水泥、粉煤灰及DTCR固化/稳定化重金属污染底泥

采用水泥、粉煤灰及有机硫稳定剂DTCR固化/稳定化处理重金属污染的底泥,考察固化体的抗压强度及重金属浸出毒性,确定了底泥固化/稳定化的最佳工艺条件。结果表明:仅用水泥固化/稳定化重金属污染底泥,固化体抗压强度随水泥用量的增加而上升,重金属浸出浓度则下降,当水泥∶干底泥质量比为0.6∶1.0时,固化体7 d抗压强度能达到0.99 MPa的标准值;进一步研究发现,水泥∶粉煤灰∶干底泥质量比为0.54∶0.06∶1.0时,重金属浸出浓度有所上升,但7 d及28 d抗压强度仍能分别达到1.2 MPa和2.8 MPa;加入DTCR后,当水泥∶粉煤灰∶DTCR∶干底泥质量比为0.54∶0.06∶0.012∶1.0时,固化体7 d及28 d抗压强度分别为1.1 MPa和2.1 MPa,醋酸缓冲溶液法浸出的Cd、Pb、Zn和Cu浓度分别为0.102、0.189、0.180和0.032 mg/L。     

垃圾焚烧飞灰中Cd、Pb、Zn的螯合稳定与水泥固化处理

采用有机硫稳定剂(DTCR)与水泥对城市垃圾焚烧飞灰进行稳定/固化处理,研究了飞灰中Cd、Pb、Zn的浸出毒性和固化体的抗压强度,比较了螯合稳定与水泥固化对Cd、Pb、Zn的处理效果、养护时间对固化体抗压强度的影响,并对飞灰的结构形貌进行了分析。结果表明,在稳定固化过程中飞灰中发生了复杂的螯合、水化反应,重金属形态由不稳定态向稳定态转变,螯合稳定对Cd的处理效果最好,水泥固化更适用于Pb、Zn。固化时间大于7 d后,飞灰中的重金属以及固化体的抗压强度已较为稳定。螯合稳定协同水泥固化的处理效果优于单一的稳定或固化方法,飞灰在固化7 d后可同时达到重金属浸出毒性和抗压强度标准,满足安全填埋要求。     

稳定剂协同水泥固化/稳定化重金属污染土壤的工程特性

采用稳定剂(SR)协同水泥(PC)固化/稳定化重金属污染土壤,以Pb、Zn浸出毒性和药剂吨处理成本为综合指标确定PC和SR的最优配比,并对固化土体进行无侧限抗压强度、不固结不排水三轴压缩实验和柔性壁渗透实验,探讨固化土体强度以及渗透特性。结果表明,最优配比为SR掺量2.5%,PC掺量8%;最优配比下固化土体中重金属铅锌的浸出浓度分别降低97.5%和74.5%,均低于固体危险废物浸出标准值。其养护28 d无侧限抗压强度达到1 080 kPa,比未固化土体对应值高9.6倍;随着PC掺量增加,固化体的有效黏聚力及有效内摩擦角均不断增大,其中最优配比固化土体有效黏聚力达到216.9 kPa,有效内摩擦角为34.8°。加入稳定剂SR使固化体渗透系数增大,但随着PC掺量增加,渗透系数急剧降低。其中最优配比固化土体渗透系数相对未固化复合污染土体降低一个数量级至10~(-6)cm·s~(-1),可有效增强土体的防渗阻隔能力,提高稳定化土壤的安全利用率。     

交联阳离子淀粉螯合剂对铬渣的处理研究

合成了作为重金属螯合剂的交联阳离子淀粉 ,并将它用于铬渣的固化实验 ,对固化体的浸出毒性、表面浸出率、抗压强度等指标进行了测试。结果表明 ,添加高分子螯合剂后的固化体的浸出毒性降低 6 6 4 % ,远远小于国家标准的1 5mg/L ;2 8d后的表面浸出率仅为 1 0 -6数量级 ;抗压强度有所下降 ,但 2 8d养护后的抗压强度大于 30MPa ,符合填埋或建筑综合利用的强度要求     

