Remediation of arsenic contaminated soil by sulfidated zero-valent iron

• Sulfidation significantly enhanced As(V) immobilization in soil by zerovalent iron. • S-ZVI promoted the conversion of exchangeable As to less mobile Fe-Mn bound As. • Column test further confirmed the feasibility of sulfidated ZVI on As retention. • S-ZVI amendment and magnetic separation markedly reduced TCLP leachability of As. In this study, the influences of sulfidation on zero-valent iron (ZVI) performance toward As(V) immobilization in soil were systemically investigated. It was found that, compared to unamended ZVI, sulfidated ZVI (S-ZVI) is more favorable to immobilize As(V) in soil and promote the conversion of water soluble As to less mobile Fe-Mn bound As. Specifically, under the optimal S/Fe molar ratio of 0.05, almost all of the leached As could be sequestrated by>0.5 wt.% S-ZVI within 3 h. Although the presence of HA could decrease the desorption of As from soil, HA inhibited the reactivity of S-ZVI to a greater extent. Column experiments further proved the feasibility of applying S-ZVI on soil As(V) immobilization. More importantly, to achieve a good As retention performance, S-ZVI should be fully mixed with soil or located on the downstream side of As migration. The test simulating the flooding conditions in rice culture revealed there was also a good long-term stability of soil As(V) after S-ZVI remediation, where only 0.7% of As was desorbed after 30 days of incubation. Magnetic separation was employed to separate the immobilized As(V) from soil after S-ZVI amendment, where the separation efficiency was found to be dependent of the iron dosage, liquid to soil ratio, and reaction time. Toxicity characteristic leaching procedure (TCLP) tests revealed that the leachability of As from soil was significantly reduced after the S-ZVI amendment and magnetic separation treatment. All these findings provided some insights into the remediation of As(V)-polluted soil by ZVI.     

磁性铁基改性生物炭去除水中氨氮

氨氮的过度排放是水体富营养化的一个重要原因.然而,随着环境法规的日益严格,传统方法处理效果难以达到要求.吸附法因高效、安全等优点近年来开始应用于去除水中的氨氮.本研究中以共沉淀法将磁性铁基材料负载到市政污泥生物炭上,结果表明其对水中氨氮有良好的去除效果.80℃下合成的材料（MB₈₀）在293 K下对氨氮的饱和吸附量可达17.52 mg·g^-1.动力学与热力学结果表明,MB₈₀吸附氨氮的过程更符合伪二级动力学和Langmuir等温线.MB₈₀对氨氮的吸附机制可归纳为静电吸引、孔隙填充、离子交换和氢键结合.且5次循环后对氨氮的吸附量仍十分理想,可达3.18 mg·g^-1.本研究的结果可以为高效去除水中氨氮提供一种行之有效的方法,并为市政污泥的处理提供新的出路.     

硫铁填料和微电流强化再生水脱氮除磷的研究

为提高再生水质量,在不同C/N和HRT条件下,对比分析硫铁复合填料和微电流作用强化再生水深度脱氮除磷效果.结果表明,硫铁复合填料和微电流作用均能够强化氮、磷的深度去除效果,且二者结合能够使反硝化系统pH值稳定在7.2~8.5之间.系统中TN主要靠异养反硝化、氢自养反硝化和硫自养反硝化作用去除,94.04%的TP是以生成磷酸铁沉淀的形式去除.分别从填料上取生物膜,进行Miseq高通量测序,构建细菌16S rRNA基因克隆文库.结果发现,在仅有海绵铁作用系统中,同时具有异养反硝化和氢自养反硝化功能的细菌所占比例达到29.47%;硫铁复合填料和硫铁微电流作用系统中,具有硫自养反硝化功能的Thiobacillus(硫杆菌属)所占比例分别达到60.47%和40.62%.因此,硫铁复合填料和微电流作用用于强化再生水深度脱氮除磷具有明显的优势.     

