Bioavailability and plant accumulation of heavy metals and phosphorus in agricultural soils amended by long-term application of sewage sludge

Amendment of agricultural soils with municipal sewage sludges provides a valuable source of plant nutrients and organic matter. Nevertheless, addition of heavy metals and risks of eutrophication continue to be of concern. Metal behaviour in soils and plant uptake are dependent on the nature of the metal, sludge/soil physico-chemical properties and plant species. A pot experiment was carried out to evaluate plant production and heavy metal uptake, soil heavy metal pools and bioavailability, and soil P pools and possible leaching losses, in agricultural soils amended with sewage sludge for at least 10 years (F20) compared to non-amended soils (control). Sewage sludge application increased soil pH, N, Olsen-extractable-P, DOC and exchangeable Ca, Mg and K concentrations. Total and EDTA-extractable soil concentrations of Cu and Zn were also significantly greater in F20, and soil metal (Cu, Mn and Zn) and P fractionation altered. Compared to the control, in F20 relative amounts of acid-extractable (Mn, Zn), reducible (Mn, Zn) and oxidisable (Cu, Zn) metal fractions were greater, and a dominance of inorganic P forms was observed. Analyses of F20 soil solutions highlighted risks of PO4 and Cu leaching. However, despite the observed increases in metal bioavailability sewage sludge applications did not lead to an increase in plant shoot concentrations (in wild plants or crop species). On the contrary, depending on the plant species, Mn and Zn tissue concentrations were within the deficiency level for most plants.     

污泥中重金属的去除及回收试验

论述了利用离子交换技术循环使用柠檬酸去除污泥中重金属,并置换回收重金属的适宜工艺条件.经柠檬酸处理后,污泥中90%以上的重金属被去除;柠檬酸处理液中的重金属用离子交换法回收,考察了树脂种类、流速、操作方式等因素对离子交换、再生效果的影响;在适宜工艺条件下,重金属的交换率均为100%,而洗脱率均接近90%;柠檬酸及离子交换树脂循环使用,重金属也得到回收,降低了处理成本.     

施用城市污泥堆肥对土壤微生物群落结构变化的影响

在温室条件下进行了15周的盆栽实验,考察了施用城市污泥堆肥后,土壤中养分含量的变化规律,重点研究了施用城市污泥堆肥对土壤微生物群落结构变化的影响。实验发现,污泥堆肥能改善土壤养分,有机质和氮、磷含量得到显著提高。经PCR—DGGE分析,施肥1周后土壤中细菌和真菌的群落结构均发生了较大的变化。随着施肥时间的延长,细菌在富含有机质及氮、磷等养分的土壤环境下大量生长,多样性提高,其优势菌群属于γ变形菌、α变形菌和芽单胞菌;随着有机质的不断消耗,细菌的生长活性受到抑制,最终由于养分的缺乏,细菌种群多样性呈现小幅度的降低,优势菌群变为绿弯菌门、γ变形菌亚纲和厚壁菌门。对于真菌,其多样性指数在堆肥前3周逐渐提升,在第3～12周的监测中呈现相对稳定的变化趋势,优势菌群主要为座囊菌纲和散囊菌纲。     

The effect of heavy metals on dinitrogen fixation by Rhizobium-white clover in a range of long-term sewage sludge amended and metal-contaminated soils

