Biogeochemistry of two types of permeable reactive barriers, organic carbon and iron-bearing organic carbon for mine drainage treatment: Column experiments

Permeable reactive barriers (PRBs) are an alternative technology to treat mine drainage containing sulfate and heavy metals. Two column experiments were conducted to assess the suitability of an organic carbon (OC) based reactive mixture and an Fe⁰-bearing organic carbon (FeOC) based reactive mixture, under controlled groundwater flow conditions. The organic carbon mixture contains about 30% (volume) organic carbon (composted leaf mulch) and 70% (volume) sand and gravel. The Fe⁰-bearing organic carbon mixture contains 10% (volume) zero-valent iron, 20% (volume) organic carbon, 10% (volume) limestone, and 60% (volume) sand and gravel. Simulated groundwater containing 380 ppm sulfate, 5 ppm As, and 0.5 ppm Sb was passed through the columns at flow rates of 64 (the OC column) and 62 (the FeOC column) ml d^− 1, which are equivalent to 0.79 (the OC column) and 0.78 (the FeOC column) pore volumes (PVs) per week or 0.046 m d^− 1 for both columns. The OC column showed an initial sulfate reduction rate of 0.4 µmol g (OC)^− 1 d^− 1 and exhausted its capacity to promote sulfate reduction after 30 PVs, or 9 months of flow. The FeOC column sustained a relatively constant sulfate reduction rate of 0.9 µmol g (OC)^− 1 d^− 1 for at least 65 PVs (17 months). In the FeOC column, the δ³⁴S values increase with the decreasing sulfate concentration. The δ³⁴S fractionation follows a Rayleigh fractionation model with an enrichment factor of 21.6‰. The performance decline of the OC column was caused by the depletion of substrate or electron donor. The cathodic production of H₂ by anaerobic corrosion of Fe probably sustained a higher level of SRB activity in the FeOC column. These results suggest that zero-valent iron can be used to provide an electron donor in sulfate reducing PRBs. A sharp increase in the δ¹³C value of the dissolved inorganic carbon and a decrease in the concentration of HCO₃⁻ indicate that hydrogenotrophic methanogenesis is occurring in the first 15 cm of the FeOC column.     

冻融交替处理下湿地土壤可溶性铁的动态变化研究

通过原位土柱模拟实验,对比研究了冻融交替下(-10℃冻结1d后5℃融化7d作为1个冻融周期,共5个周期,并以5℃恒温培养为对照)三江平原典型环形湿地土壤可溶性铁的动态变化.结果表明,冻融交替处理导致了环形湿地3种典型湿地土壤(毛苔草群落的腐殖质沼泽土、乌拉苔草群落的草甸沼泽土和小叶章群落的草甸白浆土)溶液中的pH和Eh在经过第1个冻融周期后大都先升高,而在后4个周期后再逐渐降低;在整个实验过程中冻融组的pH有84.4%低于对照,而Eh则有82.2%的高于对照;各土壤溶液中的可溶性铁都以Fe3+为主,而Fe3+的还原受到冻融交替处理的抑制,无论Fe2+、Fe3+或总铁(TFe)的含量大都低于对照,其中TFe从(1.25±0.16)mg·L-1减少到(0.62±0.08)mg·L-1;不同土类之间,腐殖质沼泽土的pH、Eh和可溶性铁含量变化趋势与草甸白浆土的变化趋势差异显著,处于过渡带的草甸沼泽土则在pH的变化趋势上更接近于草甸白浆土,而在Eh和可溶性铁含量的变化趋势上更接近于腐殖质沼泽土;各土类不同土层之间,冻融交替对湿地上层土壤的影响要小于深层土壤.     

