Occurrence of Li,B, Cu and Zn in some Egyptian Nile sediments

Lithium, boron, copper and zinc have been determined on cored and surface sediments from the delta and the drainage valley of the Nile River. The clay size fraction separated from the samples consists of montmorillonite and kaolinite as the predominant clay components, followed by illite and chlorite. Quartz and calcite are the non-clay admixtures.Lithium content varies between 7 and 48 ppm in the bulk sediments and between 28 and 61 ppm in the clay fractions, being clearly enriched in the clay material. In the clay fractions, concentration of lithium in kaolinite is indicated by a close relation between the lithium and kaolinite contents and is further supported by a close correlation with A1₂O₃.Boron in the clay fraction (62–112 ppm) appears to be concentrated in detrital illite.The concentrations of copper (26–900 ppm) and zinc (65–333 ppm) in the clay fractions correlate positively with the CO₂ percentage. Both elements tend to occur in or on the claysized grains of caleite.     

The stability of the relative content ratios of Cu,Pb and Zn in soils and sediments

The study indicates that the relative content ratios of Cu, Pb and Zn in soils and sediments tend to have stability compared to those in meteorites, rocks and organisms. This stability is considered to be associated with their geochemical properties and has no relationship to the existing environments if it is not disturbed by an anthropogenic factor. In addition, it can serve as a background reference in determining the changes in environmental quality due to human activities.     

Test of experimental set-ups for electrodialytic removal of Cu, Zn, Pb and Cd from different contaminated harbour sediments

Electrodialytic removal of heavy metals from different harbour sediments was investigated. Electrodialytic remediation experiments in laboratory scale were made with calcareous and non-calcareous harbour sediments. Two different experimental set-ups were used for the study, one with stirring of the sediment slurry, the other without stirring. The removal of heavy metals was highest in the non-calcareous sediment, where 94% Cd, 91% Zn and 73% Cu were removed after 24 days. The highest removal obtained for the calcareous sediment was 81% Cd, 76% Zn, 75% Pb and 53% Cu after 21 days, with stirred sediment slurry. Electrodialytic experiments without stirring of calcareous sediment gave high removals (84% Zn, 58% Pb and 48% Cu), but there were problems with precipitations in the sediment, which limited the removal. The stirred experiments gave the highest removals of heavy metals and the voltage was the most stable in these experiments, and thus, the stirred set-up is the best choice for experimental set-up. The order in which the heavy metals were removed from the harbour sediments was Cd>Zn>Pb>Cu.     

Risk analysis for remediation of contaminated sites: the geostatistical approach

The assessment of the risks associated with contamination by elevated levels of pollutants is a major issue in most parts of the world. The risk arises from the presence of a pollutant and from the uncertainty associated with estimating its concentration, extent and trajectory. The uncertainty in the assessment comes from the difficulty of measuring the pollutant concentration values accurately at any given location and the impossibility of measuring it at all locations within a study zone. Estimations tend to give smoothed versions of reality, with the smoothing effect being inversely proportional to the amount of data. If risk is a measure of the probability of pollutant concentrations exceeding specified thresholds, then the variability is the key feature in risk assessment and risk analysis. For this reason, geostatistical simulations provide an appropriate way of quantifying risk by simulating possible “realities” and determining how many of these realities exceed the contamination thresholds, and, finally, provides a means of visualizing risk and the geological causes of risk. This study concerns multivariate simulations of organic and inorganic pollutants measured in terrain samples to assess the uncertainty for the risk analysis of a contaminated site, an industrial site in northern Italy that has to be remediated. The main geostatistical tools are used to model the local uncertainty of pollutant concentrations, which prevail at any unsampled site, in particular by means of stochastic simulation. These models of uncertainty have been used in the decision-making processes to identify the areas targeted for remediation.     

Batch and column experiments to support heavy metals (Cu,Zn and Mn) in alluvial sediments

Laboratory batch sorption and column transport experiments were performed on heterogeneous alluvial soils with a wide range of physical characteristics from wells that are located in the region between Mogan Lake and Eymir Lake, Gölba??, Ankara. The mean values for the K _d of Cu were found to be highest in clay (32550.350 L/kg) and lowest in loamy sand (18170.76 L/kg). The minimum and maximum sorption capacity values (mean values) for Zn were found to be in clay (10985.148 mg/kg) and in silty loam (8597.14 mg/kg) units, respectively. Similarly, the minimum and maximum values for Mn were found in loamy sand (4908.695 mg/kg) and clay (7587.391 mg/kg) units. The non-linear least-squares optimization code “CXTFIT” was used to determine transport parameter values by curve-fitting. The results of the column experiments demonstrate dispersivity values within the range of 0.024–1.13 cm for soil samples.     

