堆肥+零价铁可渗透反应墙修复黄土高原地下水中铬铅复合污染

为了研究堆肥+零价铁混合可渗透反应墙(PRB)修复黄土高原地下水中铬铅复合污染的可行性,分别用堆肥、零价铁、堆肥+零价铁、堆肥+零价铁+活性炭为反应介质,通过模拟柱实验考察PRB修复铬铅复合污染黄土高原地下水的效果。结果表明,在实验进行30 d后当反应柱1和2对六价铬的去除率接近于零,而且对二价铅的去除率迅速下降时,反应柱3对2种污染物仍保持较高的去除率;反应介质质量比为10∶2∶1的反应柱4和质量比为10∶1∶2的反应柱5对污染物的去除效果均优于质量比为10∶1∶1的反应柱3;反应50 d后,添加活性炭的反应柱6对2种污染物的去除率仍在90%。这说明使用堆肥+零价铁混合可渗透反应墙修复黄土高原地下水中铬铅复合污染是可行的;且以堆肥+零价铁作为介质的反应柱去除效果优于单独以堆肥或铁粉为介质的反应柱;增加铁粉或堆肥的用量有利于铬铅复合污染的去除;且同时添加活性炭更有助于污染物的去除。     

修复铬污染地下水的可渗透反应墙介质筛选

通过实验研究筛选出一种经济、高效的用于修复铬污染地下水的可渗透反应墙(PRB)介质。实验以铬污染地下水为研究对象,分别对Fe0、Fe0+石英砂和包覆型零价铁填料进行了筛选实验,选取处理效果好且经济可行的包覆型零价铁材料作为PRB反应介质。结果表明,以包覆型零价铁材料作为PRB反应介质,大大提高了铁粉的利用效率,且缓解了系统堵塞严重的问题。以包覆型零价铁材料作为PRB反应介质修复Cr(VI)污染地下水是可行的。     

PRB技术同步去除地下水中硝酸盐和镉

为评估可渗透反应墙(PRB)技术同步去除复合污染地下水中硝酸盐和重金属的可行性,选取蛭石、活性炭、固定化微生物为PRB反应介质,采用批实验和柱实验在不同填装方式及不同水力停留时间等条件下,考察PRB技术对硝酸盐和Cd~(2+)的同步去除效果。结果表明:PRB介质为蛭石或活性炭与固定化微生物组合型填料时,Cd~(2+)对PRB去除复合污染水体中的硝酸盐影响甚微,可实现高效的同步去除;当进水NO_3-N浓度为50 mg·L-1、Cd~(2+)浓度为10 mg·L-1时,活性炭与固定化微生物的组合型反应介质对NO_3-N和Cd~(2+)去除率分别可达93.13%和95.80%,蛭石与固定化微生物的组合型反应介质对NO_3-N和Cd~(2+)去除率分别可达92.70%和99.50%,经处理后的水质可达到地下水Ⅲ级质量标准(GB/T14848-2017)。以蛭石+固定化微生物、活性炭+固定化微生物作为反应介质的PRB技术可以实现NO_3-N和Cd~(2+)的同步去除,该技术可应用于处理硝酸盐和重金属复合污染地下水。     

PRB修复渗滤液污染地下水的实验研究

可渗透反应墙（PRB）原位修复地下水污染技术，具有经济、高效等特点。采用PRB技术治理渗滤液污染的地下水，反应介质的选择和介质配比是一个关键问题。因此，以渗滤液污染地下水为研究对象，分别用零价铁粉、活性炭、沸石和陶粒4种混合介质，设计了5个PRB反应器，分别为A、B、C、D和E，对PRB修复渗滤液污染地下水的可行性和有效性进行了试验研究。设计的反应器充分考虑了反应器的渗透性能。实验结果表明：混合介质反应器A、B、C、D和E对CODcr，的平均去除率分别达到了79．6％、75．6％、77．0％、78、9％和79．9％；对NH4^＋的平均去除率分别为87．3％、82．1％、92．1％、98．8％和88．5％。验证了PRB技术处理垃圾渗滤液对处理地下水污染的可行性。     

可渗透反应墙原位修复垃圾渗滤液污染地下水

实验模拟地下环境,以垃圾渗滤液污染地下水为研究对象,分别采用沸石、无烟煤、陶粒、活性炭、炉渣、粉煤灰和零价铁作为填充材料,设计了7种地下可渗透反应器(PRB)。分2个阶段对PRB技术治理污染地下水可行性和有效性进行实验模拟研究,还研究了填充材料配比对PRB修复效率影响,分阶段调整复合填充材料配比,观察反应器产生的不同处理效果。考察了7种反应器内pH、EC和DO的变化情况及对污染物去除效果影响,分析了污染物去除机理;找出了反应器存在的某些不足之处。实验结果显示,2个阶段反应器对COD去除率都较高,分别为82.36%～88.11%和89.45%～93.65%。     