Effect of lime on speciation of heavy metals during composting of water hyacinth

Composting is attractive and inexpensive method for treatment and biomass disposal of water hyacinth. However, the major disadvantage of water hyacinth composting is the high content of heavy metals in the final compost. Addition of lime sludge significantly reduced most bioavailable fractions (exchangeable and carbonate) of heavy metals. Studies were carried on composting of water hyacinth (Eichhornia crassipes) with cattle manure and sawdust (6:3:1 ratio) and effects of addition of lime (1%, 2% and 3%) on heavy metal speciation were evaluated during 30 days of composting period. The Tessier sequential extraction method was employed to investigate the changes in speciation of heavy metals such as Zinc (Zn), Copper (Cu), Manganese (Mn), Iron (Fe), Lead (Pb), Nickel (Ni), Cadmium (Cd) and Chromium (Cr) during water hyacinth composting. Effects of physicochemical parameters such as temperature, pH and organic matter on speciation of heavy metals were also studied during the process. Results showed that, the total metal content was increased during the composting process. The higher reduction in bioavailability factor (BF) of Cu, Fe, Ni, Cd and Cr was observed in lime 2 treatment about 62.1%, 64.4%, 71.9%, 62.1% and 58.9% respectively; however higher reduction in BF of Zn and Pb was observed in lime 1 treatment during the composting process. Reducible and oxidizable fractions of Ni, Pb and Cd were not observed during the process. Addition of lime was very effective for reduction of bioavailability of heavy metals during composting of water hyacinth with cattle manure and sawdust.     

Sequence of the main geochemical controls on the Cu and Zn fractions in the Yangtze River estuarine sediments

Metal speciation can provide sufficient information for environmental and geochemical researches. In this study, based on the speciation determination of Cu and Zn in the Yangtze Estuary sediments, roles of eight geochemical controls (i.e., total organic carbon (TOC), clay, Fe/Mn in five chemical fractions and salinity) are fully investigated and sequenced with correlation analysis (CA) and principal components analysis (PCA). Results show that TOC, clay and Fe/Mn oxides are key geochemical factors affecting the chemical speciation distributions of Cu and Zn in sediments, while the role of salinity appears to be more indirect effect. The influencing sequence generally follows the order: TOC>clay>Mn oxides>Fe oxides>salinity. Among the different fractions of Fe/Mn oxides, residual and total Fe content, and exchangeable and carbonate Mn exert the greatest influences, while exchangeable Fe and residual Mn show the poorest influences.     

稳定剂对电解锰废渣中高浓度可溶性锰稳定效果的影响

为满足大宗废渣经济性处理的需要,从碱性物质、磷酸盐、碳酸盐类药剂筛选出“物美价廉”稳定剂,考察了CaO、MgO和Ca10(PO4)6(OH)2及其与NaHCO3和Na3PO4的组合对电解锰废渣中的可溶性锰的稳定化效果,并采用矿物组成分析、锰价态分析和形态变化探讨可溶性锰固定机理.结果表明:投加10%MgO锰渣中可溶性锰固定率达到100%,9%CaO+5%NaHCO3和9%CaO+5%Na3PO4的组合实现可溶性锰固定率95%以上.上述3组稳定剂将可溶性Mn2+先转变为沉淀态锰进一步转变为高价态含锰物相.后两组中NaHCO3或Na3PO4的加入促进了Mn2+向Mn3+、Mn4+的转化.     

利用大型土柱自然淋溶条件下研究土壤重金属的迁移及形态转化

为研究不同重金属在土壤中的迁移和形态转化,通过分层填装土柱,在土柱0~5 cm深度范围内添加Pb、Ag、Bi、In、Sb和Sn等重金属污染土壤,并在自然条件下淋溶4 a,分析各重金属在红壤、潮土、黑土和砂土中的迁移速率及其形态组成. 结果表明:①在>30 cm深度范围内,红壤、潮土和黑土中各重金属质量分数与其相应本底值相比变化不大;与试验前土壤相比,砂土整个剖面中6种重金属质量分数均较高. ②6种重金属在4种土壤中的残留率表现为砂土<潮土<黑土<红壤;对于0～10 cm土壤中Pb的残留率,在潮土中大于Ag和Sb,在黑土中大于Ag,在红壤中大于In,在砂土中则大于Sn. ③模拟试验后残留在土柱中的重金属主要分布在土壤表层(0～30 cm),而深层(>30 cm)较少;6种重金属在红壤、潮土、黑土和砂土中的残留率平均值分别为98.0%、65.1%、65.9%和56.5%. ④与添加污染土壤之前相比,试验后土壤中残渣态等稳定形态重金属质量分数较低,其中Pb、In和Sb均以碳酸盐结合态和有机金属络合态为主,Ag和Sn分别以有机金属络合态、双氧水可提取有机结合态和有机金属络合态、无定形铁锰氧化物结合态为主,而Bi则以碳酸盐结合态和双氧水可提取有机结合态为主. 结果显示,红壤中Pb的迁移风险较低,潮土和黑土中Ag、Sb的迁移风险较高,而砂土中Sn和Sb的迁移风险需要格外关注.      

