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1.
The distinction between 'free' metals and organically complexed metals in aqueous solutions is important for research involving the mobility or bioavailability of metals in the environment. In this study, the applicability of equilibrium dialysis (molecular weight cut-off = 1000 Da) and diffusive gradients in thin films (DGT) to determine 'free' Al, Fe(III) and Zn in four forest soil solutions was compared. The 'free' metals as measured by both methods, consist of hydrated metal cations and soluble inorganic metal complexes. In addition, dialysis measures any organic complexes < 1000 Da and DGT measures a portion of smaller labile organic complexes. The four soil solutions were prepared by water extraction of an organic soil horizon (H) from a Fimic Anthrosol, and contained either 20 or 75 mg C/l dissolved organic matter at pH 4.0 and pH 7.0. To test the performance of both methods and optimize experimental volume and time, experiments using metal nitrate solutions were carried out. In the solutions at pH 4.0, no significant differences in average 'free' metal contents were found for Al, Fe(III) or Zn. This makes DGT a viable alternative for equilibrium dialysis for the study of the complexation of all three metals in acidic soils. At pH 7.0, again no significant difference between both methods were found for Al and Fe(III), but the DGT results for Zn were significantly higher. This was likely caused by labile organic complexes that were only detected by DGT.  相似文献   

2.
This paper reviews the factors affecting trace metal behaviour in estuarine and riverine floodplain soils and sediments. Spatial occurrence of processes affecting metal mobility and availability in floodplains are largely determined by the topography. At the oxic-anoxic interface and in the anoxic layers of floodplain soils, especially redox-sensitive processes occur, which mainly result in the inclusion of metals in precipitates or the dissolution of metal-containing precipitates. Kinetics of these processes are of great importance for these soils as the location of the oxic-anoxic interface is subject to change due to fluctuating water table levels. Other important processes and factors affecting metal mobility in floodplain soils are adsorption/desorption processes, salinity, the presence of organic matter, sulphur and carbonates, pH and plant growth. Many authors report highly significant correlations between cation exchange capacity, clay or organic matter contents and metal contents in floodplain soils. Iron and manganese (hydr)oxides were found to be the main carriers for Cd, Zn and Ni under oxic conditions, whereas the organic fraction was most important for Cu. The mobility and availability of metals in a floodplain soil can be significantly reduced by the formation of metal sulphide precipitates under anoxic conditions. Ascending salinity in the flood water promotes metal desorption from the floodplain soil in the absence of sulphides, hence increases total metal concentrations in the water column. The net effect of the presence of organic matter can either be a decrease or an increase in metal mobility, whereas the presence of carbonates in calcareous floodplain soils or sediments constitutes an effective buffer against a pH decrease. Moreover, carbonates may also directly precipitate metals. Plants can affect the metal mobility in floodplain soils by oxidising their rhizosphere, taking up metals, excreting exudates and stimulating the activity of microbial symbionts in the rhizosphere.  相似文献   

3.
The impact of runoff from sulfuric soils in the heavily drained Cudgen Lake floodplain, eastern Australia on water quality and downstream coastal lake sediments has been examined. The oxidation of sulfidic soils and the transformation into sulfuric soils leads to changes not only in the upper soil profile but also affects drainage water quality and the chemistry of bottom sediments in receiving waters. Oxidation transforms the soil from a sink for sulfur and metals to a significant source for downstream environments. Sulfuric soils within the Cudgen Lake catchment contain 9.18 x 10(5) mol H+ per hectare as well as elevated concentration of metals (e.g. Al, Fe, Mn) and sulfate. These products of sulfidic soil oxidation are transported efficiently from the soil profile by the constructed drainage network and into the downstream lake system. The acid volatile sulfur (AVS), chromium reducible sulfur (CRS), total sulfur, organic carbon, and reactive iron contents present in the solid phase of the lake sediments are reported. The AVS/CRS, DOP and DOS values observed in the lake sediments show that natural monosulfide formation in the near surface sediments has been enhanced due to increased inputs of organic matter, sulfate, ferrous iron and other metals following development of the catchment. There are elevated concentrations of metals (e.g. As, Al, Cd, Cr, Hg, Zn and Pb) in the upper layer of monosulfidic lake sediments compared with the underlying pyritic sediments some of which exceed sediment quality guidelines. These metals could be released by dredging or through re-suspension during high flow conditions or enter the food chain.  相似文献   