An investigation was conducted to determine whether effective strains of Rhizobium leguminosarum biovar. trifolii capable of symbiotic N2 fixation with white clover (Trifolium repens) were present in a range of metal-contaminated soils. A number of historically sewage-amended sites (including experimental, pasture grassland and arable sites) were selected and compared with highly contaminated samples from abandoned heavy metal mines. Many sites had metal concentrations above the limits established by the UK Government, based on those developed by the European Commission (EC) for sludge-amended soils. Acetylene reduction activity (ARA) was used to screen the samples for effective N2 fixation. When the host plant was indigenous to the sward, rhizobia were found in the nodules and in the soil rhizosphere at all the sites tested. They were shown to be capable of effective symbiosis and N2 fixation, even though metal concentrations greatly exceeded the soil metal limits in some cases. However, nodulation failed to occur in some cases where T. repens was not indigenous to metal-contaminated soils. This indicated either that an ineffective rhizobial population was present, or that effective cells were absent from the soil. The influence of individual metals on ARA could not be determined conclusively because of the confounding effects of soil physicochemical variability and the presence of different metals at high concentrations together in the soil. However, Cd concentrations appeared to be particularly important in determining the presence of effective ARA in soils with no indigenous clover. In contrast to previous studies, the results presented here suggest that heavy metals may have had a quantitative effect on the free-living population of rhizobia, rather than a genetic effect.     

测定城市生活污泥中重金属的酸消解方法研究

采用HNO3-HC1O4-HF、HNO3-HC1O4、王水-HC1O4、HNO3等不同的酸消解方法对城市生活污泥进行消解。通过对这4种消解方法进行实验比较及对Cu、Ni、Zn三种金属元素浓度的测定,发现HNO3-HC1O4是适合城市生活污泥特点的消解方法。     

The behaviour of phosphorus and heavy metals in sewage sludge ashes

The effect of the combustion atmosphere and the additives (CaO and HCl) on the behaviour of phosphorus and heavy metals during sewage sludge combustion was investigated. The results demonstrated that the reduction combustion promoted the vapourisation of phosphorus and heavy metals during sewage sludge combustion. Moreover, the concentrations of phosphorus and heavy metals in the bottom ash decreased with increasing HCl ratio, and the addition of CaO can stabilise heavy metals and phosphorus. It was also observed that phosphorus and heavy metals increased with increasing CaO ratio. Lastly, the difference of the TG-DTA curves with and without additives is discussed.     

Effects of soil amendments at a heavy loading rate associated with cover crops as green manures on the leaching of nutrients and heavy metals from a calcareous soil

The potential risk of groundwater contamination by the excessive leaching of N, P and heavy metals from soils amended at heavy loading rates of biosolids, coal ash, N-viro soil (1:1 mixture of coal ash and biosolids), yard waste compost and co-compost (3:7 mixture of biosolids to yard wastes), and by soil incorporation of green manures of sunn hemp (Crotalaria juncea) and sorghum sudangrass (Sorghum bicolor x S. bicolor var. sudanense) was studied by collecting and analyzing leachates from pots of Krome very gravelly loam soil subjected to these treatments. The control consisted of Krome soil without any amendment. The loading rate was 205 g pot(-1) for each amendment (equivalent to 50 t ha(-1) of the dry weight), and the amounts of the cover crops incorporated into the soil in the pot were those that had been grown in it. A subtropical vegetable crop, okra (Abelmoschus esculentus L.), was grown after the soil amendments or cover crops had been incorporated into the soil. The results showed that the concentration of NO3-N in leachate from biosolids was significantly higher than in leachate from other treatments. The levels of heavy metals found in the leachates from all amended soils were so low, as to suggest these amendments may be used without risk of leaching dangerous amounts of these toxic elements. Nevertheless the level of heavy metals in leachate from coal ash amended soil was substantially greater than in leachates from the other treatments. The leguminous cover crop, sunn hemp, returned into the soil, increased the leachate NO3-N and inorganic P concentration significantly compared with the non-legume, sorghum sudangrass. The results suggest that at heavy loading rates of soil amendments, leaching of NO3- could be a significant concern by application of biosolids. Leaching of inorganic P can be increased significantly by both co-compost and biosolids, but decreased by coal ash and N-viro soil by virtue of improved adsorption. The leguminous cover crop, sunn hemp, when incorporated into the soil, can cause the concentration of NO3-N to increase by about 7 fold, and that of inorganic P by about 23% over the non-legume. Regarding the metals, biosolids, N-viro soil and coal ash significantly increased Ca and Mg concentrations in leachates. Copper concentration in leachate was increased by application of biosolids, while Fe concentration in leachates was increased by biosolids, coal ash and co-compost. The concentrations of Zn, Mo and Co in leachate were increased by application of coal ash. The concentrations of heavy metals in leachates were very low and unlikely to be harmful, although they were increased significantly by coal ash application.     

