Impact of anions on the heavy metals release from marine sediments

Marine sediments from Lianshan Bay in Huludao, China, were studied in laboratory. A series of simulated experiments were carried out to investigate the influences of three kinds of anions CL^-, SO4^2- and HCO3^- on the release ofCd, Pb, Cu and Zn from the sediments. The results showed that the sequences about the impact of the three anions were Cl^-〉HCO3^-〉SO4^2＋. The release potential of heavy metals in the presence of each anions was in the following order： Cd≥Cu 〉Zn≈Pb. The correlations were positive between CI content and the quantity of Cd released from the marine sediment, whereas there was no significant relationship between CI content and amount of Cu and Zn released. For SO4^2- and HCO3^-, the release of the heavy metals from marine sediments was not obvious.     

Simulating the dynamics of sulfur species and zinc in wetland sediments

In situ measurements comparing vertical SO₄²⁻ profiles in vegetated and non-vegetated sediments showed that SO₄²⁻ concentrations in vegetated sediments increased significantly at the beginning of the growing season and then gradually decreased during the rest of the growing season. Throughout the growing season, SO₄²⁻ concentrations remained higher in the vegetated sediments than in the sediments without plants. The higher SO₄²⁻ concentrations in the vegetated sediments indicate that oxygen release from roots and evapotranspiration-induced advection by plants play an important role in the dynamics of sulfur species in sediments. Since the total pool of solid-phase sulfide is relatively large compared to the mass of SO₄²⁻ in the sediments, the gradual decrease of SO₄²⁻ concentrations may result from limitation of the solid-phase sulfide that is in direct contact with or very close to the roots and rhizomes. This would mean that the main pool of solid-phase sulfide and associated trace metals are not affected by the oxygen release from roots, and the associated trace metals will not become bioavailable during the growing season.     

Fly ash content and distribution in lake sediments around a large power station: inferences from magnetic susceptibility analysis

The bulk magnetic susceptibility of sediments from artificial and natural lakes around a large coal-fired power station in NE Spain has been measured. Higher magnetic susceptibility values are found in lake sediments located SE of the power station. This distribution of susceptibility values is compatible with environmental and meterological studies of emissions from the power station, which indicate a dominant SE plume direction. Mineralogical studies, by means of X-ray diffraction and scanning electron microscopy, show that the highest susceptibility values found in the sediments are caused by magnetic iron spinels in the fly ash that is transferred to the environment by the power station particulate emissions. After the quantitative mineralogical studies of fly ash, two different methods of fly ash content determination in the sediments have been devised, showing very similar results. The low background magnetic susceptibility of the sediments in the study area and the high susceptibility resulting from the input of magnetic fly ash particles allows both delimitation of the polluted area around the power station, and quantification of the fly ash input into the natural sediments.     

Wave Enhancement of Diffusivities within Surficial Sediments

The enhancement of solute diffusivities within coastal surficial sediments as a result of wave action is examined. Fluctuating pressure gradients associated with passing waves cause interstitial water motions leading to enhanced diffusivities through the mechanism of shear dispersion. Wave amplification of diffusivities is likely to be greatest for waves of period 10 s, in shallow water, over a bottom of coarse grain. Diffusivity enhancement of hundreds of times molecular diffusivity is achievable. The mechanism is distinct from, but complements, the mechanism of rotational dispersion which has been previously described. Other mechanisms that enhance solute transport within surficial sediments rely on the interaction between wave-driven or steady flow over bottom obstructions such as biogenic structures or sand ripples. It is suggested that while the resulting advective flows may dominate solute transport within the top few 10 s of centimeters of the sediment column, shear dispersion may be more important deeper within the sediment. In any event, in contrast to these other mechanisms, shear dispersion is operative even when the seabed is flat. Application of the theory to sediments of the South Atlantic Bight would suggest that shear dispersion is capable of explaining a major part of the interstitial transport inferred from measurements.     