4.
The conservative biogeochemical behavior of dissolved Zn and Cd in a 17-km, free-flowing reach of the Coeur d'Alene River downstream of a mining district is typical of watersheds in which suspended matter concentrations are low. For watersheds impacted by acid-rock drainage (ARD), low suspended matter concentrations are more likely to be found when acid rock drainage travels through soils because much of the Fe and Al that could form adsorbing surfaces is retained within the soils. In the absence of additional sources of solid substrates, metals can be transported great distances downstream once this Fe- and Al-poor ARD seeps into surface waters. In a 46-km backwater reach of the Coeur d'Alene River, it appears that biological activity increased pH and provided the organic matter solid substrate which removed approximately 50% of the Zn and Cd. Zn removal was partially reversible as pH decreased. These observations reinforce the concept that both inorganic and organic carbon chemistry must be measured if significant. advances in our understanding of the attenuation of Zn and Cd from ARD sources are to be made.  相似文献   

5.
Two industrial by-products with high iron contents were tested for their effectiveness in the stabilisation of arsenic and trace metals in chromated copper arsenate (CCA)-contaminated soil. Steel abrasive (SA; 97% Fe(0)) and oxygen scarfing granulate (OSG; 69% Fe(3)O(4)) were applied at levels of 1% and 8% (w/w) respectively to two soils with different organic matter contents. Field lysimeter measurements indicated that SA and OSG treatments decreased the arsenic concentration in pore water by 68% and 92%, respectively, for the soil with low organic matter content, and by about 30% in pore water of soil with high organic matter content. At pH < or =6, the amended soil with low organic content contained elevated levels of manganese and nickel in their pore water, which were sufficient to induce cytotoxic effects in L-929 mouse fibroblast cells. The industrial by-products have significant potential for soil amendment at field-scale, but caution is required because of the potential release of their chemical contaminants and their reduced capacity for sorption of arsenic in organic-rich soils.  相似文献   

6.
Metals occur naturally in soil, but contents are generally increased in the urban environment due to anthropogenic activities. The presence of elevated metals in soils of the urban environment has been recognized as an important source of metal intake in children and is linked to elevated metal levels in children's blood. Several metals have undesirable health effects, especially on children due to their still developing nervous system and small body volumes. Playgrounds are where urban children spend most of their time outdoors and are also where children most frequently come in contact with soil. Elevated contents of metals in playgrounds are therefore of great concern for children's wellbeing. This study investigates the soil metal content of 25 playgrounds located in different land use areas in urban Uppsala, Sweden's fourth largest city. Uppsala covers an area of approximately 100 km2 and has a population of 136,000. The soil samples were analysed for 12 metals (Al, As, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, W, Zn) using aqua regia. Median metal contents were found to be 1.8, 3.4, 0.21, 32, 25, 2.5, 0.14, 494, 19, 26, 0.35 and 84 mg kg(-1) soil for each of the above metals, respectively. The median clay content was around 20% while the organic matter content was measured by loss on ignition at a median of 8%. The land use areas included industrial land, the city center, road verges, natural land and former industrial land. The results showed that land use did not have the expected large influence on the total metal contents of the soils tested. The clay content together with the age of the site proved to be a more important factor. Sites with elevated clay contents had in general elevated metal contents, which were explained by the relatively high adsorption capacity of clay particles. The soils at sites where land use had not been altered since the 1800s had increased metal contents compared to playgrounds constructed in the late 1900s. The immobility of metals once they had entered the soil system was the reason for increased metal content in soils of old playgrounds. It was concluded that in cities with few internal pollution sources, the soil characteristics of the site and the time the soil has been on-site to accumulate metal residues become important factors in determining the soil metal content.  相似文献   

