodelta areas, these did not constitute a permanent sink due to resuspension processes affecting these shallow depths. A resuspension experiment conducted on sediment cores from the Rhone prodelta demonstrated that metal deposited on the surface layer, especially those associated with the organic matter, may be resuspended; this should be taken into account for a complete understanding of the biogeochemical cycle of these metals.     

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.     

Assessment of pollution and ecological risk of heavy metals in the surface sediments of Ulsan Bay,Korea

Heavy metal concentrations in the surface sediments of specially managed Ulsan Bay were investigated to determine metal distribution, pollution status and its ecological risk using pollution indices (enrichment factor and geo-accumulation index), potential ecological risk index and sediment quality guidelines (SQGs). The order of mean concentration (mg/kg) of metals was Zn (361.9) > Cu (95.6) > Pb (90.7) > Cr (64.7) > Ni (32.2) > Co (16.6) > As (15.8) > Cd (0.40) > Hg (0.16) in sediments of Ulsan Bay. Spatial distribution of metals in sediments showed a significantly higher concentration near industrial complexes, indicating that metal pollution is caused by anthropogenic sources. The results of enrichment factor (EF) and geo-accumulation index (I_geo) showed that sediments were significantly accumulated with Cu, Zn, As, Cd, Pb and Hg, indicating moderate to very severe enrichment (pollution) by these metals. Based on the potential ecological risk index, Hg and Cd posed a very high and a considerable potential ecological risk. Cu and As posed a moderate potential ecological risk, while, other metals (Cr, Co, Ni, Zn and Pb) rarely posed any potential ecological risk to the coastal environments. The sediments in Ulsan Bay showed a very high level of ecological risk, dominated by Hg and Cd. Metal concentrations in sediments were 80% for Cu, 96.7% for Zn, 50% for As, 70% for Pb and 50% for Hg above the threshold effects level (TEL), respectively.     

Heavy metals in a contaminated Australian estuary—Dispersion and accumulation trend

Very high concentrations of Zn, Pb, Cu and Cd occur in the muddy bottom sediments of Lake Macquarie, a saline coastal lagoon in southeastern Australia. The trace metals emanate from industrial sources, especially a lead-zinc smelter, at the northern end of the lake. Individual metal concentrations decrease progressively away from the source area but at differing rates; Zn is most mobile and Cd appears to be deposited first. They approach natural background levels in the southern part of the lake. Mn shows a reverse trend but Ni, Co, Ag and Fe rarely rise above background levels.Shallow cores in the lake bed penetrated a metal enriched surface zone 15–35 cm thick underlain by uncontaminated sediments with natural (background) metal concentrations. Sedimentation rates determined from radiocarbon ages on shells in the cores mainly range between 0·15 and 0·5 mm yr^?1. Over the 85 years since industrialization commenced, less than 5 cm of mud has accumulated on the lake bed. Bioturbation is invoked to account for the depth to which the sediment has been enriched in heavy metals.     

辽东湾表层沉积物的重金属污染特征与质量评价

本文研究了辽东湾表层沉积物中重金属的分布及污染特征，评价其生态风险及环境质量。对辽东湾表层沉积物8种重金属（As、Cu、Cd、Cr、Hg、Ni、Pb、Zn）的空间分布进行了研究，采用Hankanson法和I_geo（地累积指数）分析了该海域重金属潜在生态风险，并评价了该海域的环境质量。在辽东湾葫芦岛附近海域、西南部六股河口东南部海域以及西部近岸海域表层沉积物中As、Cu、Cd、Cr、Hg、Ni、Pb和Zn含量偏高。地累积指数法及生态风险指数法对重金属污染程度评价结果一致，辽东湾生态环境具有潜在危害的重金属主要是Cd、Hg和As，8种重金属潜在生态风险系数由高到低依次为Cd、Hg、Cu、Pb、As、Zn、Ni和Cr，各站位重金属综合潜在生态风险指数均大于150，生态风险总体上处于中等生态风险等级。Cd和Hg是该海域沉积物重金属中主要污染物，局部区域达到中、中-强污染程度。环境质量评价表明，辽东湾表层沉积物重金属引发有害生物效应的可能性不大，但Cd和Hg显著富集，应予以重视。     