零价铁渗透性反应墙原位修复含砷地下水的柱实验研究

为了解决地下水砷污染问题,设计了3根实验柱,开展了零价铁渗透性反应墙(zero valent iron permeable reactive barrier,ZVI PRB)原位修复5价砷的实验研究,调查了ZVI PRB的长期运行效果,探索了反应介质粒径、进水As浓度、渗流速度和腐殖酸(humic acid,HA)对反应墙除砷性能的影响。结果表明,PRB 1(铁粉,30~32目)的As去除率为76.2%~93.8%,出水As浓度为9.8~41.9μg·L~(-1);PRB 2(铁粉,300~325目)的去除率为84.4%~95.9%,出水As浓度为6.5~9.5μg·L~(-1)。ZVI PRB能有效地去除地下水中砷,且PRB 2比PRB 1的性能更高效更稳定并能保证出水水质满足《生活饮用水卫生标准》(GB 5749-2006)中As限值要求(10μg·L~(-1))。在现有条件下,ZVI粒径和进水As浓度显著影响ZVI PRB的除砷性能,渗流速度基本未影响除砷性能,而HA显著抑制除砷性能。     

海绵铁作为渗透反应墙介质去除地下水中NO3--N的初步研究

采用孔隙率高、比表面积大的海绵铁作为渗透反应墙(PRB)介质,通过3批动态实验讨论了海绵铁+锰砂单层介质、海绵铁+锰砂+活性炭单层介质,以及海绵铁+锰砂和活性炭的双层介质对地下水中NO3--N的去除效果.结果表明,经过292 h的PRB动态实验,填充海绵铁+锰砂单层介质、海绵铁+锰砂+活性炭单层介质、海绵铁+锰砂与活性炭双层介质的反应器的NO3--N去除率分别达到了70.65％、84.22％、88.09％,采用海绵铁与活性炭的单层介质或双层介质的反应器对地下水中NO3--N和TN的去除效果显著增强,出水中NH4+-N浓度相对也有所降低；扫描电镜和X射线衍射分析结果表明,经过PRB动态实验后,海绵铁表面覆盖了厚厚的膜,微孔隙被许多新的物质堵塞,这会导致海绵铁的氧化还原反应能力减弱,阻碍地下水中NO3--N的进一步还原去除,这也是以后实际应用中需要解决的问题.     

PRB技术对地下水中重金属离子的处理研究

实验模拟地下环境,以受重金属离子Pb(Ⅱ)、As(Ⅲ)、Cd(Ⅱ)、Cr(Ⅵ)、Fe(Ⅱ)和总Mn污染的地下水为研究对象,利用还原铁粉、铸铁粉、铸铁粉与颗粒活性炭的混合物为可渗透反应墙(PRB)的主要介质,石英砂为辅助介质,设计了3种反应器.在有效孔隙率为60%～65%、水力停留时间为12.0～14.4 h的条件下,考察其对污染物的去除效果.结果表明:3种反应器对Pb(Ⅱ)、As(Ⅲ)、Cd(Ⅱ)、Cr(Ⅵ)均有较高的去除效果,去除率达98%以上;总Mn的去除率分别达98%、89%和66%;Fe(Ⅱ)的去除率分别达83%、56%和49%.考察了3种反应器内pH、Eh、DO的关系及对重金属离子去除效果的影响,分析了污染物的去除机理.综合考虑处理效果与成本,笔者认为以铸铁粉与石英砂的混合物为PRB的反应介质,应用PRB技术原位处理受上述重金属离子污染的地下水是可行的.     