7.
To better understand the precipitation behaviour of dissolved organic matter induced by interactions with metals, a systematic titration experiment was conducted mimicking the soil solution conditions in an acidic, sandy soil. The variables of interest included the type of metal species (Al, Fe), the redox state [Fe(II), Fe(III)], the pH (3.5, 4.0, 4.5), the metal to organic carbon (M/C) ratio and the competition between Al and Fe. Precipitation of DOM–Al appeared to be strongly correlated with M/C ratio and the pH. For Fe(II) only little precipitation occurred, while the strongest flocculation degree was found after addition of Fe(III). In contrast to Al, hardly any correlation between DOM–Fe precipitation and pH was observed. Both reduction and oxidation of Fe was found and exhibited a strong effect on the precipitated amounts of DOM and Fe. In competition, Al determined the precipitation behaviour at lower M/C ratios (<0.10), while at higher M/C ratios Fe determined the flocculation. Below a M/C ratio of 0.06 Al was the dominant metal in the precipitates, especially at lower pH levels, while the opposite trend was found at M/C ratios above 0.06. Overall, Fe(III) gave the strongest flocculation, although Al influenced the impact of Fe(III) interactions with DOM in relation to pH and M/C ratio.  相似文献   

8.
This study assessed the potential reuse of an aluminium coagulated drinking water treatment sludge (Al‐DWTS) as a main substrate in constructed wetland to replace soil for the treatment of P‐enriched wastewater. The adsorption isotherm and kinetics of phosphorus (P) removal from high‐P solution by Al‐DWTS and a local soil from Bailieborough, Ireland, were studied and compared. The P adsorption process was examined as a function of contact time, initial P concentration, pH and temperature. Data of P adsorption were well fitted to the Langmuir and the Freundlich isotherms but the Freundlich isotherm had a higher correlation coefficient. The P adsorption capacity on the Al‐DWTS and the soil tended to increase with an increase in temperature. The maximum P adsorption capacity of the Al‐DWTS and the soil was 39.4 mg P mg?1 and 9.5 mg P mg?1, respectively, at conditions of pH of 4.0 and temperature of 23°C. Kinetics studies show that adsorption in both cases followed pseudo‐second‐order kinetics. The fact that the Al‐DWTS exhibited a significantly higher P adsorption capacity at high P solution compared with the soil suggests that Al‐DWTS can be a ‘novel‐waste’ bioadsorbent with promising application in wastewater treatment engineering, such as constructed wetland systems.  相似文献   

9.
重金属污染事件频发引起了很多学者的关注,锰是一种重金属痕量元素,人体通过食物链摄入过量的锰会产生中毒效应。研究了Mn(II)的浓度、反应温度、土水比、pH值等因素对Mn(II)在黄土上吸附特性的影响。黄土对Mn(II)的吸附容量可达7.84 mg/g,等温吸附模型Langmuir、Freundlich和D-R模型都能很好地解释Mn(II)在黄土上的吸附性能。热动力学分析表明Mn(II)在黄土上的吸附是一个自发的过程,升高温度可促进吸附作用的进行。增大土水比可提高Mn(II)的去除效率,但单位黄土上Mn(II)的吸附量有个最优值。Mn(II)的初始浓度越大单位黄土的最大吸附量越小,达到最大吸附量所需的土水比越高。溶液的酸碱度是影响Mn(II)去除效果的一个重要因素,pH>10.7时Mn(II)几乎完全被去除。通过X光衍射图谱和红外光谱分析,探讨了黄土与Mn(II)的结合机理,黄土中的黏土矿物、有机质成分对重金属Mn(II)的吸附起重要作用。  相似文献   

10.
Heavy metal content (Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn) was analysed in the edible parts of two types of horticultural crops (leaf and inflorescence crops) from 30 agricultural fields in Castellón (Spain), a representative area of the European Mediterranean region. Selected soil properties relevant to control the mobility and bioavaibility of heavy metals were analysed for the general characterisation of these agricultural soils. The levels of clay, high percentages of organic matter and the presence of carbonate seem to suggest an important retention of heavy metals by these components in most of these soils. However, the high salinity in some fields (>4 dS/m) seems to facilitate the mobility of some heavy metals (e.g. Cu). The mean values of total contents of heavy metals in soils were similar to values obtained in other works on Spanish agricultural soils. However, there were some fields with a metal content (particularly Cu, Pb or Zn) higher than these works, reflecting an important anthropogenic source. In seven fields, the crop contents of Cd and/or Pb were higher than the maximum levels established by the Commission Regulation no. 466/2001 for horticultural crops. Heavy metal contents in leaf crops were higher than in inflorescence crops, except for Zn. The differences for Cd, Cr, Cu, Fe and Mn contents between these two types of crops were statistically significant. The analysis of crop heavy metal contents showed a higher absorption and/or accumulation of heavy metals in leaf crops than in inflorescence crops. Differences in crop characteristics seem to be responsible for the differential accumulation of heavy metals. Furthermore, agronomic practices and other sources of heavy metals (e.g. atmospheric deposition for Cd and Pb) may also have some influence on crop accumulation. Given the relevance of horticultural crops in the Mediterranean diet, it is highly necessary to extend the experience of this work to other areas of the European Mediterranean region.  相似文献   