利用磁信息研究潮滩重金属污染的探讨

本文以长江口潮滩沉积物的系统磁性测量为基础,对照化学分析和粒度分析等数据,初步探讨了潮滩沉积物的磁性特征与重金属元素含量的相关联系及其机理,建立了重金属元素含量与磁参数的定量关系模型,并揭示了长江口潮滩重金属污染的空间特征及其与沉积环境的联系。本项工作成功地探索了利用磁信息研究潮滩重金属污染的技术路线和应用前景,指出了在一定区域内,利用适量样品的磁性测量与重金属元素分析数据,建立其定量回归模型的可行性。从而可以在区域污染调查中,通过广泛的磁数据测量,由经验公式定量地估算不同滩地部分的重金属元素含量,以全面了解潮滩重金属污染的空间分布,分析其规律和机理。由于磁测方法具有快速、简便、经济、易行等特点,它为大范围的潮滩重金属污染研究提供了一项实用有效的辅助手段。     

Cesium migration in saturated silica sand and Hanford sediments as impacted by ionic strength

Large amounts of 137Cs have been accidentally released to the subsurface from the Hanford nuclear site in the state of Washington, USA. The cesium-containing liquids varied in ionic strengths, and often had high electrolyte contents, mainly in the form of NaNO3 and NaOH, reaching concentrations up to several moles per liter. In this study, we investigated the effect of ionic strengths on Cs migration through two types of porous media: silica sand and Hanford sediments. Cesium sorption and transport was studied in 1, 10, 100, and 1000 mM NaCl electrolyte solutions at pH 10. Sorption isotherms were constructed from batch equilibrium experiments and the batch-derived sorption parameters were compared with column breakthrough curves. Column transport experiments were analyzed with a two-site equilibrium-nonequilibrium model. Cesium sorption to the silica sand in batch experiments showed a linear sorption isotherm for all ionic strengths, which matched well with the results from the column experiments at 100 and 1000 mM ionic strength; however, the column experiments at 1 and 10 mM ionic strength indicated a nonlinear sorption behavior of Cs to the silica sand. Transport through silica sand occurred under one-site sorption and equilibrium conditions. Cesium sorption to Hanford sediments in both batch and column experiments was best described with a nonlinear Freundlich isotherm. The column experiments indicated that Cs transport in Hanford sediments occurred under two-site equilibrium and nonequilibrium sorption. The effect of ionic strength on Cs transport was much more pronounced in Hanford sediments than in silica sands. Effective retardation factors of Cs during transport through Hanford sediments were reduced by a factor of 10 when the ionic strength increased from 100 to 1000 mM; for silica sand, the effective retardation was reduced by a factor of 10 when ionic strength increased from 1 to 1000 mM. A two order of magnitude change in ionic strength was needed in the silica sand to observe the same change in Cs retardation as in Hanford sediments.     

Chlorophenols in lake bottom sediments: A retrospective study of drinking water contamination

Lake and brook bottom sediments were analyzed for chlorophenols to provide historical data of exposure assessment, after the water intake plant of a Finnish village had been found to be contaminated in 1987, and subsequently elevated non-Hodgkin lymphoma risk was detected. Highly elevated 2,3,4,6-tetrachlorophenol and pentachlorophenol levels were found in all four lake sediment cores investigated. The distribution was uneven with much higher concentrations in the estuary, in contrast to PCB compounds which were more evenly distributed within the basin. The inlet origin of the chlorophenols in the sediments was further supported by the regional distribution pattern of these compounds in the sediment and water along transects of the inlet and its tributaries. The composition of chlorophenol congeners in the sediments was similar to that in a commercial fungicide used by a local sawmill, but different from other sediment analyses reported in Finland, also implying a local source. Dating of three cores by Pb-210 and soot ball chronology indicated that the contamination of the watercourse started in the early 1970s at the latest but possibly earlier. This would provide the latency time required for tumour appearance in the 1970s and 1980s.     

Analysis of heavy metal distribution in superficial estuarine sediments (estuary of Bilbao, Basque Country) by open-focused microwave-assisted extraction and ICP-OES

Open-focused microwave-assisted extraction and ICP-OES determination of As, Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn from surface sediments of the estuary of Bilbao (Basque Country, North of Spain) was carried out. All the samples were collected at three different tributaries of the estuary (Asua, Galindo and Nerbioi-Ibaizabal) every two months during 1999. The digestion procedure was proposed from the conclusions of a fractionated factorial design, and the precision and accuracy of the method was verified using a certified reference sediment (RTC008-050). The results of the analysis were statistically treated by means of principal component analysis and correlation analysis. The principal component analysis of sediment data (32 samples × 9 metals) indicated different patterns of contamination regarding the tributary and sampling station. The two main patterns observed were a steady increment of the metal concentration along all the campaigns in the samples collected in the Galindo River and a seasonal variation in the Nerbioi-Ibaizabal River, with higher metallic content during summertime and lower content during wintertime.     

