南京玄武湖底泥重金属形态与环境意义

通过对玄武湖12个底泥样品采用连续提取的方法,分别获得湖中6种金属的总量和形态分布数据,并用因子分析的方法对金属总量进行统计分析.金属总量结果表明,部分样点的Ni和大部分样点的Cr、Pb、Zn超过背景值,显示有轻度污染,这与玄武湖周围的地理环境和人类活动对底泥重金属的影响有关.对金属形态分析的结果表明,在所测金属中残渣态是主要的存在形式,其次比例较高的是有机物和硫化物结合态,而Pb、Zn有潜在的生物危害性.     

Extended Sediment Quality Rating for Trace Elements in Urban Waters – Case Study Klinke,Germany

The European Water Framework Directive (WFD) commits European Union member states to achieving good ecological status in all water bodies by 2015. For sediments the definition of good chemical status is based on numerical sediment quality guidelines. The aqua regia fraction is thus used for the evaluation of heavy metal concentrations in sediments. The chemical constituents in sediments responsible for mobility and toxicity are not considered generally. This article presents the combining of the sequential BCR procedure, for determining the chemical species of relevant elements, with the geoaccumulation index principle a numerical classification method for sediment quality guidelines. Using the BCR method it can be demonstrated that changes in element speciation can lead to more highly mobile species of trace elements which may affect the hazardous potential of sediments despite the “good chemical status” classification for aqua regia digestions. The Klinke stream is an urban surface water body located in Magdeburg, the state capital of Saxony‐Anhalt, Germany. Using this stream as an example it is shown that this additional information helps to describe the dynamics and discharge of the trace elements Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Rb, Sr, Mo, Pd, Cd, Sb, Ba, Pb, Bi, and U into the Elbe River from urban water bodies.     

Spatial distribution and bonding forms of heavy metals in sediments along the middle course of the River Elbe (km 287ċ390)

Sediments of eight groyne fields along the middle course of the River Elbe (river km 287?390) were geochemically studied. The 78 sediment samples were analysed for pH and grain size distribution. The grain size fraction < 2 μm was used for mineralogical and chemical analysis: semiquantitative clay mineral analysis; total element content (Al, Ca, Fe, K, Mn, Cd, Cr, Cu, Ni, Pb, Zn), total inorganic and organic C, and bonding form fractionation with a six‐step sequential chemical extraction. The latter was performed on selected samples (n = 32). The sediments along the Elbe's course are still contaminated with heavy metals far above the local geogenic background level. An enrichment factor of more than 15 was calculated for zinc. Cr and Ni are the elements with the lowest enrichment. The bonding form analysis of selected heavy metals shows a dominance of relatively immobile bonding forms, e. g. the moderately reducible and the residual fraction, which implies a relative low mobility potential. Only Zn poses a higher potential threat to the environment, since it has a higher percentage of the first three extracted phases: adsorbed, carbonate, and easily reducible fraction.     

In‐Situ Sonication for Enhanced Recovery of Aquifer Microbial Communities

Sampling methods for characterization of microbial communities in aquifers should target both suspended and attached microorganisms (biofilms). We investigated the effectiveness and reproducibility of low‐frequency (200 Hz) sonication pulses on improving extraction efficiency and quality of microorganisms from a petroleum‐contaminated aquifer in Studen (Switzerland). Sonication pulses at different power levels (0.65, 0.9, and 1.1 kW) were applied to three different groundwater monitoring wells. Groundwater samples extracted after each pulse were compared with background groundwater samples for cell and adenosine tri‐phosphate concentration. Turbidity values were obtained to assess the release of sediment fines and associated microorganisms. The bacterial community in extracted groundwater samples was analyzed by terminal‐restriction‐fragment‐length polymorphism and compared with communities obtained from background groundwater samples and from sediment cores. Sonication enhanced the extraction efficiency up to 13‐fold, with most of the biomass being associated with the sediment fines extracted with groundwater. Consecutive pulses at constant power were decreasingly effective, while pulses with higher power yielded the best results both in terms of extraction efficiency and quality. Our results indicate that low‐frequency sonication may be a viable and cost‐effective tool to improve the extraction of microorganisms from aquifers, taking advantage of existing groundwater monitoring wells.     