11.
Adsorption equilibriums of principal herbicides on paddy soils in Japan   总被引:4,自引:0,他引:4  
Herbicides used in paddy fields during the flooding season can easily cause pollution by run-off into rivers or by other routes. It is very important to know the adsorption characteristics that influence their fate in the soil. The adsorption equilibriums have often been expressed by Henry equations, and the values of equilibrium constant, Kd, are estimated from the adsorption constants, K(OC), based on organic carbon contents of soils. There is little information concerning the equilibrium values expressed by the Freundlich equations, and insufficient information on the actual concentration levels in the paddy field. Therefore, adsorption equilibriums of the five principal herbicides: esprocarb, mefenacet, pretilachlor, simetryn and thiobencarb, on five kinds of paddy soil in Japan were investigated. It was found that their equilibrium values were better expressed by the Freundlich equation for concentration levels for the paddy fields, and that the values for the adsorption coefficient, n, varied from 1.0 to 1.6. Values for the coefficient, k, were in the range of 29-420 mg(1 - 1/n) l(1/n)/kg-dry, and the values were poorly related to solubilities in water or to the octanol-water partition coefficients of the herbicides. For each herbicide, except for simetryn, the values of k among the soils differed by 2-3 times, and no correlation could be found with the organic carbon contents, specific surface areas, pH, cation exchange capacity or major minerals of the soils. The adsorption equilibriums calculated from the values of adsorption constant Kd by the values of K(OC) in the literature were found to be very different from the experimental equilibriums. From the experimental values of coefficient k and n of the Freundlich equation, the maximum runoff concentrations of the herbicides were preliminarily estimated by a simple equilibrium model.  相似文献   

12.
A study was carried out in the Villaviciosa Estuary (Asturias, NW Spain) to determine the effects of polderization on soil properties and soil organic carbon content. The results showed that the polderized soils were more acidic and contained less carbonates and a higher soil organic carbon (SOC) content than the natural soils. The organic carbon stock in the reclaimed soils ranged from 83.2 to 91.8 t ha(-1), whereas in natural soils was approximately 43.7 t ha(-1). The degree of humification of the surface humic acids also indicated that the stability and degree of decomposition of the organic matter was higher in the reclaimed soils than in natural soils.  相似文献   

13.
The potential of cattle manure vermicompost and Brazilian soils (whole soils and soils incubated with vermicompost) was assessed for adsorption of heavy metals such as Cu(II) and Cd(II) from aqueous solutions. Experimental data have been fitted to Langmuir and Freundlich isotherms to obtain the characteristic parameters of each model, with R 2 values from 0.89 to 0.99. Based on the maximum adsorption capacity obtained from the Langmuir isotherm the affinity of the studied metals for the vermicompost and soils have been established as Cu(II) > Cd(II). The values of the separation factor, R L, which has been used to predict affinity between adsorbate and adsorbent were between zero and 1, indicating that sorption was very favourable for Cu(II) and Cd(II) in synthetic solution. Addition of vermicompost to soils resulted in higher distribution coefficient, K d, as compared with whole soils. The thermodynamic parameter, the Gibbs energy changes, was calculated for each system and the negative values obtained confirm that the adsorption processes are spontaneous. The ΔG° values for the substrates were between ?2.630±1.41 kJ mol?1 and ?13.700±1.250 kJ mol?1. Adsorption tests from multimetal systems confirm the affinity order obtained in the individual metal tests. The adsorption capacity for Cu(II) measured in individual tests is not reduced by the presence of Cd(II). There is also desorption of Cu(II) and Cd(II) previously bound to vermicompost, whole soils and soils incubated with vermicompost by DTPA. The experiment indicates the importance of cattle manure vermicompost and oxisol amended with vermicompost in relation to Cu(II) and Cd(II) adsorption from aqueous solution.  相似文献   