Resistant sorption of in situ chlorobenzenes and a polychlorinated biphenyl in river Rhine suspended matter

The desorption kinetics of in situ chlorobenzenes (dichlorobenzenes, pentachlorobenzene and hexachlorobenzene) and 2,4,4^′-trichlorobiphenyl (PCB-28) were measured with a gas-purge technique for river Rhine suspended matter sampled in Lobith, The Netherlands. This suspended matter is the main source of sediment accumulation in lake Ketelmeer. In lake Ketelmeer sediment earlier observations showed that slow and very slow fractions dominate the desorption profile.

For the river Rhine suspended matter, only for PCB-28 a fast desorbing fraction of around 1.6% could be detected. The observed rate constants were on the average 0.2 h⁻¹ for fast desorption, 0.004 h⁻¹ for slow desorption, and 0.00022 h⁻¹ for very slow desorption. These values are in agreement with previous findings for the sediment from lake Ketelmeer and with available literature data on fast, slow, and very slow desorption kinetics.

The results from this study show the similarity of desorption profiles between river Rhine suspended matter, and the top layer sediment from lake Ketelmeer. This indicates that slow and very slow fractions are already present in material forming the top layer of lake Ketelmeer, and were not formed after deposition of this material in the lake. The absence of detectable fast fractions for most compounds could be caused by the absence of recent pollution of the suspended matter. But, the observations may also be explained by a rapid disappearance of compounds from the fast fraction due to a combination of a high affinity of very slow sites for these compounds, and their relatively high volatility.     

Growth of Plants on TBT-contaminated Harbour Sludge and Effect on TBT Removal (10 pp)

Background Worldwide, large amounts of sediments have to be dredged annually from waterways and harbours. These sediments are sometimes polluted with a variety of toxic compounds. In some countries, including Belgium, the load with the biocide tributyltin (TBT) from ship coatings prohibits the dumping of harbour sludge into the sea. Land-based dumping is a commonly used alternative. Objective This research investigated the feasibility to use land-deposited harbour sludge for plant production. In a field trial, the growth of 38 more or less salt-tolerant plant species on low and high TBT-contaminated sediments was studied. The elimination of TBT from sludge with and without vegetation was compared. The uptake of TBT and its degradation products di- and monobutyltin (DBT and MBT) into harvest products under field conditions was determined. - Experimental Set-up. Sediments dredged in May 2003 from the brackish waters of the port of Antwerp were analysed in the laboratory for soil texture, pH, electroconductivity, sodium, magnesium, potassium, calcium, ammonium, nitrate, total nitrogen, chloride, sulphur and the organotins TBT, DBT and MBT. The sediments were lagooned for one year to dewater, desalinate and improve their structure. Salt-tolerant domestic and wild plants were selected and sown in May 2004. In August 2004, plants were harvested and the produced biomass was determined. Samples were taken from vegetated and non-vegetated top and bottom sediments and from plants growing above soil and analysed for TBT, DBT and MBT. Results The fresh sediments showed a good supply with nutrients and a neutral pH, but were rather saline (EC 14 mS cm-1 of the saturated paste extract). The salinity decreased to 3.7 mS cm-1 during lagoonation. The high and the low contaminated sediment had initially 43 and 1.6 mg TBT kg-1 dry weight, respectively. Besides TBT, several other contaminants were present in the sediments at critical levels. The biomass production of the plant species from the field trial ranged from 0.2 to 13 tons dry mass per hectare. Plants performing excellently were barley, sorghum, rape seed, a clover/grass mix and reed. If at all, a positive influence of TBT on plant growth was seen. TBT was degraded significantly faster (>40%) below barley. The uptake of TBT, DBT and MBT into stem and leaves of reed, grass and clover was very low, but measurable and not related to concentrations in soil. No uptake of TBT or its metabolites into corn of barley was found. Discussion This study confirmed former results: the toxicity of TBT to higher plants is low, and even high levels in soils would not be a hindrance for crop production. The removal of TBT seemed to be increased by both lagooning and plant growth, although the target values for sea dumping in use in certain European countries were not reached. A plausible explanation for the faster degradation of TBT under vegetation is that oxygen is a limiting factor, and plants dewater the soil, thus aerating it. The uptake of the organotins TBT, DBT and MBT into harvest products is probably due to attached soil particles. Conclusions To summarize, barley was the optimal species: it grew very well despite the salinity of the dredged sediments, it had a significantly positive effect on TBT removal; it showed no measurable uptake of TBT or the other butyltins into the harvested product; and it is a cash crop well established in European agriculture. Outlook The amounts of dredged sediments are high, and good soils are becoming increasingly rare. The feasibility of using dredged sediments for non-food production, such as energy crops, should be investigated by a critical risk assessment.