夏季珠江口沉积物?水界面重金属分布特征及其影响因子研究

珠江口受复杂径?潮动力耦合作用的影响,河口重金属迁移转化机制复杂多变。本文基于2018年夏季珠江口及其邻近海域海水和沉积物的调查资料,研究了珠江口多动力因子驱动下7种重金属元素汞、砷、锌、镉、铅、铜和铬的沉积、迁移和积累机制。结果表明:相比于溶解态重金属（水体中）的赋存状况,吸附态重金属（沉积物中）更稳定,污染也更严重;采用皮尔逊相关分析和主成分分析计算出重金属元素与环境因子之间的响应关系,溶解态重金属主要以稀释混合过程为主,吸附态重金属受有机碳和氧化还原作用的影响较大;沉积物?水界面重金属的分配系数显示出铅和铬易被吸附在颗粒物上,而镉和汞易溶解在水体中,揭示了河口复杂动力影响下元素在不同介质的形态转换特征;除了镉?铬、镉?铜和铬?砷这3组元素间不显著相关,其他元素间的显著相关性表明了重金属元素具有相似的来源,并采用主成分分析探讨了重金属元素的潜在来源,主要来源为工业废水,农业和大气沉降次之。研究结果可为有效控制重金属的排放和河口污染治理提供重要支撑。     

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.     

Impact of trace metals on denitrification in estuarine sediments of the Douro River estuary,Portugal

Denitrification influences the nitrogen budget in estuaries by removing fixed nitrogen from the inorganic pool; rates are dependent on both geological and geographic conditions as well as increasing anthropogenic impacts. In this study the effects of copper (Cu), chromium (Cr), zinc (Zn), cadmium (Cd) and lead (Pb), on the denitrification pathway were evaluated in subtidal and intertidal sediments of the Douro River estuary. Dinitrogen, N₂O and NO₂⁻ production rates were measured in triplicate slurries of field samples under different treatments of metal concentrations. Results demonstrated that similar metal amendments led to different site responses for denitrification, suggesting that variations in sediment properties (metal concentrations, grain size, organic matter content, etc.) and/or differences in denitrifying community tolerance modulate the level of metal toxicity. Denitrifying communities in subtidal muddy sediments were not affected by increasing concentrations of metals. In contrast, intertidal sandy sites revealed high sensitivity to almost all trace metals tested; almost complete inhibition by Cr (95%) and Cu (85%) was observed for 98 and 79 μg per gram of wet sediment respectively, and by Zn (92%) at the highest concentration added (490 μg per gram of wet sediment). Moreover, the addition of trace metals stimulated N₂O and NO₂⁻ accumulation in intertidal sandy (Zn, Cu, Cr and Cd) and muddy sediments (Cu and Zn), demonstrating a pronounced inhibitory effect on specific steps within the denitrification enzymatic system. In summary, the results obtained suggest that, according to the type of estuarine sediment, trace metals cannot only reduce total N removal from an estuary via denitrification but also can enhance the release of N₂O, a powerful greenhouse gas.     

Geochemical signature as paleoenvironmental markers in Holocene sediments of the Tinto River estuary (Southwestern Spain)

High absolute concentrations of metals associated to sulfide deposits located at the river source (Fe, Cu, Zn, Pb, Cd, and As) have been determined from the study of major and trace element concentrations in sediment samples obtained in two vibracores in the Tinto River estuary. In most cases, the enrichment factor (EF) for these metals is over 2. Cu, Zn and As have much higher EF, over 10 in surficial samples. Fe oxy-hydroxide precipitation in high-chlorinity zones and its scavenging effect on metals is the main control process on the chemical composition of sediment. Vertical evolution of the sedimentary and geochemical characteristics of the cores show that the estuary has undergone a process of progressive shallowness and a relative increase in acidic river water volume with respect to seawater. This effect has originated a downstream displacement of acid mixing processes affecting the estuary, which is reflected in higher metal concentrations in sediments of the outer zones of the system.     

A statistical study of environmental factors controlling concentrations of heavy metals in the burrowing bivalve Scrobicularia plana and the polychaete Nereis diversicolor

Multiple regression analyses indicate that the most important factors controlling Ag, Cd, Co, Cu, Pb and Zn concentrations in the estuarine bivalve Scrobicularia plana and the polychaete Nereis diversicolor are the concentrations of these metals in surface sediments and the partitioning of sediment-bound metals between different sediment constituents. Extraction of the sediments with 1-n HCl provides more information about the bioavailability of the metals than do extractions with five other techniques. Biologically available Cd and Co in solution contribute significantly to Cd and Co concentrations in both Scrobicularia and Nereis. Concentrations of Ag in Scrobicularia are reduced where Cu concentrations in sediments are high. An unexplained increase in concentrations of Cu in Scrobicularia at specific stations in six estuaries suggests that under certain very anoxic conditions the availability of copper may be exceptionally high.     