三峡库区丰都-忠县段消落带不同高程土壤镉及其形态的分布特征

镉(Cd)是目前三峡库区消落带主要的污染物之一,其迁移和形态转化直接威胁水环境安全.选择库区丰都-忠县段消落带,按照高程差异分别于不同土地利用类型(农田、林地、果园和村庄)下采集土壤样品,利用化学连续提取法测定Cd的形态组成,探讨影响消落带土壤中Cd及其形态空间分布的关键因素.结果表明,消落带土壤中Cd的平均含量为0.65 mg/kg,可交换态及碳酸盐结合态是土壤中Cd的主要形态,占比达到41.21%,残渣态和铁锰氧化物结合态次之,有机物及硫化物结合态占比最低.不同土地利用类型下消落带土壤Cd的含量整体上不存在显著性差异,表明当地人类活动对土壤Cd的直接贡献较弱.消落带土壤Cd及其形态的含量与高程呈显著负相关,且在160～165 m区域发生明显转变,水位变化导致的泥沙沉积可能是控制消落带Cd空间分布的主要因素.此外,土壤理化性质,尤其是细颗粒泥沙对Cd及其形态分布具有明显影响,将来需重点关注泥沙理化属性对Cd迁移及形态转化的影响.     

An Assessment on Metal Sources by Multivariate Analysis and Speciation of Metals in Soil Samples Using the BCR Sequential Extraction Procedure

The concentrations of Cr, Mn, Fe, Ni, Cu, Zn, and Pb metals in soil samples (N = 21) were determined by flame atomic absorption spectrometry. The modified Community Bureau of Reference (BCR) sequential extraction procedure (three‐step) was used in order to evaluate mobility, availability, and persistence of heavy metals in soil samples taken from an agricultural area in Erciyes University Campus. The operationally defined fractions isolated using the BCR procedure were: acid extractable, reducible, and oxidizable. The mobility sequence based on the sum of the BCR sequential extraction stages was: Mn (70.2%) > Pb (62.9%) > Ni (26.7%) > Cr (15.4%) > Zn (14.4%) > Cu (12.9%) > Fe (1.24%). Multivariate statistical analysis was used to define the possible origin of heavy metals in soils. Correlation analysis, principal component analysis (PCA), and cluster analysis (CA) were applied to the data matrix to evaluate the analytical results and to identify the possible pollution sources of heavy metals. PCA results revealed that the sampling area was mainly influenced from three sources, namely natural, airborne emissions from domestic heating and traffic.     

Heavy metals mobility in harbour contaminated sediments: the case of Port-en-Bessin

Metallic contaminants associated with sediments showed various behaviours depending on physicochemical conditions. A contaminated sediment core from a harbour in the Bay of Seine was sampled to derive information about metal solubilization from anoxic sediment. In these anaerobic surroundings, physicochemical processes depended on the organic matter cycle, on vertical variation of redox conditions and on precipitation conditions of iron and manganese. In the studied core, anoxic conditions were developed at -15 cm depth. A three-step sequential extraction procedure, modified from the BCR method (now the SM&T), was applied to the anoxic sediment in order to evaluate the potential mobility of fixed metals. Zinc was the most labile metal, recovered in the first extraction stages, and was associated with the non-residual fraction of sediment. Lead was the least labile metal, with up to 70% associated with the residual fraction of the sediment. Copper was associated with organic matter, and its mobility was controlled by the concentration and degradation of the organic fraction. Discharge of organic-rich dredged sediments at sea results in degradation of contained organic matter and may affect the environmental impact of these metals significantly. These results therefore help to improve the waste management of such contaminated sediments.     

Chemical forms of Pb, Zn and Cu in the sediment profiles of the Pearl River Estuary

The chemical forms of heavy metals (Pb, Zn and Cu) in sediment cores of the Pearl River Estuary were studied using a sequential chemical extraction method. The isotope ratios of 206Pb/207Pb in various chemical fractions were also measured to assess the potential Pb sources. Zinc and Cu were mainly associated with the residual fraction. The Fe-Mn oxide and organic/sulphide fractions were the next important phases for Zn and Cu, respectively. For Pb, different chemical partitioning patterns were found among different sediment cores. Most Pb was associated with the residual fraction in the sediments. In some sediment profiles, the major phase of Pb in the top layers was the Fe-Mn oxide fraction. The proportion of Pb in the Fe-Mn oxide fraction decreased significantly with increasing depth. Among the different depths, the 206Pb/207Pb isotope ratios in the residual fraction remained fairly stable, with a mean value of 1.202, which may represent the natural background value. The 206Pb/207Pb ratios in the exchangeable fraction were the lowest among the five fractions, particularly in top sediments, showing the anthropogenic inputs of heavy metals from recent rapid industrial development in the surrounding region. For the other three non-residual fractions, there was a similar trend of increasing 206Pb/207Pb ratios down the profile. Results from this study are useful in assessing both the chemical changes for heavy metals in marine sediments and the potential of heavy metal release into the water environment of an estuary area.     