Enhancing bioremediation of diesel oil and gasoline in soil amended with an agroindustry sludge

This paper presents a study of the bioremediation of diesel oil and gasoline by a series of controlled laboratory tests. Sludge from an agroindustry was used to enhance bioremediation of both gasoline and diesel oil mixed with a soil mass to compare its efficiency with that of a mineral fertilizer. Effects of soil microbiology and soil mixtures were investigated by means of evolution of CO2, microorganism populations at 90 days, pH at 65 and 95 days, mineral nitrogen, and gas chromatographic analysis of the benzene, toluene, methyl tertiary butyl ether, C8, and C9+total aromatics at the end of the experiments. Treatments containing sludge showed better soil conditions after 170 days of treatment (inorganic nitrogen and microbiota activity) compared with gasoline and diesel oil without amendments. Samples had no detectable traces of the measured hydrocarbons at 170 days of treatment.     

Heavy metal accumulation in wheat plant grown in soil amended with industrial sludge

The concentrations of different forms of Zn, Cu, Mn, Ni, Cd, Cr, Pb and Fe metals were determined for the roadside sludge collected from pickling-rolling and electroplating industrial area. In sludge the relative abundance of total heavy metals were Fe>Mn>Cr>Ni>Cu>Pb>Zn>Cd and DTPA-extractable metals were in the order--Fe>Ni>Mn>Cr>Cu>Zn>Pb>Cd. Pot-culture experiment was conducted in soils amended with sludge (0%, 10%, 20%, 30%), pretreated with lime (0%, 0.5% and 1%). The soils were alkaline in nature (pH>8.3) with organic carbon contents were 0.34% and 0.72%. The most abundant total and bio-available metal was Fe. Two wheat seedlings were grown in each pot containing 3kg sludge-amended or control soil and the experiment was conducted till harvesting. Application of sludge increased both total and bio-available forms of metals in the soils, while lime application decreased the bioavailability of heavy metals in sludge-amended soils. The content of organic carbon showed positive correlation with all metals except Zn, Cr and Pb. CEC also showed a strong positive correlation (R2>0.7) with Fe, Mn, Cu, Ni and Cd. Though wheat plants are not accumulators, the translocation efficiency was appreciably high. The translocation factor from shoot to grain was found smaller than that of root to shoot of wheat plants. This makes an implication that the heavy metal accumulation was proportionally lesser in grain than in shoot. In, 10% sludge with 0.5% lime-amended soils; each of these toxic heavy metals was found to be within permissible range (USEPA). Hence, on the basis of present study, the best possible treatment may be recommended.     

Effect of ageing on the availability of heavy metals in soils amended with compost and biochar: evaluation of changes in soil and amendment properties

Remediation strategies using soil amendments should consider the time dependence of metal availability to identify amendments that can sustainably reduce available pollutant concentrations over time. Drying-wetting cycles were applied on amendments, soils and soil + amendment mixtures, to mimic ageing at field level and investigate its effect on extractable Cd, Cu, Ni, Pb and Zn concentrations from three contaminated soils. The amendments investigated were municipal waste organic compost and biochars. The amendments, soils and mixtures were characterised by their physicochemical properties at different ageing times. The amendments were also characterised in terms of sorption capacity for Cd and Cu. The sorption capacity and the physicochemical properties of the amendments remained constant over the period examined. When mixed with the soils, amendments, especially the compost, immediately reduced the extractable metals in the soils with low pH and acid neutralisation capacity, due to the increase in pH and buffering capacity of the mixtures. The amendments had a relatively minor impact on the metal availability concentrations for the soil with substantially high acid neutralisation capacity. The most important changes in extractable metal concentrations were observed at the beginning of the experiments, ageing having a minor effect on metal concentrations when compared with the initial effect of amendments.