电增强零价铁强化厌氧氨氧化处理高氮养猪废水

为解决ZVI(零价铁)电极表面的钝化问题,实现anammox(厌氧氨氧化)工艺稳定、高效地运行,采用EEZVI-UASB(电增强零价铁-升流式厌氧污泥床)技术处理养猪废水,研究了EEZVI电极电压、ρ(COD_Cr)及脱氮贡献率的相关性. 结果表明,在温度为(35±1)℃、pH为6.80～7.10、电极电压为0.60 V的条件下,EEZVI-UASB对NH₄+-N和NO₂--N的去除率均维持在较高的水平;NH₄+-N去除率＞90.00%,NO₂--N去除率＞96.00%,TN平均去除率>90.00%. 当EEZVI电极电压为0.60 V时,AAOB(厌氧氨氧化菌)的活性为91.10 mg/(g·d)(以NH₄+-N计);EEZVI-UASB中的优势功能菌主要为Pseudomonas属,其菌属16S rDNA的PCR扩增相似性达97%;系统中同时存在着反硝化、anammox、甲烷化等反应;其中anammox占主导作用,其对TN去除率的贡献率为54.10%~93.30%,反硝化及其他反应对TN去除率的贡献率为6.70%~45.90%.      

铁活化过二硫酸盐湿法氧化去除一甲胺恶臭气体

CH₃NH₂(一甲胺)作为一种重要的工业原料而被大量使用,其嗅阈值低,具有刺鼻的鱼臭味,是一种典型的恶臭气体. 选取PS(过二硫酸盐)作为氧化剂,采用湿法吸收氧化去除CH₃NH₂. 在探讨CH₃NH₂的吸收性能的基础上,比较了4种方式〔Fe2+活化PS、CA(柠檬酸)螯合Fe2+活化PS、Fe0活化PS、CA联合Fe0活化PS〕对CH₃NH₂湿法氧化去除效果的影响. 结果表明:CH₃NH₂ 气体在酸性条件下易溶于水;单独用Fe2+或Fe0活化PS处理CH₃NH₂时,Fe0活化后的去除效果明显优于Fe2+;然而,在联合使用螯合剂CA之后,Fe2+活化的去除效果反而优于Fe0. CA螯合Fe2+的CH₃NH₂去除率由单独Fe2+活化时的32%升至64%,Fe0活化与CA联合Fe0活化去除率均提升至40%. 究其原因,可能是由于不同活化方式下Fe2+释放速率不同所致,释放速率直接影响了Fe2+的存在时间,Fe2+活化PS速率对于氧化去除效果有影响,并最终影响CH₃NH₂的脱除.      

Optimizing synthesis conditions of nanoscale zero-valent iron (nZVI) through aqueous reactivity assessment

Nanoscale iron particles (nZVI) is one of the most important engineered nanomaterials applied to environmental pollution control and abatement. Although a multitude of synthesis approaches have been proposed, a facile method to screen the reactivity of candidate nZVI materials produced using different methods or under varying synthesis conditions has yet been established. In this study, four reaction parameters were adjusted in the preparation of borohydride-reduced nZVI. The reductive properties of the resultant nanoparticles were assayed independently using two model aqueous contaminants, Cu(II) and nitrate. The results confirm that the reductive reactivity of nZVI is most sensitive to the initial concentration of iron precursor, borohydride feed rate, and the loading ratio of borohydride to ferric ion during particle synthesis. Solution mixing speed, in contrast, carries a relative small weight on the reactivity of nZVI. The two probing reactions (i.e., Cu(II) and nitrate reduction) are able to generate consistent and quantitative inference about the mass-normalized surface activity of nZVI. However, the nitrate assay is valid in dilute aqueous solutions only (50 mg·L⁻¹ or lower) due to accelerated deactivation of iron surface at elevated nitrate concentrations. Additional insights including the structural and chemical makeup of nZVI can be garnered from Cu(II) reduction assessments. The reactivity assays investigated in this study can facilitate screening of candidate materials or optimization of nZVI production parameters, which complement some of the more sophisticated but less chemically specific material characterization methods used in the nZVI research.