纳米零价铁及其双金属体系对菲的降解研究

以实验室合成的纳米零价铁(n ZVI)及其双金属(n ZVI/Cu和n ZVI/Ni)为反应材料,对菲(Phenanthrene)的去除进行研究.表征结果表明:纳米颗粒平均粒径均为80~100 nm,主要以α-Fe0的形式存在.批实验结果表明,5 g·L-1的n ZVI,n ZVI/Cu和n ZVI/Ni对菲溶液均有去除效果,其去除效率依次为n ZVI/Nin ZVI/Cun ZVI.溶液初始p H为7.5时,5 g·L-1的n ZVI/Ni去除88%0.5 mg·L-1的菲只需3 h,而n ZVI/Cu和n ZVI分别需要29 h和40 h.3种纳米铁对菲的去除率均随着n ZVI投加量的增加而升高,随着菲溶液初始浓度的增加而降低.反应温度的升高可提高n ZVI/Ni对菲的去除效率,高温时(≥30℃)菲的降解遵循一级反应动力学模型.p H对反应影响不大.GC-MS结果表明,n ZVI/Ni降解菲溶液主要为催化加氢反应,而n ZVI/Cu和n ZVI对菲溶液的去除主要为吸附作用.     

改性活性炭对废水中甲醛的吸附研究

通过浸渍-焙烧的方法制得铁改性活性炭,并将之应用于废水中甲醛的吸附.分别考察了吸附时间、初始溶液质量浓度、吸附剂投加量对改性活性炭吸附甲醛效果的影响,并研究了铁改性活性炭对甲醛水溶液的等温吸附及动力学.结果表明:在25℃、活性炭投加量为10 g/L、吸附时间为360 min时,铁改性活性炭对甲醛的去除率为91.8％;用准一级、准二级及内扩散动力学模型拟合吸附过程,准二级动力学模型符合该吸附过程;用Langmuir和Freundlich模型描述等温吸附过程,该吸附过程服从Langmuir模型,饱和吸附量为3.396 7mg/g.     

不同水分条件下铁基氧化物对土壤砷的稳定化效应研究

应用等温吸附试验及室内模拟培养的方法,研究了Fe2O3、Nano-Fe2O3和铁锰双金属氧化物(FMBO)等铁基氧化物对砷的吸附特性和对不同含水量土壤中砷的稳定化效应.从等温吸附试验结果来看,3种铁基氧化物对As(V)和As(Ⅲ)的吸附过程符合准二级动力学方程,12 h后基本达到吸附平衡,吸附等温线符合Langmuir方程,FMBO对As(V)和As(Ⅲ)的吸附容量显著大于Fe2O3和Nano-Fe2O3,且对As(Ⅲ)的饱和吸附容量大于As(V),能够起到氧化和吸附的双重作用.从对不同含水量土壤中砷的稳定化效果来看,Nano-Fe2O3和FMBO在风干和田间持水量土壤中均能达到90%以上的稳定化效率,显著高于Fe2O3;在土壤水分饱和条件下,FMBO的稳定化效率仍保持在93.5%以上,且能够将土壤中As(Ⅲ)氧化成As(V),而Fe2O3和Nano-Fe2O3分别仅为29.4%、81.4%.3种铁基氧化物的添加会使土壤中砷的结合态发生变化,Fe2O3、NanoFe2O3主要使砷由F1非专性吸附态和F2专性吸附态向F4结晶铁锰或铁铝水化氧化物结合态转变,添加FMBO主要向F3无定形或弱结晶铁锰或铁铝水化氧化物结合态转变.总体看来,在非饱和状态的土壤,Nano-Fe2O3和FMBO均为良好的稳定化材料,而对于长期淹水的稻田或地下水位较高的地区,或者由于降雨造成土壤滞水等情况,FMBO可以作为一种优良的稳定化材料用于土壤砷污染修复.     

新型水处理材料海绵铁在废水处理中的应用研究

作为一种新型多功能水处理材料,海绵铁具有优越的物理化学性能。通过吸附、微电解、絮凝沉淀、直接还原和间接氧化等作用,海绵铁在水体去污的过程中显现了较强的处理能力。在总结海绵铁去除水中难降解有机物和重金属离子等污染物的研究现状的基础上,提出海绵铁在应用中存在的问题及改进方向。海绵铁与微生物在降解水体污染物的过程中存在互促作用,因而生物海绵铁体系有更强的处理能力,将成为海绵铁材料用于水处理的开发研究新方向。     