     

Fate and effects of nutrients and heavy metals in experimental salt marsh ecosystems

Fate and effects of the macro nutrients nitrogen and phosphorus, and the heavy metals zinc, copper and cadmium, brought into experimental salt marsh ecosystems via sediment supply, were studied over a three-year period. The supply of sediment from the Marsdiep (at a low and high rate) and from the harbour of Delfzijl (at a high rate) led to an increase of the macro nutrients and heavy metals in the top soil. The growth of the salt marsh plants Aster tripolium, Puccinellia maritima and Spartina anglica and the uptake of the macro nutrients and heavy metals by the plants was only slightly affected by the addition of sediment. A high load of sediment led to an increase in growth or in the concentrations of the macro nutrients or heavy metals in the plants at a number of sampling dates, but only minor differences between treatments were found. From a mass balance constructed over a three-year study period it could be concluded that about 50% of the macro nutrients and heavy metals were retained in the salt marsh sediment. This was equal to the retained amount of organic matter, indicating that retention of the elements was closely related to retention of organic matter. The 50% loss of the macro nutrients and heavy metals probably occurred via ebb tides after resuspension of sediment and organic matter.     

Phytotoxicity of atrazine and alachlor in soil amended with sludge,manure and activated carbon

Abstract

Greenhouse studies were conducted to determine the influence of waste‐activated carbon (WAC), digested municipal sewage sludge (DMS), and animal manure on herbicidal activity of atrazine [2‐chloro‐4‐(ethylamino)‐6‐(isopropylamino)‐s‐trazine] and alachlor [2‐chloro‐2’,6'‐diethyl‐N‐(methoxymethyl)acetanilide] in a Plainfield sandy soil. Amendments generally reduced bioactivity against oat (Avena sativa L.) and Japanese millet (E. crus‐galli frumentacea). The extent to which herbicide phytotoxicity was inhibited depended upon the application rate and the kind of soil amendment. WAC, applied at the loading rate of 2.1 mt C/ha, showed a significant inhibitory effect on both herbicides. In DMS‐ and manure‐amended soil, the reduction of atrazine activity was not significant at the rate of 8.4 mt C/ha, but reduction of alachlor activity was significant at the rate of 4.2 mt C/ha. Despite inhibition of herbicidal activity, the ED₅₀ of atrazine and alachlor was below 2 ppm in most of the amendment treatments. Before adopting carbon‐rich waste amendments as management practices for controlling pesticide leaching in coarse‐textured soils, further studies are needed to characterize how alterations in sorption, leaching and degradation may affect herbicidal activity.     

Microbially mediated cadmium sorption/desorption processes in soil amended with sewage sludge

A multi-compartment system was used to study the importance of microorganisms for Cd desorption from soil amended with sewage sludge and simultaneous resorption of the mobilized metal by soil constituents. Using this system made it possible to study the participation of microorganisms (Arthrobacter, Trichoderma), montmorillonite, humic acids, and iron oxides in resorption of the released Cd. A filter-sterilized water extract of root-free soil of pH 6.7 (RF) or RF supplemented with glucose (RFG) were used to mobilize Cd from soil at 14 degrees C in 48 h. Cadmium found in those extracts after 48-h incubation was recognized as bioavailable. Changes in pH values and enrichment of soil extracts with organic acids and siderophores resulted from microbial growth. RFG with lower pH and a higher content of ligands mobilized, on average, 40% of Cd introduced with sewage sludge amended soil, whereas RF mobilized only 20% of it. Sequential extractions of Cd at time 0 and Cd remaining in soil showed that RFG had mobilized Cd mostly from the fraction bound with Fe and Mn oxides. Microbial biomass accounted for only up to 3.4% (w/w) of the soil constituents used in the experiments but resorbed 25% of mobilized Cd. The chemical composition of mobilizing soil extracts and the solid-to-mobilizing-extracts volume ratio had a significant effect on the amount of bioavailable Cd. The results of the study suggest that microbial metabolites were involved in Cd mobilization, while the biomass of microorganisms was involved in Cd resorption as a biosorbent.     