铸铁和椰壳活性炭混合介质修复高浓度Cr(Ⅵ)污染地下水研究

铬是人体和动物必需的微量元素之一。但高浓度的铬,尤其是地下水中的Cr(Ⅵ)可能对人体健康和环境造成很大的危害,因此研究高浓度Cr(Ⅵ)污染地下水的修复技术至关重要。应用铸铁和椰壳活性炭作为模拟柱中渗透反应格栅(PRB)的反应介质,为了防止实验过程发生堵塞,添加适当河沙,通过铸铁的还原作用及椰壳活性炭的吸附作用研究PRB对高浓度Cr(Ⅵ)污染地下水的修复效能。结果表明:铸铁、椰壳活性炭、河沙的质量比为3∶1∶4、Cr(Ⅵ)为400 mg/L条件下,完全穿透时反应材料对Cr(Ⅵ)整体去除率为67.0%,PRB反应介质寿命为165d;侧孔Cr(Ⅵ)浓度随时间延长而逐渐增大,离进水口越近,材料去除Cr(Ⅵ)的能力降低越快;出水及沿程在没有Cr(Ⅵ)检出时pH为4.5～7.0,出水有Cr(Ⅵ)检出时pH均大于7.0;出水中无Cr(Ⅵ)检出时,总铁(TFe)含量较高,Fe(Ⅲ)含量较少,有大量Fe(Ⅱ)产生,出水有Cr(Ⅵ)检出时,对应的Fe(Ⅲ)和TFe检出浓度均较低,说明柱体内铸铁材料基本钝化完全。     

铁屑耦合生物麦饭石的PRB系统修复含铬酸根与硝酸根地下水

针对污染地下水中铬酸根和硝酸根迁移速度快,可渗透反应墙(PRB)常规活性材料修复效果差等问题,以铁屑、麦饭石和硫酸盐还原菌(SRB)为活性材料,构建4组耦合PRB动态柱修复地下水中Cr(Ⅵ)和NO-3-N。结果表明,4#(铁屑、麦饭石和SRB)柱修复效果较1#(麦饭石)、2#(铁屑、麦饭石)和3#(麦饭石和SRB)柱好,且稳定,对Cr(Ⅵ)和NO-3-N平均去除率分别是97.7%和97.34%,可见,以铁屑、麦饭石和硫酸盐还原菌为活性材料的耦合PRB系统修复地下水中Cr(Ⅵ)和NO-3-N具有有效性与可行性。     

Zero valent iron remediation of a mixed brominated ethene contaminated groundwater

The suitability of a granulated zero valent iron (ZVI) permeable reactive barrier (PRB) remediation strategy was investigated for tribromoethene (TriBE), cis-1,2-dibromoethene (c-DBE), trans-1,2-dibromoethene (t-DBE) and vinyl bromide (VB), via batch and large-scale column experiments that were subsequently analysed by reactive transport modelling.The brominated ethenes in both batch and large-scale column experiments showed rapid (compared to controls and natural attenuation) degradation in the presence of ZVI. In the large-scale column experiment, degradation half-lives were 0.35 days for TriBE, 0.50 days for c-DBE, 0.31 days for t-DBE and 0.40 days for VB, under site groundwater flow conditions, resulting in removal of brominated ethenes within the first 0.2 m of a 1.0 m thick ZVI layer, indicating that a PRB groundwater remediation strategy using ZVI could be used successfully.In the model simulations of the ZVI induced brominated ethene degradation, assuming a dominant reductive β-elimination pathway via bromoacetylene and acetylene production, simulated organic compound concentrations corresponded well with both batch and large-scale column experimental data. Changes of inorganic reactants were also well captured by the simulations. The similar ZVI induced degradation pathway of TriBE and TCE suggests that outcomes from research on ZVI induced TCE remediation could also be applied to TriBE remediation.     

Removal of added nitrate in the single, binary, and ternary systems of cotton burr compost, zerovalent iron, and sediment: Implications for groundwater nitrate remediation using permeable reactive barriers

Recent research has shown that carbonaceous solid materials and zerovalent iron (Fe(0)) may potentially be used as media in permeable reactive barriers (PRBs) to degrade groundwater nitrate via heterotrophic denitrification in the solid carbon system, and via abiotic reduction and autotrophic denitrification in the Fe(0) system. Questions arise as whether the more expensive Fe(0) is more effective than the less expensive carbonaceous solid materials for groundwater nitrate remediation, and whether there is any synergistic effect of mixing the two different types of materials. We carried out batch tests to study the nature and rates of removal of added nitrate in the suspensions of single, binary, and ternary systems of cotton burr compost, Peerless Fe(0), and a sediment low in organic carbon. Cotton burr compost acted as both organic carbon source and supporting material for the growth of indigenous denitrifiers. Batch tests showed that cotton burr compost alone removed added nitrate at a greater rate than did Peerless Fe(0) alone on an equal mass basis with a pseudo-first-order rate constant k=0.0830+/-0.0031 h(-1) for cotton burr compost and a k=0.00223+/-0.00022 h(-1) for Peerless Fe(0); cotton burr compost also removed added nitrate at a faster rate than did cotton burr compost mixed with Peerless Fe(0) and/or the sediment. Furthermore, there was no substantial accumulation of ammonium ions in the cotton burr compost system, in contrast to the systems containing Peerless Fe(0) in which ammonium ions persisted as major products of nitrate reduction. It is concluded that cotton burr compost alone may be used as an excellent denitrification medium in a PRB for groundwater nitrate removal. Further study is needed to evaluate performance of its field applications.     