Electrokinetic iron pan generation in unconsolidated sediments: implications for contaminated land remediation and soil engineering

Electrokinetic remediation is an emerging technology that has generated considerable interest as a technique for the in situ remediation of clay-rich soils and sediments. Despite promising experimental results, however, at present there is no standardised universal electrokinetic soil/sediment remediation approach. Many of the current technologies are technically complex and energy intensive, and geared towards the removal of 90% or more of specific contaminants, under very specific field or laboratory-based conditions. However, in the real environment a low-tech, low-energy contaminant reduction/containment technique may be more appropriate and realistic. Such a technique, FIRS (Ferric Iron Remediation and Stabilisation), is discussed here. The FIRS technique involves the application of a low magnitude (typically less than 0.2 V/cm) direct electric potential between two or more sacrificial, Fe-rich, electrodes emplaced in, or either side of, a contaminated soil or sediment. The electric potential is used to generate a strong pH (and E_h) gradient within the soil column (pH 2–13), and force the precipitation of an Fe-rich barrier or “pan” in the soil between the electrodes. Geochemical and geotechnical data for FIRS-treated sediments from the Ravenglass estuary, Cumbria, UK indicate that the technique can significantly reduce contaminant concentration in treated soil, by remobilisation of contaminants and concentration on, or around, the Fe-rich barrier. Arsenic, in particular, seems highly amenable to the FIRS treatment, due to its solubility under the high pH conditions generated near to the cathode, and its marked geochemical affinity with the freshly precipitated Fe oxides and oxyhydroxides in the Fe barrier. Geotechnical tests indicate that the Fe barrier produced by the technique is practically impervious (permeability = 10⁻⁹ m/s or less), and has moderate mechanical strength (UCS ∼11 N/mm²). Notably, a large increase in shear strength in the treated soil near to the anode electrode (due to Fe cementation and/or dewatering) is also observed, without significant loss of porosity. The data indicate that the FIRS technique shows considerable promise as an in situ method for contaminated land remediation and soil water containment, and for improving the mechanical properties of soils (contaminated or otherwise) for civil engineering purposes.     

Formation of pyrite in freshwater sediments: Implications for C/S ratios

The vertical distribution of pyrite, acid volatile sulphide (AVS), carbon, and total S (St) were determined directly in the sediments of three lakes of different trophic status. The results showed that freshwater pyrite formation reflects the redox status of the sediment or overlying waters. It appears to form chiefly in reducing sediments which are subject to oxidizing influences, by either a low turnover of organic carbon or periodic incursions of oxygen. Although there are high concentrations of AVS in the near-surface sediments of productive lakes, very little is diagenetically converted to pyrite.The feasibility of using sulphur ratios to diagnose whether rocks were formed in marine or freshwater environments is assessed. New values for FeS₂/FeS of 0.5-5 show that this ratio does not provide a reliable test. Values of C/Sp, where Sp represents pyrite sulphur, lie within the range of 160–700 and are much higher than previously measured ratios of C/S_t of 1–50. These new determinations show that, if pyrite sulphur is unequivocally measured, C/S ratios may be a more sensitive indicator of salinity than had been previously thought.     

Geochemistry of Cu, Co, Ni, Zn, Cd and Cr in the surficial sediments of a tropical estuary, southwest coast of India: a granulometric approach

 Geochemical characteristics of six trace metals – Cu, Co, Ni, Zn, Cd and Cr – in the bulk sediment and sand, silt and clay fractions of a tropical estuary on the southwest coast of India have been studied and discussed. In bulk sediment, the trace metal concentration is controlled mainly by the textural composition of the sample. Mud, sandy mud and sandy silt register higher concentrations of trace metals than that in sand-dominant sediments. The granulometric partitioning studies also re-affirmed the role of particle size in enriching the trace metals. The silt and clay fractions exhibit 7–8 times the enrichment of Cu and Cd compared to that in sand. The enrichment factors of Zn, Cr, Ni and Co in the silt and clay fractions, compared to that in sand, are 5–6, 4–5, 2–5 and 2–3 times, respectively. The trace metals in the sand fraction, particularly Ni and Cr, exhibit strong positive correlation with the heavy mineral content of the samples. It clearly indicates a heavy mineral pathway to the trace metals in the sand fraction. Cu and Co in silt and clay fractions exhibit a marked decrease towards the high saline zones of the estuary. This is attributed to the desorption of Cu and Co from particulate phases during estuarine mixing. Contrary to Cu and Co, the content of Zn in the clay fraction shows a marginal increase towards the estuarine mouth. This could be explained by the influx of Zn-rich contaminant discharges from Zn-smelting industries located slightly north of the estuarine mouth. The released Zn will effectively be held in the lattices of the clay mineral montmorillonite, which also exhibits a marked increase towards the estuarine mouth. The anomalously high values of Cd in some places of the Central Vembanad estuary is attributed to the local pollution. Received: 10 July 1995 · Accepted: 3 June 1996     