利用污泥进行水体中重金属生物吸附研究现状及展望

对国内外利用废水处理等工业过程中所产生的污泥作为生物吸附剂吸附水体中重金属的研究现状进行了综述和分析,包括其预处理技术、反应机理、主要影响因素、处理效果以及反应器工艺等。同时,对该技术未来的发展趋势进行了展望,指出依托现有废水处理设施进行集约化开发将是该工艺的发展方向。     

Sequential extraction of heavy metals during composting of sewage sludge

The major limitation of soil application of sewage sludge compost is the total heavy metal contents and their bioavailability to the soil-plant system. This study was conducted to determine the heavy metal speciation and the influence of changing the physico-chemical properties of the medium in the course of composting on the concentrations, bioavailability or chemical forms of Cu, Zn, Pb and Ni in sewage sludge. Principal physical and chemical properties and FTIR spectroscopical characterization of sludge compost during treatment show the stability and maturity of end product. The total metal contents in the final compost were much lower than the limit values of composts to be used as good soil fertilizer. Furthermore, it was observed by using a sequential extraction procedure in sludge compost at different steps of treatment, that a large proportion of the heavy metals were associated to the residual fraction (70-80%) and more resistant fractions to extraction X-NaOH, X-EDTA, X-HNO3 (12-29%). Less than 2% of metals bound to bioavailable fractions X-(KNO3+H2O). Heavy metal distribution and bioavailability show some changes during composting depending on the metal itself and the physico-chemical properties of the medium. Bioavailable fractions of all elements tend to decrease except Ni-H2O. Zn and mainly Cu present more affinity to organic and carbonate fractions. In contrast, Pb is usually preferentially bound to sulfide forms X-HNO3. Nickel shows a significant decrease of organic form. Significant degrees of correlation were found between heavy metal fractions and changes of some selected variables (e.g. pH, ash, organic matter, humic substance) during the course of composting. Mobile fractions of metals are poorly predictable from the total content. The R2 value was significantly increased by the inclusion of other variables such as the amount of organic matter (OM) and pH.     

Electrokinetic enhancement removal of heavy metals from industrial wastewater sludge

An enhanced electrokinetic process for removal of metals (Cr, Cu, Fe, Ni, Pb, Zn) from an industrial wastewater sludge was performed. The electrokinetic experiments were conducted under a constant potential gradient (1.25 V cm(-1)) with processing fluids of tap water (TW), sodium dodecylsulfate (SDS) and citric acid (CA) for 5 days. Results showed that metal removal efficiency of heavy metals for EK-TW, EK-SDS and EK-CA systems are 11.2-60.0%, 37.2-76.5%, and 43.4-78.0%, respectively. A highest metal removal performance was found in EK-CA system. The removal priority of investigated metals from sludge by EK process was found as: Cu > Pb > Ni > Fe > Zn > Cr. The results of sequential extraction analysis revealed that the binding forms of heavy metals with sludge after electrokinetic process were highly depend upon the processing fluid operated. It was found that the binding forms of metals with sludge were changed from the more difficult extraction type (residual and sulfate fractions) to easier extraction types (exchangeable, sorbed, and organic fraction) after treatment by electrokinetic process. Results imply that if a proper treatment technology is followed by this EK process to remove metals more effectively, this treated sludge will be more beneficial for sludge utilization afterwards. Before it was reused, the risk associated with metals of more mobile forms to the environment need to be further investigated. The cost analysis was also evaluated for the investigated electrokinetic systems.     