Removal of added nitrate in cotton burr compost, mulch compost, and peat: mechanisms and potential use for groundwater nitrate remediation

We conducted batch tests on the nature of removal of added nitrate in cotton burr compost, mulch compost, and sphagnum peat that may be potentially used in a permeable reactive barrier (PRB) for groundwater nitrate remediation. A rigorous steam autoclaving protocol (121 degrees C for 2h each day for three consecutive days) for the cotton burr compost and autoclaving of all labware and the nitrate working solutions resulted in drastically different results compared to the non-autoclaved treatment. In the non-autoclaved cotton burr compost, added nitrate at 20 mg N l(-1) decreased rapidly and was not detected after 3d; whereas, the autoclaved cotton burr compost showed persistent nitrate above 15.5 mg N l(-1) even after 10d, which is comparable with nitrate concentrations above 17.6 mg N l(-1) in a treatment using NaN(3) at 1000 mg l(-1). Dewaxed cotton burr compost showed decreased nitrate reduction compared to the pristine cotton burr compost. No nitrate reduction was detected in the dewaxed sphagnum peat. It is concluded that nitrate removal in the organic media is controlled by microbiologically mediated processes. The use of readily available cotton burr and mulch composts may offer a cost-effective method of nitrate removal from contaminated groundwater.     

Electrochemical removal of nitrate using ZVI packed bed bipolar electrolytic cell

The present study investigates the performance of the zero valent iron (ZVI, Fe⁰) packed bed bipolar electrolytic cell for nitrate removal. The packing mixture consists of ZVI as electronically conducting material and silica sand as non-conducting material between main cathode and anode electrodes. In the continuous column experiments for the simulated groundwater (initial nitrate and electrical conductivity of about 30 mg L⁻¹ as N and 300 μS cm⁻¹, respectively), above 99% of nitrate was removed at the applied potential of 600 V with the main anode placed on the bottom of reactor. The influx nitrate was converted to ammonia (20% to maximum 60%) and nitrite (always less than 0.5 mg L⁻¹ as N in the effluent). The optimum packing ratio (v/v) of silica sand to ZVI was found to be 1:1-2:1. Magnetite was observed on the surface of the used ZVI as corrosion product. The reduction at the lower part of the reactor in acidic condition and adsorption at the upper part of the reactor in alkaline condition are the major mechanism of nitrate removal.     

Performance of a field-scale permeable reactive barrier based on organic substrate and zero-valent iron for in situ remediation of acid mine drainage

A permeable reactive barrier (PRB) was installed in Aznalcóllar (Spain) in order to rehabilitate the Agrio aquifer groundwater severely contaminated with acid mine drainage after a serious mining accident. The filling material of the PRB consisted of a mixture of calcite, vegetal compost and, locally, Fe⁰ and sewage sludge. Among the successes of the PRB are the continuous neutralisation of pH and the removal of metals from groundwater within the PRB (removals of >95 %). Among the shortcomings are the improper PRB design due to the complexity of the internal structure of the Agrio alluvial deposits (which resulted in an inefficient capture of the contaminated plume), the poor degradability of the compost used and the short residence time within the PRB (which hindered a complete sulphate reduction), the clogging of a section of the PRB and the heterogeneities of the filling material (which resulted in preferential flows within the PRB). Undoubtedly, it is only through accumulated experience at field-scale systems that the potentials and limits of the PRB technology can be determined.     

Chromate transport through columns packed with surfactant-modified zeolite/zero valent iron pellets

Chromate transport through columns packed with zeolite/zero valent iron (Z/ZVI) pellets, either untreated or treated with the cationic surfactant hexadecyltrimethylammonium (HDTMA), was studied at different flow rates. In the presence of sorbed HDTMA, the chromate retardation factor increased by a factor of five and the pseudo first-order rate constant for chromate reduction increased by 1.5-5 times. The increase in rate constant from the column studies was comparable to a six-fold increase in the rate constant determined in a batch study. At a fast flow rate, the apparent delay in chromate breakthrough from the HDTMA modified Z/ZVI columns was primarily caused by the increase in chromate reduction rate constant. In contrast, at a slower flow rate, the retardation in chromate transport from the HDTMA modified Z/ZVI columns mainly originated from chromate sorption onto the HDTMA modified Z/ZVI pellets. Due to dual porosity, the presence of immobile water was responsible for the earlier breakthrough of chromate in columns packed with zeolite and Z/ZVI pellets. The results from this study further confirm the role of HDTMA in enhancing sorption and reduction efficiency of contaminants in groundwater remediation.     