Uptake of Zn,Cu, Pb,and Cd by water hyacinth in the initial stage of water system remediation

The removal efficiency of water hyacinth for Zn, Cu, Pb and Cd after their entry into an undisturbed fresh water body was studied using minicosms placed within a reservoir. Variable parameters were water pH (6 or 8), single or multi-metal additions, and the plant biomass. The initial concentrations of Zn, Cu, Pb and Cd in water (500, 250, 250 and 50 μg/L, respectively) quickly decreased in the order Pb ≈ Cu ? Cd ≈ Zn in the first days. Metal removal was more efficient at pH 8 than at pH 6, and it was only slightly higher for single metals compared to multi-metal additions. After 8 days the remaining amounts of metals relative to their initial concentrations for multi-metal pollution treatments were 8% and 24% (Cu), 11% and 26% (Pb), 24% and 50% (Cd), and 18% and 57% (Zn) at pH 8 and pH 6, respectively. Increasing plant biomass promoted faster metal removal. The bioconcentration factor (the ratio of the metal concentration in whole plants to the initial metal concentration in water) exceeds 2000 for all metals (with the exception of Zn and Cd at pH 6). It was concluded that the water hyacinth can be successfully used for fast removal of metals in the initial stage of water body remediation.     

Chemical speciation of Cd,Cu, Pb,and Zn in mixed freshwater,seawater, and brine solutions

A theoretical model was developed to study the chemical speciation of the trace elements Zn, Cd, Cu and Pb aqueous solutions and their responses to variations in ionic strength and complexation. Two mixing solutions were investigated, a freshwater-seawater system and a freshwater-brine system. The brine was a calcium, sodium-chloride solution with a molal ionic strength of two. Trace element associations with the ligands OH^?, Cl^?, CO^2?₃, SO^2?₄, and HCO^?₃ were considered at pHs from 3.5 to 11.0 at 25°C. In general, the relative importance of the various ligand-trace element complexes can be predicted from a comparison of their stability constants. However, the effect of pH on the importance of a given complex is not readily apparent from the stability constants. Freshwater-seawater mixtures, as might be found in a totally mixed estuary, show that seawater composition is the dominant control on chemical complexing. Chloride complexing is similar for lead and zinc in the freshwater-brine mixtures. This similarity may account in part for the association of lead and zinc in strata-bound ore deposits.     

Model for the distribution of sulfate reduction and methanogenesis in freshwater sediments

A model, based on the in situ physiological characteristics of methanogens and sulfate reducers, was developed to describe the distribution of methanogenesis and sulfate reduction in freshwater sediments. The model predicted the relative importance of methane production and sulfate reduction in lakes of various trophic status and generated profiles of sulfate, acetate, methanogenesis, and sulfate reduction comparable to the profiles that are expected based on field studies. The model indicated that at sulfate concentrations greater than 30μM a sulfate-reducing zone develops because sulfate reducers maintain acetate concentrations too low for methanogens to grow. At lower sulfate concentrations a methanogenic zone develops because the dual limitations of low sulfate concentrations and acetate consumption by methanogens prevents sulfate reducers from growing. The model and a compilation of previously published field data indicate that, within the reported range of sulfate concentrations, the relative importance of methanogenesis and sulfate reduction in freshwater sediments is primarily dependent upon the rates of organic matter decomposition.     

Sources, input pathways, and distributions of Fe, Cu, and Zn in a Chesapeake Bay tidal freshwater marsh

Tidal freshwater marshes exist at the interface between watersheds and estuaries, and thus may serve as critical buffers protecting estuaries from anthropogenic metal pollution. Bi-weekly samples of newly deposited marsh sediments were collected and analyzed for Cu, Zn, and Fe concentrations over 21 months from July 1995 to March 1997 in five distinct habitats at the head of Bush River, Maryland. Bi-weekly anthropogenic metal enrichments ranged from 0.9–4.7. Anthropogenic excess metal loadings averaged over 1996 ranged from 6–306 and 25–1302 μg cm⁻² year⁻¹ between sites for Cu and Zn, respectively. Based on Fe-normalized trace metal signatures, Susquehanna River sediment does not significantly contribute to upper Bush River. Organic matter was found to dilute total metal concentrations, whereas past studies suggested organics enhance labile metal content. Analysis of metal input pathways shows that marsh metals are primarily imported from nearby subtidal accumulations of historic watershed material by tidal flushing. Received: 29 April 1999 / Accepted: 7 December 1999     