Evaluation of phosphorus bioavailability in El Mex Bay and Lake Mariut sediments

Phosphorus (P) fractions and their bioavailability in the sediments from El Mex Bay and Lake Mariut in Egypt were investigated using different chemical extraction methods. Sodium bicarbonate (NaHCO3) extractable P (Olsen-P) was the largest fraction (14.42%), followed by algal available P (AAP) (3.56%), water soluble P (WSP) (0.79%), and readily desorbable P (RDP) (0.06%) for El Mex Bay. While AAP con-tributed 9.94% to total P in sediments from Lake Mariut, Olsen-P 8.53%, WSP 4.11%, and RDP 0.92%. Summation of the bioavailable P fractions didn't exceed the sediment quality guidelines, and, therefore, P doesn't represent a danger to marine organisms. Correlation coefficients showed that no apparent relations between total P (TP) and iron (Fe), aluminum (Al), and calcium (Ca) in the sediments. Fur-thermore, Fe:P ratio was less than 15 indicting that there was not enough Fe in surface sediments to bind to P at most of the sampling sites. The positive correlation between TP and organic matter (OM) for Lake Mariut and El Mex Bay sediments indicated that the organic matter content of the sediment was a useful predictor of the total phosphorus content. Data from this study constitute a baseline of phosphorus bioavailability in sediments from El Mex Bay and Lake Mariut and could be used as a reference for future studies on the changes of bioavailable and residual phosphorus fractions over time.     

Diagenesis and anthropogenesis of metals in the recent Holocene sedimentary record of the Ría de Vigo (NW Spain)

To contribute to establishing a historical baseline for future evaluations of the environmental quality of the Ría de Vigo (NW Spain), we report metal contents determined in eight gravity cores obtained at representative locations in 1990 - before the installation of any wastewater treatment plants - and in fractions thereof that were obtained by the BCR sequential extraction method. The results suggest that early diagenesis had been influenced by both hydrodynamic conditions and organic matter input (the latter especially in areas devoted to mariculture), and that anthropogenic inputs had also affected the concentrations and between-fraction distribution of Cu, Pb, Zn and other metals in surficial sediments.     

The distribution and speciation of trace metals in surface sediments from the Pearl River Estuary and the Daya Bay, Southern China

Surface sediments collected from the Pearl River Estuary (PRE) and the Daya Bay (DYB) were analyzed for total metal concentrations and chemical phase partitioning. The total concentrations of Cr, Cu, Ni, Pb, and Zn in the PRE were obviously higher than those in DYB. The maximum concentrations of trace metals in DYB occurred in the four sub-basins, especially in Dapeng Cove, while the concentrations of these metals in the western side of the PRE were higher than those in the east side. Such distribution pattern was primarily due to the different hydraulic conditions and inputs of anthropogenic trace metals. The chemical partitioning of metals analyzed by the BCR sequential extraction method showed that Cr, Ni, and Zn of both areas were present dominantly in the residual fraction, while Pb was found mostly in the non-residual fractions. The partitioning of Cu showed a significant difference between the two areas.     

Comparison of Extraction Procedures for Assessing Soil Metal Bioavailability of to Wheat Grains

Agricultural soils have been analyzed to elucidate whether the trace metal distribution changes in relation to agricultural activities and to predict environmental risk. In addition to the extractability of Cu, Mn, Ni, Pb, and Zn in soils was compared by single extraction (hydrochloric acid (HCl), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), calcium chloride (CaCl₂), water (H₂O)), and sequential extraction procedures. The modified Community Bureau of Reference (BCR) sequential extraction procedure (three‐step) used to extraction of metals in soil samples. The extraction capacity of the analyzed metals was found by using single extraction procedures in the order: HCl > EDTA > DTPA > CaCl₂ > H₂O. A single correlation analysis was used to investigate the relationship between extractable metal concentrations in soil solutions and metal accumulation in wheat grains. Simple correlation analyses indicated that the extractable Pb and Ni of soils by HCl, EDTA, and DTPA single extraction procedures were significantly correlated with the metal contents of wheat grains. For CaCl₂, H₂O, and BCR extraction procedures there was a relatively poor correlation between the extractable Cu, Mn, Ni, Pb, and Zn of soils and metal contents of wheat grains.     