14.
生物覆盖层是一种新型生活垃圾填埋场覆盖层,对比传统的压实黏土覆盖层其具有较高的甲烷氧化能力,减少垃圾填埋场甲烷的释放。生物炭作为生物覆盖介质,除了提高土壤甲烷氧化能力之外,其较大的比表面积还能增加甲烷吸附能力。为更好地理解生物炭对土壤的甲烷吸附特性的影响,通过批量吸附试验研究生物炭改性土在不同甲烷初始浓度与生物炭掺量下的甲烷吸附能力。试验结果表明添加生物炭能提高土壤甲烷吸附能力,相比较原土,炭掺量为20%的改性土最大甲烷吸附量提高了一个量级,甲烷吸附能力得到明显提高主要得益于生物炭的多孔结构。并且生物炭改性土的吸附特性均符合Lagergren准二级吸附动力模型和Langmuir等温吸附模型。  相似文献   

15.
Nowack B 《Water research》2002,36(18):4636-4642
Phosphonates are used in large quantities in industry and household products as scale inhibitors and chelating agents. They are not biodegraded during wastewater treatment but are removed by adsorption processes. Field measurements from different wastewater treatment plants affirm that they are removed almost completely during wastewater treatment. Adsorption of nitrilotrismethylenephosphonic acid onto activated sludge, amorphous iron oxide and humic acids (HAs) was studied under controlled conditions. The adsorption onto HAs decreases sharply with increasing pH with negligible adsorption at pH above 6.5. Adsorption onto amorphous iron oxide follows a Langmuir behavior. The presence of 1 mM Ca doubles the maximum surface capacity at pH 7. Adsorption onto activated sludge is not very pH sensitive and is explained to a large extent by adsorption onto amorphous iron oxides, but the contribution of organic matter or other mineral phases cannot be ruled out.  相似文献   

16.
Stabilized landfill leachate has previously been treated with activated carbon (AC); however, information on the selectivity of AC depending upon the pore size is minimal. Isotherm and kinetic experiments were conducted using three commercially available AC products, one micro-porous and two meso-porous. Equilibrium adsorption and intra-particle diffusion of organic matter from stabilized leachate was studied. Isotherm experimental data were fitted to Langmuir, Freundlich, and Redlich-Peterson isotherm models in non-linear forms. Of the three isotherm models, the Redlich-Peterson model provided the best fit to the experimental data and showed a similar organic matter adsorption capacity (approximately 0.2 g total organic carbon (TOC) g−1 AC) for both micro-porous and meso-porous AC. The organic matter effective intra-particle diffusion coefficients (De) in both AC types were on the order of 10−10 m2 s−1 for AC particle sizes greater than 0.5 mm. Meso-porous ACs showed slightly higher De compared to micro-porous AC. Rapid small-scale tests showed a maximum of 80% TOC removal from leachate by each AC investigated. Fluorescence spectroscopy showed a preferential adsorption of fulvic-type organic matter with an increase in empty bed contact time by each AC.  相似文献   

17.
Rangsivek R  Jekel MR 《Water research》2005,39(17):4153-4163
Infiltration of stormwater runoff contaminated with metals is often questionable in several cases due to its long-term potential to cause deterioration of groundwater quality. To ensure the quality of filtrate, a pre-treatment of contaminated runoff is required. This study investigates the processes of copper and zinc ion removal from stormwater runoff using zero-valent iron (ZVI, Fe0). Kinetic and equilibrium tests were performed with laboratory-prepared and in situ stormwater runoff samples collected from roof, street and highway catchments. Based on the results, a substantial portion of Cu2+ is reduced and transformed to insoluble forms of Cu0 and Cu2O. Unlike copper, the adsorption and co-precipitation associated with freshly precipitated iron oxides play important roles for the removal of Zn2+. Investigations under various water quality conditions demonstrated a relatively minor impact on Cu2+ uptake rates. However, the different conditions apparently altered the removal stoichiometry and phases of the copper deposits. The removal rates of Zn2+ increase with higher dissolved oxygen (DO), ionic strength (IS), temperature (T) and pH. Dissolved organic carbon (DOC) in runoff samples forms complexes with metals and Fe2+, thereby kinetically decreasing the metal uptake rates. Furthermore, depending on its composition, a larger molecular weight organic fraction was found to preferentially compete for the adsorption sites. The study demonstrates that ZVI is a promising medium for achieving comparable capacity to a commercial adsorbent like granular ferric hydroxide (GFH). Long-term performance of ZVI, however, may be limited and governed by the formation of non-conductive layers of iron and cuprous oxides.  相似文献   