Organic sulphur fixation in freshwater lake sediments and the implication for US ratios

A comparative analysis of two sediment cores from perialpine lakes (L. Zürich and L. Geneva) helped to clarify pathways of sulphur fixation in freshwater sediments. Despite greater than three-fold differences in lake water sulphate concentration equal amounts of sulphur are fixed in the sediments. The maximum sedimentary sulphur concentrations attain 1% (dry weight) which is similar to the sulphur content of modem, near-shore marine sediments. This is also expressed in low C _org/S_tot ratios which range from 2.5–8.
An analysis of the sulphur pools showed that organic sulphur compounds are the main components of the sedimentary sulphur, accounting for ˜ 80% and ˜ 60% of the total sulphur in Lakes Zürich and Geneva, respectively. The largest single sulphur pool is the sulphate-esters, which comprise 40–60% of the total sedimentary sulphur. Substantial amounts of the organic sulphur compounds must be formed within the sediment by boundary-layer microbial communities at the oxic-anoxic transition zone. This possibly suggests rapid recycling of sulphur in suboxic zones. Because of low concentration of SO²₄-_- in the watermass, the zone of sulphate reduction is very thin. This coupled with the mobility of some sulphide oxidizing microbial colonies (e.g. Beggiutoa ) potentially results in an almost complete recycling of the sulphur pool near the sediment-water interface. Reduced sulphur caught in this cycling process is unavailable for sedimentary pyrite formation. The C_org/S_pyriteratios for these sediments are thus high. If organically bound sulphur is not completely transformed into pyrite during late diagenesis, the C_org/ S_pyrite ratio can serve as a sensitive indicator for the salinities of anaent depositional environments.     

Comparison of three procedures (single,sequential and kinetic extractions) for mobility assessment of Cu,Pb and Zn in harbour sediments

The mobility of Cu, Pb and Zn in harbour sediments was investigated using single, sequential and kinetic extraction techniques. Each type of extraction provides different information on the mobility of these elements in the environment. The single HCl extraction assesses general mobility, the sequential extraction assesses geochemical partitioning and kinetic extraction allows quickly and slowly mobilized elements to be identified. Kinetic extraction also allows the influence of extraction duration to be assessed. The results presented in this paper highlight the complementary information provided by different types of mobility studies. The lack of correlation between element mobility and total metal concentration emphasises the inadequacy of using total metal concentrations in risk assessment.     

徐州市矿山环境保护与治理工程研究

随着徐州市矿山环境保护与治理工程的实施,徐州市因采煤塌陷及开山采石造成的生态环境问题及景观破坏得到改善,废弃闲置的土地资源得到有效利用。通过分析徐州市矿山环境保护与治理的现状,以生态优先、以人为本及经济效益和示范效应为原则,部署废弃露采矿山治理、采煤塌陷地复垦及绿色矿山建设的重点工程,从资金筹措、技术支撑及政策保障等方面提出重点工程实施的保障措施。     

Mineral deposits and Cu–Zn–As dispersion–contamination in stream sediments from the semiarid Coquimbo Region,Chile

This paper presents Cu–Zn–As geochemical data from stream sediment surveys carried out in the three main watersheds of the Coquimbo Region of Chile. This mountainous semiarid realm occupies an area of 40,656 km² between 29° and 32°S. Given that the area has a long historical record of mining activities, important environmental disturbances were expected. However, despite the detection of three major geochemical anomalies for Cu, Zn, or As, only one can be unmistakably linked to the development of mining–metal recovery procedures (Andacollo–Panulcillo). An investigation of the other two anomalies (Elqui and Hurtado) reveals three major causes that fully or partially account for them: (1) the type of ore deposit and associated hydrothermal alteration; (2) the regional structural setting (intensity of fracturing); and (3) climate–landscape. Cu–Au–As epithermal deposits/prospects along the so-called El Indio belt are here regarded as the sources of both the Elqui and Hurtado anomalies. The strong advanced argillic alteration present in some of the epithermal deposits/prospects of the El Indio belt may have induced the loss of the buffering capacity of rocks, and therefore favoured metal dispersion during later oxidation–leaching of sulphides. This applies to the Elqui and Hurtado anomalies. Conversely, given that the potassic, propylitic and phyllic alterations do not affect the buffering capacity of rocks, only minor metal dispersion is observed in relation to the Los Pelambres porphyry copper deposit. Besides, the epithermal belt is located within a highly fractured Andean domain (3,000–4,000 m of altitude), which may have conditioned the fast unroofing of ore deposits, contributed to enhanced circulation of meteoric waters, and eventually, to strong oxidation, and leaching of metals. Metal dispersion is aggravated during rainy years in response to strong El Niño episodes.     