低水泥含量垃圾焚烧飞灰重金属离子蒸养固化实验研究

对垃圾焚烧飞灰(以下简称飞灰)的矿物组成、微观形貌及其重金属浸出浓度进行了测试分析,结果表明,飞灰中Cd与Pb的浸出浓度远高于《生活垃圾填埋场控制标准》(GB 16889—2008)规定的限值,在进行安全填埋之前需固化处理。引入水泥蒸养固化技术,减少水泥掺量,增加粉煤灰掺量来处理飞灰。研究了不同配比下固化体的抗压强度以及不同飞灰掺量对固化体浸出浓度的影响。结果表明,蒸养后的固化体抗压强度基本都能达到安全填埋的要求,其重金属浸出浓度都低于GB 16889—2008规定的限值,可以进行安全填埋。     

城市生活垃圾焚烧飞灰水泥固化技术研究

用硫铝酸盐水泥对城市垃圾焚烧飞灰(简称飞灰)进行固化实验,研究了飞灰重金属浸出特性,分析了飞灰掺量、浸提剂p H值对重金属浸出特性以及飞灰掺量对不同龄期(3、7、28 d)飞灰固化体抗压强度的影响,并对飞灰及其固化体进行XRD分析。结果表明,在HJ/T 299-2007和HJ/T 300-2007两种不同浸出体系下,飞灰中Cu、Zn、Cd、Pb、Cr和Mn等重金属浸出浓度差别较大,建议应根据评价目标合理选择重金属浸出测量方法。其中,飞灰中Pb的浸出浓度超过《危险废物鉴别标准浸出毒性鉴别》(GB 5085.3-2007)限值的3.35倍,因此被列为危险废物,应妥善处理。除飞灰掺量小于40%时的固化体Cd符合标准,其余飞灰固化体Pb和Cd的浸出浓度仍超过《生活垃圾填埋场污染控制标准》(GB 16889-2008)限值,故达不到卫生填埋的要求。固化体抗压强度随飞灰掺量增大而降低,重金属浸出浓度与之相反。飞灰掺量为40%时,固化体中重金属浸出浓度随浸提剂p H值降低而增大,但p H值大于5时,未测出重金属浸出。XRD结果表明:飞灰中可溶性盐参与水泥水化反应,重金属Cr以CrO_2-4的形式固化于钙矾石中。     

3种含铁材料对重金属和砷复合污染底泥稳定化处理

选用3种含铁材料FeCl3、Fe(OH)3和FePO4,开展重金属和砷(As)复合污染底泥的稳定化处理实验,并用毒性浸出测试(TCLP)的结果和底泥交换态重金属(Pb、Cd、Cu、Zn)及As的含量来评价其稳定化效果。结果表明,(1)FeCl3和FePO4降低了底泥pH值,Fe(OH)3轻微地提高了底泥pH值。(2)FeCl3活化了底泥中Pb、Cd、Cu、Zn,使其浸出量和交换态含量增加,对As浸出量的影响不大,但使底泥中As交换态含量明显降低,且在最大添加量(8.00 g/kg)时As交换态含量未检测出;Fe(OH)3降低了Cd交换态和浸出量,稍增加了As交换态和浸出量,但对Pb、Cu、Zn交换态和浸出量影响不明显;FePO4明显降低了Pb的浸出量和交换态含量,略微降低了交换态Cd、Zn含量,对交换态Cu影响不大,但明显增加了As的浸出量和交换态含量。综上,FeCl3对As具有较好的稳定化效果,但明显活化了底泥中的4种重金属;Fe(OH)3亦对底泥中Cd有一定稳定化效果;FePO4对Pb的稳定化效果较好,但明显活化了底泥中的As。显然,3种含铁材料都不能实现底泥中重金属和As的同时稳定化。     