Two Experimental Methods to Determine the Speciation of Cadmium in Sediment from the River Neckar

The binding forms of Cd to an anaerobic sediment of low sulfide content from Lauffen reservoir (River Neckar, Germany) were studied using two different approaches, i. e. sequential extraction (modified from published protocols) and titrimetric study of the pH-dependent Cd release. Thermodynamic equilibrium calculations were applied to calculate both the release pattern of Cd during the titrations and the speciation of Cd within the single fractions of the extraction protocol. The calculations were based on measured sediment parameters such as hydrous ferric oxide (HFO), acid volatile sulfide, carbonate content and total Cd content, and the extractants (oxalate, acid etc.) used. The results of the two independent approaches coincided well in that they both assigned more than two thirds of the total Cd content to be adsorbed to organic matter. Cd bound as CdS is of little importance. Sequential extraction after a 3-month oxidation period at pH 7 revealed a shift of Cd from being mainly bound in stronger surface complexes with organic matter to being mainly bound in weaker surface complexes with organic matter and HFO, and thus becoming more bioavailable. This study suggests that the use of sequential extraction although being frequently criticized due to its operational character can be used to determine binding forms of metal ions if they are accompanied by 1) careful supporting experiments, 2) analysis of important sediment parameters, and 3) the use of thermodynamic equlibrium models which can help to understand Cd speciation within the extraction fractions.     

Distribution,fractionation, and contamination assessment of heavy metals in offshore surface sediments from western Xiamen Bay,China

Surface sediment samples were collected at 21 offshore sites in western Xiamen Bay, Southeast China.Total concentrations of Li, V, Cr, Co, Ni, Cu, Zn, Sr, Mn,Pb, Ba, Fe, and Ti were determined by inductively coupled plasma-optical emission spectrometry; Hg was determined by atomic fluorescence spectrometry. A modified BCR sequential extraction procedure was used to extract fractions of the above elements. Concentrations of Pb, Cr, and Hg at most sites met the primary standard criteria of Marine Sediment Quality except site S12 for Pb and S7 for Cr, while concentrations of Zn at 17 sites and Cu at seven sites exceeded the criteria. The mean concentration of Hg was three times higher than the background, with a possible source being the Jiulong River. Fe, Ti, Ba, Co, V, and Li dominated the residual phase, mainly from terrestrial input.Ni, Cr, Pb, and Hg in the non-residual phase varied largely between sites. Sr, Mn, Cu, and Zn were mainly in the nonresidual fraction. Most sites showed considerable ecological risk; exceptions were site S7(very high) and sites S10,S11, and S14(moderate). Cu showed moderate-to-high pollution and Pb exhibited no-to-low pollution, while other metals had a non-pollution status according to their ratios of secondary phase to primary phase(RSP). Results of two assessment methods showed moderate pollution and a veryhigh ecological risk for Cu, Zn, Ni, and Cr at site S7, which might be due to the local sewage treatment plant.     

巢湖蓝藻聚集对重金属迁移释放的影响

以巢湖蓝藻水华聚集地西半湖表层沉积物与蓝藻为对象,研究了表层沉积物重金属(Cd、Cr、Cu、Zn、Pb、Ni和Mn)总量的分布特征.同时,利用BCR连续提取法对沉积物中重金属Cd和Mn的形态进行分析,模拟探究蓝藻腐殖化过程中重金属含量的变化,探讨了蓝藻腐殖化对重金属吸附-释放的影响.结果表明,各采样点表层沉积物重金属含量均不同程度超出背景值,且距离南淝河越近越突出.潜在迁移指数表明整个西半湖沉积物中重金属Cd比Mn更易形成二次污染.相关性分析显示重金属Cd和Mn各形态含量和总量之间均表现出极显著正相关.巢湖西半湖属于典型的藻型湖,Cd和Mn的来源和分布均与蓝藻聚集密切相关,结合实验室模拟蓝藻腐殖化过程对重金属的吸附-释放规律,认为蓝藻腐殖化过程会对Cd和Mn的迁移释放产生影响.     

