A study of marine pollution caused by the release of metals into seawater following acid spills

This study examined the potential metal pollution induced by the accidental spill of different acids into seawater. The acids sink to the bottom according to their densities and subsequently react with marine sediments. The acids selected for this study were acetic, hydrochloric, nitric, sulfuric, and phosphoric acids; the metallic elements selected were Cr, Cu, Fe, Mn, Pb and Zn. The sediment was collected in Brest Harbour. The percentages of metals released from this sediment in the presence of various concentrations of acids in seawater were important; concentrations of approximately 7 mg L⁻¹ for Mn and 60 mg L⁻¹ for Zn were observed under our experimental conditions. We also examined the rate of release of these metals from the sediment into the seawater in the presence of the different acids and under different experimental conditions. We found that most of the metallic elements were released from the sediments into the seawater during the first fifteen minutes of exposure. After this time, a high degree of pollution was induced if acids leached into seawater were not rapidly diluted.     

Influence of mangrove reforestation on heavy metal accumulation and speciation in intertidal sediments

To investigate the influence of mangrove reforestation on heavy metal accumulation and speciation in intertidal sediments, core sediments from a restored mangrove forest and adjacent mud flat in Yifeng Estuary (southeastern China) were analyzed. The chemical speciation of heavy metals (Pb, Zn, Cu, Cr and Ni) was determined according to a sequential extraction procedure. Special attention was paid to the upper 20 cm of sediment, in which metal accumulation was enhanced and speciation was obviously modified. Mangrove reforestation decreased the concentrations of all metals in the acid-soluble fraction and increased metal concentrations in the oxidizable fraction. Increased Pb, Zn and Cu concentrations and decreased Ni and Cr concentrations were observed in the reducible fraction. These results suggest that mangrove reforestation facilitated the accumulation of heavy metals in the upper sediment layers but decreased their bioavailability and mobility.     

Anthropogenic influence on the degradation of an urban lake - The Pampulha reservoir in Belo Horizonte, Minas Gerais, Brazil

The artificial reservoir Lagoa da Pampulha in central Brazil has been increasingly affected by sediment deposition and pollution from urban and industrial sources. This study investigates water chemistry and heavy metal concentrations and their fractionation in the lake sediment using ICP-OES, ICP-MS, and XRD analyses. Fractionation analysis was done by sequential extraction under inert gas as well as after oxidation. The lake exhibits a permanent stratification with an oxygen-free hypolimnion below 2 m depth. Nutrient concentrations are enriched for phosphorous components (SRP, PO₄). In the sediment it was not possible to detect oxygen. Carbon, sulfur, and most of the analyzed heavy metals are enriched in the top sediment layer with a pronounced downward decrease, indicating the presence of an anthropogenic influence. Statistical analysis, including correlations and a Principal Component Analysis (PCA) of depth-related total concentration data, helps to distinguish presumably anthropogenic heavy metals from geogenic components. Some samples with high element concentrations in the sediment also show elevated concentrations in their pore water. Analyses of element distribution between sediment and pore water suggest a strong bonding of heavy metals to the anoxic sediment. The trend towards elevated solubility in the pore water of oxidized samples is clear for most of the analyzed elements. Fractionation analysis reveals characteristic associations of selected elements to specific mineral bonding forms. In addition, it indicates that the behavior of heavy metals in the sediment is strongly influenced by organic substances. These substances provide buffering against oxidation, acidification, and metal release. The high nutrient loading causes reducing conditions in the lake sediment. These conditions trigger the accumulation of sediments rich in S²⁻, which stabilizes the fixation of heavy elements. In the future, care must be taken to reduce the supply of contaminants and to prevent the release of heavy metals from sediments dredged for remediation purposes.     