铜渣基磷酸铁化学键合材料固化重金属Pb

铜渣堆积会造成资源浪费和环境污染等问题,利用铜渣与磷酸盐反应制备铜渣基磷酸铁化学键合材料(CBIPCs),并用其固化重金属Pb。研究铜渣与磷酸二氢铵(m(CS)/m(P))配比、缓凝剂以及硝酸铅掺量对CBIPCs固化重金属Pb的影响。结果表明:随着硝酸铅掺量的增加,固化体抗压强度降低,Pb毒性浸出浓度略增大;在m(CS)/m(P)=3:1和硼砂掺量为2%的条件下,当硝酸铅掺量为12%,固化体自然养护28 d的抗压强度仍达到24.5 MPa,Pb毒性浸出浓度为0.086 mg·L~(-1),远低于《危险废物鉴别标准浸出毒性鉴别》(GB 5085.3-2007)要求的最高限值5.0 mg·L~(-1)。XRD和SEM/EDS分析表明,固化体中生成了PbHPO_4、Pb_3(PO_4)_2、Pb_5(PO_4)OH等铅类磷酸盐产物,并被胶凝相物质紧密包裹。铜渣与磷酸盐反应制备的铜渣基磷酸铁化学键合材料(CBIPCs),可通过化学键合和物理固封双重作用实现对重金属Pb的稳定固化。     

交联阳离子淀粉螯合剂对铬渣的处理研究

合成了作为重金属鳌合剂的交联阳离子淀粉，并将它用于铬渣的固化实验，对固化体的浸出毒性、表面浸出率、抗压强度等指标进行了测试。结果表明，添加高分子鳌合剂后的固化体的浸出毒性降低66．4％，远远小于国家标准的1．5mg／L；28d后的表面浸出率仅为10^-6数量级；抗压强度有所下降，但28d养护后的抗压强度大于30MPa，符合填埋或建筑综合利用的强度要求。     

河道底泥重金属浸出毒性分析及其固化/稳定化效果

城市内河由于长期承纳污染物导致其底泥受到污染,特别是其中重金属污染严重。选取某城市纳污河淤泥为试验对象,发现底泥Cr、Cu、Ni和Zn含量和浸出浓度均较高。为使其达到资源再利用要求,研究了一种污泥改性剂对其固化/稳定化的效果。结果显示,当改性剂掺量为10%时,已能够显著提高淤泥各个龄期强度。固化淤泥重金属浸出浓度在7d时已明显降低,且随养护时间增长进一步降低。改性剂掺量为13%时,固化淤泥Cu、Ni和Zn浸出浓度可降低90%以上,而Cr浸出浓度也可降低80%左右。实验表明,污泥改性剂处理后淤泥抗压强度提高,同时有害物质得到有效的稳定。     

Solidification/stabilisation of electric arc furnace waste using low grade MgO

This study aims to evaluate the potential of low grade MgO (LGMgO) for the stabilisation/solidification (S/S) of heavy metals in steel electric arc furnace wastes. Relevant characteristics such as setting time, unconfined compressive strength (UCS) and leaching behaviour assessed by acid neutralisation capacity (ANC), monolithic and granular leaching tests were examined in light of the UK landfill Waste Acceptance Criteria (WAC) for disposal. The results demonstrated that all studied mix designs with Portland cement type 1 (CEM1) and LGMgO, CEM1-LGMgO 1:2 and 1:4 at 40% and 70% waste addition met the WAC requirements by means of UCS, initial and final setting times and consistence. Most of the ANC results met the WAC limits where the threshold pH values without acid additions were stable and between 11.9 and 12.2 at 28 d.Granular leaching results indicate fixation of most of the metals at all mix ratios. An optimum ratio was obtained at CEM1-LGMgO 1:4 at 40% waste additions where none of the metals leaching exceeded the WAC limits and hence may be considered for landfill disposal.The monolithic leaching test results showed that LGMgO performed satisfactorily with respect to S/S of Zn, as the metal component present at the highest concentration level in the waste exhibited very little leaching and passed the leaching test requirement at all mix ratios studied. However, its performance with respect to Pb, Cd and Cr was less effective in reducing their leaching suggesting a higher cumulative rate under those leaching regimes.     