Measuring and modeling vertical gradients in suspended sediments in the Solimões/Amazon River

Accurately measuring sediment flux in large rivers remains a challenge due to the spatial and temporal cross‐sectional variability of suspended sediment concentrations in conjunction with sampling procedures that fail to accurately quantify these differences. This study presents a field campaign methodology that can be used to improve the measurement of suspended sediment concentrations in the Amazon River or similarly large rivers. The turbidity signal and Rouse model are together used in this study to define the spatial distribution of suspended sediment concentrations in a river cross‐section, taking into account the different size fractions of the sediment. With this methodology, suspended sediment fluxes corresponding to each sediment class are defined with less uncertainty than with manual samples. This paper presents an application of this methodology during a field campaign at different gauging stations along a 3,000‐km stretch of the Solimões/Amazon River during low water and flood periods. Vertical concentration profiles and Rouse model applications for distinctive sediment sizes are explored to determine concentration gradients throughout a cross‐section of the river. The results show that coupling both turbidity technology and the Rouse model may improve our understanding of the spatial distribution of different sediments fractions sizes in the Solimões/Amazon River. These data are very useful in defining a pertinent monitoring strategy for suspended sediment concentrations in the challenging context of large rivers.     

Free and bound polybrominated diphenyl ethers and tetrabromobisphenol A in freshwater sediments

Both free and bound fractions of polybrominated diphenyl ethers (PBDEs) and tetrabromobisphenol A (TBBPA) in sediment were examined. The free fraction was operationally defined as the fraction of each target compound extracted with a solvent mixture of hexane/acetone by Soxhlet extraction, while the bound fraction was the portion released from the sediments by alkaline hydrolysis following the solvent extractions. Tri- to hepta-BDEs and TBBPA were detected in the bound fraction. Bound PBDEs accounted for 0.2-2.8% of the total PBDEs and bound TBBPA accounted for 6.5-48% of the total TBBPA, in surface sediments. In sediment cores, these percentages ranged from 1.8% to 42% for bound PBDEs and 22-92% for bound TBBPA. The percentages of bound materials showed an increasing trend with the sediment depth. Sequestration of PBDEs and TBBPA within sediments might be an important geochemical fate of these brominated flame retardants.     

Controls on carbon and nitrogen export in an eroding catchment of south‐eastern Queensland,Australia

Effects of gully and channel erosion on the export of sediments are in general well understood, but the effects on carbon (C) and nitrogen (N) export remain an open question. We examined these effects and the role of flow magnitude, total wet season rainfall, catchment size and the C and N content and solubility of most probable sediment sources in a subtropical catchment. We sampled the baseflow and the rising stage of high‐flow events for one wet season and analysed 5 years of water quality data from event sampling stations. Total suspended sediment was the main variable explaining N export followed by rainfall, flow and catchment size. N was exported mainly in particulate organic form and C in dissolved form. The quality of most probable sediment source fractions explains these results and points to fractionation during transport into C and N richer and C and N poorer fractions, with travel distance ultimately determining the average quality of transported sediment for different flow magnitudes. Erosion would have caused a lower C and N concentration in sediments, a lower proportion of mineralized N, a larger proportion of dissolved organic C and a larger C : N ratios of the soluble fraction as compared with unincised grassed valleys. This would alter the rates of nutrient cycling and energy flow within and across ecosystem compartments in streams receiving this export. Copyright © 2014 John Wiley & Sons, Ltd.     

Distribution and source differentiation of PAHs and PCBs among size and density fractions in contaminated harbor sediment particles and their implications in toxicological assessment

Sediment samples collected from Kaohsiung Harbor (Taiwan) were analyzed for 15 priority polycyclic aromatic hydrocarbons (PAHs) and 118 individual polychlorinated biphenyl (PCB) congeners in various particle size fractions and two density fractions. The PAHs in the low density fraction were a much more sensitive and effective indicator of the PAH source than those in the sediment as a whole. Hierarchical cluster analysis of PAH analytes in the low density sediments revealed significant differences in compositional patterns between locations and among size fractions. In the sediment samples from both study sites, the low density fraction particles had up to 155 and 150 times higher concentrations of PAHs and PCBs, respectively, than those in the corresponding high density fractions. In addition, the total toxic benzo[a]pyrene and 2,3,7,8-tetrachlorodibenzodioxin (TCDD, dioxin) equivalents in the sediment low density fractions were much higher (up to 170 and 273 times, respectively) than the corresponding high density fractions.     

Trace elements migrating from tailings to rock varnish laminated sediments in an old mining region from Nelson,Nevada, USA

The dispersion and influence of soluble and particulate trace elements(TEs) present in the materials from abandoned mines is an imminent problem on terrestrial and aquatic environments.The goal of this research is to provide a broader view of such transport,assessing particle size distribution and TE interactions(e.g.,scavenging) with mine tailings and locally derived sediments transported by water in arid region.Sand grains from wash sediment were collected from a dry ephemeral wash in Nelson,N...