A survey of trace element distribution in tissues of stone crabs (Menippe mercenaria) from South Carolina coastal waters

The stone crab (Menippe mercenaria) is an important component of the estuarine food web as both predator and prey. Stone crabs live in sediment, primarily consume oysters, and as a result, have the potential to accumulate significant quantities of pollutants including metals. In South Carolina, the stone crab is becoming a targeted fishery as an ecologically sustainable seafood choice. To date, no studies have reported metals in stone crab tissues. This study examined the distribution of major and minor trace elements in chelae and body muscle, gill, and hepatopancreas. Crabs were collected from three tidal areas within Charleston County, South Carolina, with differing upland use. Results were compared by collection location and by tissue type. Concentrations of some metals associated with anthropogenic activities were up to three times higher in crabs from sites adjacent to more urbanized areas. Concentrations in edible tissues were below historical FDA levels of concern.     

Regeneration and Reuse of a Seaweed‐Based Biosorbent in Single and Multi‐Metal Systems

A seaweed‐waste material resulting from the processing of Ascophyllum nodosum was previously shown to be very efficient at removing Zn(II), Ni(II) and Al(III) both in single and multi‐metal waste streams. In this study, the regeneration of the biosorbent using an acid wash resulted in the release of high metal concentrations during multiple desorption cycles. Maximum desorption efficiencies (DE) of 183, 122 and 91% were achieved for Zn(II), Ni(II) and Al(III), respectively, for subsequent metal loading cycles, significantly exceeding the desorption rates observed for conventional sorbents. The regeneration of the sorbent was accomplished with very little loss in metal removal efficiency (RE) for both single and multi‐metal systems. Values of 92, 96 and 94% RE were achieved for Zn(II), Ni(II) and Al(III), respectively, for the 5^th sorption cycle in single metal aqueous solutions. A slight decrease was observed for the same metals in multi‐metal systems with maximum REs of 85, 82 and 82% for Zn(II), Ni(II) and Al(III), respectively. This study showed that the novel sorbent derived from a seaweed industrial waste would be suitable for multiple metal sorption cycles without any significant loss in RE.     

Determination of Trace Levels of Nickel and Manganese in Soil,Vegetable, and Water

A simple and reliable method for rapid and selective extraction and determination of trace levels of Ni²⁺ and Mn²⁺ was developed by ionic liquid (IL) based dispersive liquid–liquid microextraction coupled to flame atomic absorption spectrometry (FAAS) detection. The proposed method was successfully applied to the preconcentration and determination of nickel and manganese in soil, vegetable, and water samples. After preconcentration, the settled IL‐phase was dissolved in 100 µL of ethanol and aspirated into the FAAS using a home‐made microsample introduction system. Injection of 50 µL of each analyte into an air–acetylene flame provided very sensitive spike‐like and reproducible signals. Effective parameters such as pH, amount of IL, volume of the disperser solvent, concentration of the chelating agent, and effect of salt concentration were inspected by a (2^5‐1) fractional factorial design to identify the most important parameters and their interactions. Under optimum conditions, preconcentration of 10 mL sample solution permitted the detection of 0.93 µg L^?1 Ni²⁺ and 0.52 µg L^?1 Mn²⁺ with enrichment factors 77.2 and 82.6 for Ni²⁺ and Mn²⁺, respectively. The accuracy of the procedure was evaluated by analysis of a certified reference material (CRM TMDW‐500, drinking water).     