底泥污染物释放动力学研究

采用模拟试验方式和新型微生物数量测定方法 ,研究了沼泽化湖泊底泥和受污染河流底泥在不同扰动状态下 ,底泥耗氧速率、氮和磷污染物释放动力学过程。结果表明 :( 1)底泥耗氧速率是同样条件下上覆水耗氧速率的 48倍 ,而在扰动状态下 ,底泥耗氧速率达到上覆水耗氧速率的 5 96— 93 6倍 ,扰动底泥显著增大其耗氧速率 ,底泥污染越严重 ,其耗氧速率越大 ,对水体产生的影响也越大。 ( 2 )扰动底泥可以显著增大底泥的氮磷释放速率 ,氮的释放受有机氮的氨化、氨氮的硝化、硝酸盐氮的反硝化以及氨氮被微生物吸收转化为有机氮等的影响 ;磷的释放过程受厌氧过程和底泥颗粒吸附的影响 ,耗氧速率高的底泥具有更大的氮磷释放潜力。 ( 3 )微生物数量在底泥污染物释放动力学中起着关键性作用 ,新型方法可以快速检测微生物总量。试验结果对于水环境的管理、受污染水体的修复 ,以及底泥的处理处置等都具有重要的指导意义     

Determining the experimental leachability of copper, lead, and zinc in a harbor sediment and modeling

The potential leaching of pollutants present in harbor sediments has to be evaluated in order to choose the best practices for managing them. Little is known about the speciation and mobility of heavy metals in these specific solid materials. The objective of this paper is to determine and model the leachability of copper, lead, and zinc present in harbor sediments in order to obtain essential new data. The mobility of inorganic contaminants in a polluted harbor sediment collected in France was investigated as a function of physicochemical conditions. The investigation relied mainly on the use of leaching tests performed in combination with mineralogical analysis and thermodynamic modeling using PHREEQC. The modeling phase was dedicated to both confirm the hypothesis formulated to explain the experimental results and improve the determination of the main physico-chemical parameters governing mobility. The experimental results and modeling showed that the release of copper, lead, and zinc is very low with deionized water which is due to the stability of the associated solid phases (organic matter, carbonate minerals, and/or iron sulfides) at natural slightly basic conditions. However, increased mobilization is observed under pH values below 6.0 and above 10.0. This methodology helped to consistently obtain the geochemical parameters governing the mobility of the contaminants studied.     

A review on the application of microbial toxicity tests for deriving sediment quality guidelines

The results of microbial toxicity tests are needed for the risk assessment of polluted sediments. In comparison with animals the anaerobic microorganisms are more tolerant to natural sediment conditions whereas they are more sensitive for a number of specific pollutants. Microbial toxicity tests from a literature search were classified in seven categories. Category A, B and C use polluted sediments and are applied for sediment monitoring. In category D, a pure chemical is added and the organisms and the test conditions were derived from sediment. Therefore this category can be used for setting sediment quality guidelines which protect sediment functions for the toxic effects of chemicals. In category E, organisms from a polluted site are separated from the sediment and are tested with pure chemicals. Organisms from a more polluted site can be more tolerant to a local pollutant. This is called pollution-induced community tolerance and can be used as evidence for the occurrence of toxic effects in a specific sediment. In category F pure chemicals are tested with a pure culture of microorganisms under sediment conditions. The results of category F tests can be combined with single species tests with animals and plants to obtain sediment quality guidelines sufficient for species protection. This can be compared with the sediment quality guidelines which protect sediment functions. When one of these quality guidelines is exceeded for a compound at a specific location a category E test can be used to determine whether the compound shows toxic effects in that sediment.     