灯心草部分生理生化指标对土壤复合重金属胁迫的响应

通过盆栽试验,以叶绿素含量和POD、SOD、CAT3种抗氧化酶活性作为观测指标,研究了Cu、Cd、Pb、Zn和As复合重金属胁迫下灯心草部分生理生化指标的变化趋势和机理.结果表明,灯心草的生理毒害效应呈明显的剂量-效应关系.表现为与对照相比,叶绿素含量减少,叶绿素a/b值降低,叶片失绿现象明显.随着复合重金属胁迫浓度的增加,灯心草3种酶活性均呈先升后降的变化趋势,但出现抗性酶活性高峰所对应的重金属浓度不同,表现出不同的特征变化趋势.总体来说,在接近土壤环境质量标准低浓度设计范围内,酶活性有逐渐被激活的趋势.但在高浓度水平下,酶活性普遍受到抑制.生长在铅锌尾矿和模拟矿毒水污染土壤中的灯心草叶绿素合成受到显著抑制(P＜0.05),但POD和CAT两种酶活性均高于对照.     

Measurement of symbiotic nitrogen-fixation in leguminous host-plants grown in heavy metal-contaminated soils amended with sewage sludge

Rates of nitrogen fixation by Rhizobium in symbiosis with leguminous host-plants including white clover, broad bean and peas have been established in soils that have been amended experimentally with heavy metal-contaminated sewage sludges. Results from 15N-dilution experiments for the measurement of N2 fixation have shown that adverse heavy metal effects are apparent on symbiotic N2 fixation rates for white clover grown in inter-specific competition with ryegrass under mixed sward conditions, compared to white clover grown in pure sward. Further experiments on broad bean and pea indicated a significant, but minor-inhibitory metal-related effect on the rate of N2 fixation compared to untreated soils and soils amended with a relatively uncontaminated sludge. The implications of the results with respect to sludge utilisation in agriculture are discussed.     

电感耦合等离子体质谱法测定土壤中重金属有效态浓度

采用电感耦合等离子体质谱(ICP/MS)法,结合内标技术,高效、快速地测定了土壤中Cu、Zn、Pb、Cd、Ni、Cr、Hg、As和Se 9种元素的有效态浓度.Cu、Zn、Pb、Cd、Ni、Cr、Hg的有效态采用0.1 mol/L NaNO3浸提,所得浸提液上机前预先稀释10倍;As和Se的有效态采用稀HCl浸提.结果表明,在测定所有空白、标准溶液及样品时均在线加入500 靏/L 45Sc/72Ge/209Bi内标溶液,有效地克服了基体效应、接口效应和仪器波动所产生的影响;0.15%(质量分数)NaCl\|1.0%(体积分数)HCl作为Hg标准溶液固定液,可保证1 靏/L Hg标准溶液7 d有效期;9种元素有效态的仪器检出限均在靏/L级以下,方法检出限<0.030 mg/kg,平均加标回收率为81%～121%,相对标准偏差为0.02%～1.21%.     

Tolerance and uptake of heavy metals by Trichoderma atroviride isolated from sludge

A strain of Trichoderma atroviride, isolated from sewage sludge obtained from a water treatment plant located in Madrid (Spain), has been studied for tolerance to heavy metals (copper, zinc and cadmium) and for its capacities to uptake these metals. It was found that this fungus is capable of surviving high metal concentrations, apparently as a result of the natural selection of resistant cells. Also, growth and metal uptake have been assayed in samples where the fungus was cultured in the presence of a single metal and in the presence of a combination of two or three cations, where additive and synergistic interactions were observed. Finally, metal uptake by this strain has been studied under different nutritional conditions. It was found that the highest values of metals removal were achieved for autolysed mycelia while the lowest levels were observed in the presence of glucose.