Distribution and Enrichment of Heavy Metals in Recent Sediments of Safaga Bay,Egypt

The present study was undertaken for assessing the level of heavy metals such as iron, manganese, zinc, copper, nickel, cadmium, lead, and cobalt in recent sediment samples of Safaga Bay, Egypt. Concentration of heavy metals in sediments shows significant variability and ranges from 863.37 to 1144.93 ppm for Fe, 64.29–586.8 ppm for Mn, 2.7–12.68 ppm for Zn, 3.01–7.2 ppm for Pb, 1.53–3.29 ppm for Ni, 0.55–1.57 ppm for Co, 0.16–1.37 ppm for Cu, and 0.22–0.4 ppm for Cd.

Sediment pollution assessments were carried out using an enrichment factor and geoaccumulation index. The calculation of enrichment factor showed that Cd is enriched by 4.1 due to phosphate sources in Safaga Bay. The Geoaccumulation index results revealed that there are positive and negative correlations between Fe, Zn, Mn, Pb, Ni, Cu, Co, and Cd indicating that these metals have complicated geochemical behaviors.     

Trace metals in the Göta river estuary

The concentrations of the trace metals Cd, Cu, Fe, Ni, Pb and Zn in the Göta River estuary have been investigated. The following metal fractions have been determined: acid-leachable, dissolved, labile and particulate.The estuary represents a salt wedge type estuary and is situated in a densely populated region of Sweden. The metal concentrations found for the dissolved fraction is in the range of what can be considered as background levels for freshwater. It is difficult to evaluate any estuarine processes other than conservative mixing for Cd, Cu, Ni and Zn. The dissolved levels in the freshwater end member are Cd, 9–25 ngl^?1; Cu, 1·1–1·4 μgl^?1; Fe, 20–75 μg l^?1: Ni, 0·7–0·9 μg l^?1: Pb 0·09–0·2 μg l^?1; and Zn, 6–7 μg l^?1:The results from the acid-leachable fraction show that at high suspended load the particles sediment in the river mouth. The trace metal levels in this fraction are subject to large variations.     

Metal concentrations in sediments and clams in four Moroccan estuaries

Metals (Cd, Cu, Ni, Zn, Mn and Fe) were analyzed seasonally over three years in sediments and in tissues of the clam Scrobicularia plana in four Moroccan Atlantic estuaries: Loukkos, Sebou, Bou Regreg and Oum er Rbia. Of these metals, Cd was at the lowest concentrations in sediment. Concentrations of Cu, Zn, and to a lesser extent Ni, in sediments suggest greater contamination in Sebou and Bou Regreg than in the other estuaries. The fluctuations of Mn and Fe concentrations in the fine surface sediments reflect their continental origin and show seasonal variations that indicate soil run-off following rain events. Concentrations of Cu, Zn, and especially Ni in clam tissues in these estuaries were generally higher than in some other common bioindicator bivalve species. The seasonal variations in S. plana's tissue metal concentrations are linked to patterns of reproductive activity for all metals except Cd and possibly Zn, whose tissue concentrations may be regulated. Mn and Fe concentrations in S. plana were positively correlated to sediment levels of these metals.     

邻近城市土壤重金属对九龙江口沉积土壤的影响

在研究建立于漳州地区生态地球化学调查基础上,对河口湾沉积物的重金属与人口高度集中的城市地区土壤重金属的分布特征进行了对比,分析了人为活动对河口的影响,结果表明,城区与河口湾表层样品都舍有相对区域基准值较高的Hg、Cd,而且Hg富集系数要远高于Cd的富集系数。分析两种元素来源与迁移方式可知,Hg由于可通过气态形式迁移而对河口影响更大。城区与河口湾样品的重金属进行聚类分析与主因子分析结果表明：城区土壤的As、Zn、Mo、Ni、Cr和Mn主要来自基岩来源。Pb、Se、Cd可以作为人为污染的指示元素,Hg、Sn显示与其他元素具有相对独立的行为。河口湾的元素组合与城区重金属基本相似,但Pb、Cu、Se、Mo、Cd显示出两种因素都有较大影响,可以指示人为影响与基岩源的双重作用。