Comparison of the characteristics of flow-through and flow-around leaching tests of Solidified heavy metal wastes

This paper introduces a research work on studying the possibility of using a flow-through leaching test method to simulate the leaching behaviour of the cement-based stabilized/solidified (S/S) hazardous wastes. Both the flow-through leaching and the more common flow-around (dynamic leaching) test methods were carried out in the study to compare the leaching behaviour of the solidified waste under different leaching environments. The solidified waste samples were prepared from five kinds of heavy metals with two kinds of binders. The metals were Pb2+, Zn2+, Cu2+, Ni2+ (positive ions as nitrate), and Cr6+ (as a negative ion in potassium dichromate), and the binders were type I Ordinary Portland Cement (OPC) and Pulverised Fuel Ash (PFA). The results of two series of flow-through and flow-around leaching experiments are reported and compared in this paper. Mathematical models for simulating the leaching behaviour of the flow-through and flow-around leaching conditions were used to determine the diffusivities of the contaminants. The results show that, since the matrix of the solid waste in a flow-through leaching test is always being degraded, the diffusivities continuously increased during the leaching period. The range of the diffusivities was 10E-8 to 10E-3 cm2/s, which corresponds to the case of liquid phase diffusion. But in the case of the flow-around (dynamic leaching) test, the range of the diffusivities was 10E-18 to 10E-9 cm2/s which was similar to solid phase diffusion, and the variation of the diffusivity with time was not regular.     

Evaluation of the potential impact of polluted sediments using Manila clam Ruditapes philippinarum: bioaccumulation and biomarker responses

An assessment was made to monitor the short-term impact of heavily polluted sediments that may move out from the brackish man-made Lake Shihwa outside of the sea dike due to operations of a tidal power plant. Here, we exposed the Manila clam Ruditapes philippinarum collected from the western coast of Korea to natural sediment under lab condition for 96?h. Sediments were collected from Lake Shihwa and outside of the sea dike representing polluted and reference conditions, respectively. The results of chemical analysis revealed that the concentrations of nonylphenol and heavy metals in water and sediment from the inner region of Lake Shihwa were significantly higher than those of reference sediments. After 48 and 96?h of exposure, 30 specimens of clams were sampled from each experimental condition, and concentrations of nonylphenol and metals were measured in clams, water, and sediments. Several biomarkers, including concentrations of metallothionein-like proteins, and activities of the antioxidant enzymes glutathione S-transferase and catalase were determined in clams to characterize the effects of polluted sediments to clams. After 96?h of exposure, R. philippinarum assimilated nonylphenol up to 71 times compared to initial concentrations. However, there was no apparent uptake of heavy metals into the clams. Additionally, antioxidant enzymes exhibited higher activities in clams exposed to the polluted sediment. The results of the present study with physiological responses in R. philippinarum suggest that sediment transportation caused by the operation of a tidal power plant in Lake Shihwa will have striking effects on benthic organisms in the adjacent coastal area.     

pH对污水污泥中污染物浸出的影响

研究pH对污泥中污染物浸出的影响可以为投海过程中海洋水体酸碱性变化对污泥中污染物浸出的影响及其变化规律提供理论依据。为了得出不同pH值对污泥中污染物浸出的影响，采用CEN/TS 14429：2005浸出实验对上海5个污水处理厂脱水污泥中重金属、溶解性有机碳、溶解性硫化物和主要离子的浸出情况进行了研究，同时分别以超纯水和海水为浸提剂研究在相应pH范围内盐度对上述指标浸出的影响。结果表明，Zn、Cd、Pb和As在酸性和碱性条件下浸出量较高，在中性或接近中性条件下浸出量则最低，且海水中Zn和Cd的浸出量比超纯水中高；Cu在碱性条件下的浸出量明显比酸性条件高；在所研究的pH范围内，5个污泥样品中溶解性有机碳的浸出量均随pH的升高而增高；仅酸挥发性硫含量最高的S5在海水中有较明显的溶解性硫化物浸出；部分污泥样品中的氮在酸性纯水中有较高的浸出量，海水中浸出量较少；而无论海水或纯水中，磷在强酸和强碱条件下均有明显浸出。     