Modelling the long-term performance of zero-valent iron using a spatio-temporal approach for iron aging

Zero-valent iron (ZVI) permeable reactive barriers (PRBs) have become popular for the degradation of chlorinated ethenes (CEs) in groundwater. However, a knowledge gap exists pertaining to the longevity of ZVI. The present investigation addresses this situation by suggesting a numerical simulation model that is intended to be used in conjunction with field or column tests in order to describe long-term ZVI performance at individual sites. As ZVI aging processes are not yet completely understood and are still subject to research, we propose a phenomenological modelling technique instead of a common process-based approach. We describe ZVI aging by parameters that characterise the extent and rate of ZVI reactivity change depending on the propagation of the precipitation front through ZVI. We approximate degradation of CEs by pseudo-first order kinetics accounting for the formation of partially dechlorinated products, and describe ZVI reactivity change by scaling the degradation rate constants. Three independent modelling studies were carried out to test the suitability of the conceptual and numerical model to describe the observations of accelerated column tests. All three tests indicated that ZVI reactivity declined with an increasing number of exchanged pore volumes. Measured and modelled concentrations showed good agreement, thereby proving that resolving spatial as well as temporal changes in ZVI reactivity is reasonable.     

Assessing the Cr(VI) reduction efficiency of a permeable reactive barrier using Cr isotope measurements and 2D reactive transport modeling

In Thun, Switzerland, a permeable reactive barrier (PRB) for Cr(VI) reduction by gray cast iron was installed in May 2008. The PRB is composed of a double array of vertical piles containing iron shavings and gravel. The aquifer in Thun is almost saturated with dissolved oxygen and the groundwater flow velocities are ca. 10-15m/day. Two years after PRB installation Cr(VI) concentrations still permanently exceed the Swiss threshold value for contaminated sites downstream of the barrier at selected localities. Groundwater δ(53/52)Cr(SRM979) measurements were used to track Cr(VI) reduction induced by the PRB. δ(53/52)Cr(SRM979) values of two samples downstream of the PRB showed a clear fractionation towards more positive values compared to four samples from the hotspot, which is clear evidence of Cr(VI) reduction induced by the PRB. Another downstream sample did not show a shift to more positive δ(53/52)Cr(SRM979) values. Because this latter location correlates with the highest downstream Cr(VI) concentration it is proposed that a part of the Cr(VI) plume is bypassing the barrier. Using a Rayleigh fractionation model a minimum present-day overall Cr(VI) reduction efficiency of ca. 15% was estimated. A series of 2D model simulations, including the fractionation of Cr isotopes, confirm that only a PRB bypass of parts of the Cr(VI) plume can lead to the observed values. Additionally, the simulations revealed that the proposed bypass occurs due to an insufficient permeability of the individual PRB piles. It is concluded that with this type of PRB a complete and long-lasting Cr(VI) reduction is extremely difficult to achieve for Cr(VI) contaminations located in nearly oxygen and calcium carbonate saturated aquifer in a regime of high groundwater velocities. Additional remediation action would limit the environmental impact and allow to reach target concentrations.     

Remediation of RDX- and HMX-contaminated groundwater using organic mulch permeable reactive barriers

Organic mulch is a complex organic material that is typically populated with its own consortium of microorganisms. The organisms in mulch breakdown complex organics to soluble carbon, which can then be used by these and other microorganisms as an electron donor for treating RDX and HMX via reductive pathways. A bench-scale treatability study with organic mulch was conducted for the treatment of RDX- and HMX-contaminated groundwater obtained from a plume at the Pueblo Chemical Depot (PCD) in Pueblo, Colorado. The site-specific cleanup criteria of 0.55 ppb RDX and 602 ppb HMX were used as the logical goals of the study. Column flow-through tests were run to steady-state at the average site seepage velocity, using a 70%:30% (vol.:vol.) mulch:pea gravel packing to approach the formation's permeability. Significant results included: (1) Complete removal of 90 ppb influent RDX and 8 ppb influent HMX in steady-state mulch column effluent; (2) pseudo-first-order steady-state kinetic rate constant, k, of 0.20 to 0.27 h(-1) based on RDX data, using triplicate parallel column runs; (3) accumulation of reduced RDX intermediates in the steady-state column effluent at less than 2% of the influent RDX mass; (4) no binding of RDX to the column fill material; and (5) no leaching of RDX, HMX or reduction intermediates from the column fill material. The results of the bench-scale study will be used to design and implement a pilot-scale organic mulch/pea gravel permeable reactive barrier (PRB) at the site.