海绵状零价铁修复硝酸盐污染地下水试验研究

研究以50~100目的海绵状铁粉为还原剂,采用静态试验方法,研究了铁对硝酸盐氮的还原作用及其影响因素,分析了铁粉用量、铁炭比、pH值、硝酸盐氮初始浓度、温度以及铁粉表面预处理对硝酸盐去除率的影响。试验结果表明,最佳铁氮质量比为400∶1,铁粉投入过多对硝酸盐的去除率没有进一步促进;活性炭的加入有助于零价铁(Fe0)还原硝酸盐,降低反应后溶液中的NH+4-N浓度,试验最佳的铁炭比为1∶2;溶液的初始pH值降低有利于硝酸盐氮的去除;硝酸盐氮初始浓度越大,反应的平均速率越高;升高温度和酸洗预处理,有利于提高硝酸盐的去除率;产物分析表明,试验过程中,去除的NO-3-N含量中约60%以上转化为NH+4-N,NO-2-N浓度很低。     

零价铁-过二硫酸盐连续运行体系去除水中硝基苯

水中硝基苯(NB)的高毒性对人体健康具有极大的危害,因此,本文建立了零价铁-过二硫酸盐(Fe0-PS)连续运行体系以降解水中NB.研究结果表明,单独Fe0柱可还原降解NB,Fe0对不同浓度NB的还原效果均较好,随着流速的减慢及初始pH的降低,NB还原效果变好;但还原体系中总有机碳(TOC)基本没有去除,只是生成了中间产物苯胺(AN).Fe0-PS联合体系中,随着PS的投加,产生的Fe2+活化PS,发生了类Fenton反应,从而使还原产物AN得以氧化降解,TOC去除率可达54.8%;随着Fe0填充量的增加,氧化产物Fe2+随之增加,还原产物AN随之减少.可见,Fe0-PS连续运行体系,以Fe2+为媒介巧妙结合还原与氧化作用,能有效去除NB.     

Graphene-supported nanoscale zero-valent iron：Removal of phosphorus from aqueous solution and mechanistic study

Excess phosphorus from non-point pollution sources is one of the key factors causing eutrophication in many lakes in China,so finding a cost-effective method to remove phosphorus from non-point pollution sources is very important for the health of the aqueous environment. Graphene was selected to support nanoscale zero-valent iron(nZVI)for phosphorus removal from synthetic rainwater runoff in this article. Compared with nZVI supported on other porous materials,graphene-supported nZVI(G-nZVI) could remove phosphorus more efficiently. The amount of nZVI in G-nZVI was an important factor in the removal of phosphorus by G-nZVI,and G-nZVI with 20 wt.% nZVI(20% G-nZVI)could remove phosphorus most efficiently. The nZVI was very stable and could disperse very well on graphene,as characterized by transmission electron microscopy(TEM) and scanning electron microscopy(SEM). X-ray photoelectron spectroscopy(XPS),Fourier Transform infrared spectroscopy(FT-IR) and Raman spectroscopy were used to elucidate the reaction process,and the results indicated that Fe-O-P was formed after phosphorus was adsorbed by G-nZVI. The results obtained from X-ray diffraction(XRD) indicated that the reaction product between nZVI supported on graphene and phosphorus was Fe3(PO4)2·8H2O(Vivianite). It was confirmed that the specific reaction mechanism for the removal of phosphorus with nZVI or G-nZVI was mainly due to chemical reaction between nZVI and phosphorus.     

Zn2+对铁氧化物吸附苄嘧磺隆的影响

研究2种人工合成的铁氧化物对磺酰脲类除草剂--苄嘧磺隆(bensulfuron-methyl,BSM)的吸附,以及Zn2 对供试样品吸附苄嘧磺隆的影响.实验结果表明,用Langmuir、Freundlich、Temkin等方程对供试样品加入Zn2 后吸附BSM的数据进行了拟合,发现供试样品吸附苄嘧磺隆的等温曲线较好地符合Freundlich方程.加入Zn2 后,铁氧化物吸附苄嘧磺隆的量较未加Zn2 有较大幅度的增加,但在苄嘧磺隆的平衡质量浓度较低(＜4 mg/L)时,氧化物吸附苄嘧磺隆的量不随Zn2 浓度的增加而增加;在苄嘧磺隆的平衡质量浓度较高(＞6 mg/L)时,氧化物吸附苄嘧磺隆的量随Zn2 浓度的增加而增加.这可能是Zn2 和苄嘧磺隆被吸附时存在竞争和协同交互作用的结果.