Environmental assessment of different advanced oxidation processes applied to a bleaching Kraft mill effluent

Basic research on remediation of polluted sediment by leaching has, to date, been carried out exclusively with suspended material. For economic reasons, only solid-bed leaching is applicable to large-scale processes. Abiotic and microbial solid-bed leaching were comparatively studied in a percolator system using ripened and therefore permeable heavy metal polluted river sediment. In the case of abiotic leaching, sulfuric acid was supplied to the sediment by circulating water; the lower the pH of the percolating water, the higher the percolation flow, and the lower the solid-bed height was, the faster the heavy metals were solubilized. However, the pH and percolation flow are subjected to restrictions: strongly acidic conditions result in dissolution of mineral components, and the percolation flow must not exceed the bed permeability. And a high solid bed is an economic requirement. In the case of bioleaching, elemental sulfur added to the sediment was oxidized to sulfuric acid within the package which, in turn, solubilized the heavy metals. Here, the percolation flow and the solid-bed height did not affect the rate of metal solubilization. Solid-bed leaching on a larger scale will thus be much more efficient applying bioleaching with sulfur as the leaching agent than abiotic leaching with sulfuric acid.     

Regiospecific dechlorination of spiked tetra- and trichlorodibenzo-p-dioxins by anaerobic bacteria from PCDD/F-contaminated Spittelwasser sediments

Samples were taken from sediment of the River Spittelwasser (district Bitterfeld, Germany), which is highly polluted with PCDD/Fs and other chloroorganic compounds. The sediment cores were separated into 10-20 cm thick layers, spiked with 50 microM of 1,2,3,4-tetrachlorodibenzo-p-dioxin and incubated for 8 months under anaerobic conditions in the presence of cosubstrates. Reductive dechlorination of the tetrachlorinated congener and formation of tri- and dichlorinated products were observed in all biologically active incubations. Analysis of subcultures spiked with 1,2,3- and 1,2,4-trichlorodibenzo-p-dioxin, respectively, revealed two different dechlorination pathways within the sediment cores. Pathway M was characterized by the simultaneous dechlorination of peri- and lateralchlorine atoms, whereas sequence SP was restricted to the dechlorination at positions flanked by chlorine atoms on both sides.     

Effect of different types of elemental sulfur on bioleaching of heavy metals from contaminated sediments

The application of two different types of elemental sulfur (S0) was studied to evaluate the efficiency on bioleaching of heavy metals from contaminated sediments. Bioleaching tests were performed in suspension and in the solid-bed with a heavy metal contaminated sediment using commercial sulfur powder (technical sulfur) or a microbially produced sulfur waste (biological sulfur) as substrate for the indigenous sulfur-oxidizing bacteria and thus as acid source. Generally, using biological sulfur during suspension leaching yielded in considerably better results than technical sulfur. The equilibrium in acidification, sulfur oxidation and metal solubilization was reached already after 10-14 d of leaching depending upon the amount of sulfur added. The metal removal after 28 d of leaching was higher when biological sulfur was used. The biological sulfur added was oxidized with high rate, and no residual S0 was detectable in the sediment samples after leaching. The observed effects are attributable to the hydrophilic properties of the biologically produced sulfur particles resulting in an increased bioavailability for the Acidithiobacilli. In column experiments only poor effects on the kinetics of the leaching parameters were observed replacing technical sulfur by biological sulfur, and the overall metal removal was almost the same for both types of S0. Therefore, under the conditions of solid-bed leaching the rate of sulfur oxidation and metal solubilization is more strongly affected by transport phenomena than by microbial conversion processes attributed to different physicochemical properties of the sulfur sources. The results indicate that the application of biological sulfur provides a suitable means for improving the efficiency of suspension leaching treatments by shortening the leaching time. Solid-bed leaching treatments may benefit from the reuse of biological sulfur by reducing the costs for material and operating.