18.
A laboratory incubation experiment was conducted to investigate the influence of organic matter content on arsenic speciation and mobilization in chromated copper arsenate (CCA)-contaminated soils. The study was performed with four synthetic CCA-contaminated soils, with a range of organic matter content (mixture of peat moss and poultry manure) varying between 0.5% and 15% (w/w), under unsaturated and aerobic conditions for 40 days. Changes in water-soluble arsenic speciation (As(V), As(III), MMAA, DMAA) were monitored over time in soil extracts by HPLC-ICP-MS and in the soil solid phase (As(III), As(V)) by a solvent extraction method. Irrespective of organic matter content, As(V) was the predominant soil bound and aqueous phase arsenic species. However, over 40 days, a high soil organic matter content (7.5% and 15%) was able to entail formation of soil bound As(III). Moreover, total water-soluble arsenic was positively correlated with dissolved organic carbon (r(2)=0.88). However, the organic matter content did not influence arsenic speciation in the soluble fraction; neither As(V) reduction nor arsenic biomethylation occurred within 40 days. An increase in dissolved organic carbon content promoted both As(V) and As(III) solubilization in soils. Also, over time, organic matter contents of 7.5% and 15% entailed the persistence of soluble As(V), likely due to the high content of dissolved organic compounds which prevented its sorption onto soil. Based on this data, the environmental risk of aerobic CCA-contaminated soils rich in organic matter may be due to an enhanced availability of soluble As(V) over time, rather than to the formation of the more toxic and more mobile As(III).  相似文献   

19.
The concentrations of C, Fe, Mn, Zn, Cu, Pb and Cd were determined monthly in decomposing roots of Halimione portulacoides, using litterbag experiments, in two salt marshes of the Tagus estuary with different levels of contamination. Although carbon concentrations varied within a narrow interval during the experiment, litter decomposed rapidly in the first month (weight loss between 0.051 and 0.065 g d(-1)). The time variation of metals was examined in terms of Me/C ratios and metal stocks. Ratios of Fe/C and Mn/C and their metal stocks increased in spring, presumably due to the precipitation of oxides in the surface of decomposing roots. Subsequent decrease of Fe/C and Mn/C ratios suggests the use of Fe and Mn oxides, as electron acceptors, in the organic matter oxidation. Zinc, Cu, Pb and Cd ratios to C were, in general, higher than at initial conditions implying that metal that leached out was slower than carbon. However, metal stocks decreased during the experiment indicating that incorporation or sorption of metals in Fe and Mn oxides did not counterbalance the amount of Zn, Pb and Cd released from decomposing litter. An exception was observed for Cu, since stock in the less contaminated marsh (Pancas) increased during the decomposition, indicating that litter was efficient on Cu binding under more oxidising conditions. These results emphasize the importance of litter decomposition and sediment characteristics on metal cycling in salt marshes.  相似文献   

20.
The effects of copper-based fungicide residues on some physico-chemical properties of soils in some cocoa-producing areas of Nigeria were investigated. The results show that the fungicide residues cause significant increases in the soil pH, organic matter and copper concentrations while lowering the concentrations of inorganic nitrogen, available phosphorus, exchangeable potassium and sodium. Slight increases were also observed for the cation exchange capacity (CEC) and exchangeable Ca2+ and Mg2+ but there are no significant changes in the Zn, Fe and Mn concentrations with fungicide treatment. It is concluded that the copper-based fungicide residues predispose the soils to nitrogen, phosphorus and potassium (N, P and K) deficiencies and perhaps copper toxicity if not properly managed.  相似文献   

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