The history of Cu,Pb, and Zn inputs to Narragansett Bay,Rhode Island as recorded by salt-marsh sediments

The distribution of metals with depth in sediment cores sampled from industrialized estuaries can reveal long-term trends in loadings to the waterbody. Salt marsh cores were sampled from five locations from the head to the mouth of Narragansett Bay and from one location from a marsh inside a lagoon on the coast of Block Island Sound with the intent of reconstructing historical loadings of Pb, Cu, and Zn to this estuary. Concentrations of Fe and Mn were measured as indicators of redox conditions of the sediment column. Chronologies were developed using accretion rates determined previsly from²¹⁰Pb analyses of the same cores. Excess metal inventories and enrichment over pre-industrial concentrations were greater in upper bay cores reflecting the location of sources at the head of the estuary. The bay cores were similar with respect to the distributions of Cu, Pb, and Zn. Concentrations of all metals began to increase over background levels at depths corredponding approximately to the year 1900. Most of the cores showed peak concentrations of Cu and Pb in the early 1950s and 1970s. Distributions of Zn were more variable among cores, showing peaks in the early 1920s in some cores and in the 1950s and 1970s in others. In general, the observed distributions in the bay cores are consistent with estimated long-term trends in loadings from atmospheric and sewage sources. The metal distributions in the lagoon core appear to reflect atmospheric loadings. However, there are features in some cores that are not explainable using the estimated trends in source inputs. There also is not a 1∶1 correspondence between changes in sediment metal concentrations and changes in loadings. It is likely that this method of reconstruction would benefit from a more detailed characterization of sources, but comparison of sediment and historical records do show that attempts to reduce loadings to the bay have been successful.     

MC-ICP-MS测定积累植物中Cu、Zn同位素的化学分离方法研究

多接收器等离子体质谱仪(MC-ICP-MS)高精度同位素组成的准确测定,依赖于对样品中待测元素的分离纯化.本研究比较了两种溶样方法对有机样品积累植物海州香薷的消解效果,检测了AG MP-1阴离子交换树脂对样品中Cu、Zn的分离效果,并测定了样品中的Cu、Zn同位素组成.结果表明:①两种不同溶样方法均能有效地破坏累植物海州香薷样品中的有机质;②AG MP-1树脂能有效分离纯化植物中的Cu、Zn,经过AG MP-1树脂一次交换分离和二次交换分离的植物根样品的Cu接收液基体元素的去除基本没有差别,经过一次交换分离的Zn溶液,基体元素也基本除去,可以用于MC-ICP-MS对Cu、Zn同位素组成高精度的测定;③Cu、Zn同位素组成测定误差不大于仪器的长期重现性,表明样品的化学处理过程、各离子交换树脂柱分离交换过程和仪器测试过程均有很好的重现性,符合样品测定的要求.     

Groundwater protection in fractured media: a vulnerability-based approach for delineating protection zones in Switzerland

A vulnerability-based approach for delineating groundwater protection zones around springs in fractured media has been developed to implement Swiss water-protection regulations. It takes into consideration the diversity of hydrogeological conditions observed in fractured aquifers and provides individual solutions for each type of setting. A decision process allows for selecting one of three methods, depending on the spring vulnerability and the heterogeneity of the aquifer. At the first stage, an evaluation of spring vulnerability is required, which is essentially based on spring hydrographs and groundwater quality monitoring. In case of a low vulnerability of the spring, a simplified method using a fixed radius approach (“distance method”) is applied. For vulnerable springs, additional investigations must be completed during a second stage to better characterize the aquifer properties, especially in terms of heterogeneity. This second stage includes a detailed hydrogeological survey and tracer testing. If the aquifer is assessed as slightly heterogeneous, the delineation of protection zones is performed using a calculated radius approach based on tracer test results (“isochrone method”). If the heterogeneity is high, a groundwater vulnerability mapping method is applied (“DISCO method”), based on evaluating discontinuities, protective cover and runoff parameters. Each method is illustrated by a case study.