巢湖沉积物重金属富集特征与人为污染评价

本文分析了巢湖主要入湖河流河口区表层沉积物及西部湖心区沉积岩芯中Al、Fe、Ni、Cr、Cu、Zn、Pb、Li、V等金属元素变化特征,采用地球化学方法对金属元素变化的"粒度效应"进行矫正,并以Li、V为参照元素对矫正结果进行检验;参考历史沉积物,对河口区及西部湖心区沉积物重金属人为污染特征进行分析;结合沉积岩芯210Pb年代结果,估算西部湖心区近150a来Ni、Cr、Cu、Zn、Pb等重金属元素的人为污染贡献量.结果表明,河口表层沉积物重金属污染具有显著的空间差异,南淝河河口重金属人为污染最重,其中Ni、Cr、Cu、Zn、Pb的人为污染贡献量分别为12.2、32.2、25.3、479.9和76.0 mg/kg,分别占总含量的35%、37%、64%、92%和77%;其次是柘皋河河口,主要重金属污染元素为Cu、Zn和Pb,人为污染贡献量达57.6、57.0和19.5 mg/kg,分别占总含量的73%、47%和36%;而派河、白石山河、杭埠河等河口表层沉积物中重金属元素人为污染程度较弱.巢湖西部湖心区主要污染元素为Cu、Zn、Pb,人为污染开始于1950s,1980年以来其人为污染贡献量显著增加,平均为16.2、245.6、47.8 mg/(m2.a),分别占各元素沉积通量的23%、61%和37%;Ni人为污染开始于1980s初期,人为污染贡献量平均为12.6 mg/(m2.a),占其沉积通量的13%左右;Cr基本未受人为污染影响.西部湖心区沉积岩芯及南淝河河口表层沉积物中重金属污染程度均表现为Zn>Pb>Cu,而且南淝河河口沉积物重金属污染程度显著高于西部湖心区.结合主要入湖河流径流量与河口沉积物重金属污染特征,认为巢湖西部湖心区重金属污染主要通过南淝河输入,来自合肥等城市的废水是主要的污染源.     

Geochemical and mineralogical study of a site severely polluted with heavy metals (Maatheide, Lommel, Belgium)

The former zinc smelter site ‘de Maatheide’ in Lommel (Belgium) was severely polluted with heavy metals and the pollution spread into the surroundings by rain water leaching and wind transportation. This study focuses on the processes of immobilization and natural attenuation that took place on the site. Three important factors were found. Firstly, the high pH values (pH 7–8) in the topsoil influence the mobility of heavy metals. Secondly, the spodic horizons below the polluted top layer seem to accumulate heavy metals, thereby slowing down their release into the environment. Finally, the glassy phases and iron oxi/hydroxides that are present can encapsulate heavy metals during their formation/recrystallization, thereby immobilizing them. An additional shielding effect results from the reaction rims of goethite around the contaminant phases, which partially inhibit the weathering process and release of contaminants. This shielding effect is an important factor to take into account when modelling contaminant release.     

Zinc speciation in steel plant atmospheric emissions: A multi-technical approach

Epidemiological studies have provided evidence for the association of air particulate matter (PM) and heavy metals concentrations with adverse health effects for human population but also for environment. Even if the knowledge of PM and metals concentration is important, it has been clearly demonstrated that the chemical form of an element is essential to understand its environmental behaviour and its potential toxicity. Studies have demonstrated that zinc (Zn), particularly in its soluble forms, induces inflammatory response in lungs. As steel plant is an important heavy metals emitter, and as atmospheric emissions are rich in Zn, the aim of our work was to determine Zn bearing phase and speciation in steel work air particulate matter by a multi-technical approach including physical methods like SEM, Extended X-Rays Absorption Fine Structure (EXAFS) and chemical techniques like ICP-AES and sequential leaching. Results show that Zn is mainly associated with two phases, (i) one insoluble phase which has been clearly identified, as Zn–Fe oxide and similar to franklinite, and (ii) one easily soluble phase, containing calcium and probably associated with carbonates which present a greater toxical potential for environment and human health.     

Impacts of the dumping site on the environment: Case of the Henchir El Yahoudia Site, Tunis, Tunisia

The Henchir El Yahoudia landfill is one among many uncontrolled dumping sites in Tunisia with no bottom liner. It is located at the southeastern edge of Sijoumi Sebkha. The site has been exploited since 1963 until 1994. It constitutes a peculiar case because of its situation, its exploitation mode and the nature of buried wastes. Leachate analysis shows that they are strongly charged with nitrogen (especially ammoniacal and kadjedahl), organic compounds with a high biodegradability and a charge of metallic elements exceeding the Tunisian norm NT 106-002. Sediment analyses show that the highest rate of heavy metals and organic matter coincides with clay-richest layers, characterized by the highest specific-surface values. The percolation of these pollutants until the groundwater between 0.5 and 5 m has provoked a pollution characterized by high rates of organic matter (BOD, COD and nitrogen) and heavy metals. To cite this article: A. Marzougui, A. Ben Mammou, C. R. Geoscience 338 (2006).