Defining quality assurance guidance for effective selection of technical grade zero-valent iron production batch for groundwater remediation using permeable reactive barrier.

Zero-valent iron (ZVI) applied to the remediation of contaminated groundwater (GW) in situ, especially using engineered permeable reactive barriers (PRBs), has been proven to be an effective reactive material. However, many of ZVI brands do not represent tailored reagents specifically regarding destroying pollutants in GW. Thus, their reactivity towards certain contaminants in GW may vary significantly in a wide range even with different production batches of the same ZVI brand. This issue has rarely been known and consequently not addressed to a higher extend so far. Therefore, this study implemented extensive, long-term column experiments followed by short-term batch experiments for chlorinated volatile organic compounds (cVOCs) degradation for developing a semi-empirical test methodology to thoroughly resolve this pivotal issue by achieving an improved quality assurance guidance regarding proper field-scale emplacement of different ZVI brands and their production batches. The results showed that during column experiments perchloroethylene (PCE) led to a significant degradation up to a certain period but sulfate-reducing microorganisms enhanced the dehalogenation and led approximately to 100 % PCE removal. However, the efficacy varied for different ZVI brands, i.e., Gotthart Maier (GM) and Sponge Iron (Responge®). Furthermore, it could be shown that it might even vary among different production batches of the same ZVI brand. It was also observed that evolution of sulfate-reducing microorganisms may improve the efficacy of PCE degradation vastly that occur at different intensities with different ZVI brands and their respective production batches over time. Further, comparing comprehensive long-term column (kobs = 0.0488 1/h) and short-term batch experiments (kobs = 0.07794 1/h) as well as refined kinetic analyses (kobs = 0.0424 1/h) clearly prove that an appropriate guidance protocol for successful full-scale in situ remediation is required for properly select the right ZVI brand and production batch before it is loaded to a PRB in the field.

Degradation of pharmaceuticals and other emerging pollutants employing bi-metal catalysts/magnesium and/or (green) hydrogen in aqueous solution.

Contaminations by pharmaceuticals, personal care products, and other emerging pollutants in water resources have become a seriously burgeoning issue of global concern in the first third of the twenty-first century. As societal reliance on pharmaceuticals continues to escalate, the inadvertent introduction of these substances into water reservoirs poses a consequential environmental threat. Therefore, the aim of this study was to investigate reductive degradation, particularly, catalytic hydrogenation regarding model pollutants such as diclofenac (DCF), ibuprofen (IBP), 17α-ethinylestradiol (EE2), or bisphenol-A (BPA), respectively,  in aqueous solutions at lab scale. Iron bimetals (zero valent iron, ZVI, and copper, Cu, or nickel, Ni) as well as zero valent magnesium (Mg, ZVM) in combination with  rhodium, Rh, or palladium, Pd, as hydrogenation catalysts (HK), were investigated. Studies were executed through various short-term batch experiments, with multiple sample collections, over a total range of 120 min. The results indicated that DCF was attenuated at over 90 % when exposed to Fe-Cu or a Fe-Ni bimetal (applied as a single model pollutant). However, when DCF was part of a mixture alongside with IBP, EE2, and BPA, the attenuation efficacy decreased to 79 % with Fe-Cu and 23 % with Fe-Ni. Conversely, both IBP and BPA exhibit notably low attenuation levels with both bimetals, less than 50 %, both deployed as single substances or in mixtures. No reaction (degradation) products could be identified employing LC-MS, but sometimes a release of the parent pollutant when applying an acetic acid buffer could be noted to a certain extent, suggesting adsorption processes on corrosion products such as iron hydroxide and/or oxides. Surprisingly, Mg in combination with Rh (Rh-HK) or Pd (Pd-HK) showed a significantly rapid decrease in the concentrations of DCF, EE2, and BPA, in part up to approximately 100 %, that is, within a few minutes only in part due to hydrogenation degradation reactions (related reaction products could actually be identified by LC-MS; adsorption processes were not observed here). Moreover, kinetic modeling of the DCF degradation with Mg-Rh-HK was conducted at different temperatures (15 °C, 20 °C, 25 °C, 35 °C) and varied initial concentrations (2.5 mg/L, 5.0 mg/L, 7.5 mg/L, 10.0 mg/L). The outcomes prove that the degradation of DCF at the Rh-HK's surface followed a modified first-order kinetics, most probably by catalytic hydrodehalogenation and subsequent hydrogenation of the aromatic moieties (molecular hydrogen was provided by the corrosion of Mg). From the determined reaction rate constants at four different temperatures, the activation energy was estimated to be 59.6 kJ/mol by means of the Arrhenius equation what is in good agreement with similar results reported in the literature. This coupled hydrodehalogenation and hydrogenation approach may be upscaled into a new promising technical process for comprehensively removing such pharmaceuticals and similar pollutants in sewage plants in a single step, furthermore, even in combination with adsorption by activated carbon and/or ozonation which have already been established at some sewage plants in Switzerland and Germany recently.

Performance of field-scale permeable reactive barriers: An overview on potentials and possible implications for in-situ groundwater remediation applications.

Permeable reactive barriers (PRBs) are significant among all the promising remediation technologies for treating contaminated groundwater. Since the first commercial full field-scale PRB emplacement in Sunnyvale, California, in 1994-1995, >200 PRB systems have been installed worldwide. The main working principle of a PRB is to treat a variety of contaminants downstream from the contaminated source zone ("hot spot"). However, to accurately assess the longevity of PRBs, it is essential to know the total contaminant mass in the source area and its approximate geometry. PRBs are regarded as both a safeguarding and an advanced decontamination technique, depending on the contamination scenario and its outcome during the operational lifetime of the barrier. In the last three decades, many PRBs have performed very well, that is, met expected clean-up goals at a variety of contaminated sites. However, there is still the necessity of thoroughly evaluating the implications of the performance of different PRB designs and reactive or adsorptive materials worldwide. Therefore, this study presents a comprehensive overview of field-scale PRBs applications and their long-term performance after on-site emplacements. This paper provides in-depth insight into this passive in-situ remediation technology for treating and even eliminating a contaminated plume over a long time in the subsurface. The overview will help all stakeholders worldwide understand the implications of PRBs and guide them to take all the required measures before its on-site application to avoid any potential failure.

An integrated permeable reactive barrier and photobioreactor approach for simultaneous removal of nitrate, phosphate and hexavalent chromium: A combined batch and continuous flow study.

In this study, simultaneous removal of nitrate (NO3-), phosphate (PO43-) and hexavalent chromium (Cr(VI)) from wastewater was investigated using a novel integrated filtration unit consisting of adsorbent based permeable reactive barrier (AB-PRB) and biosorption based photobioreactor (BSB-PBR). AB-PRB was comprising a mixture of low-cost adsorbents in an optimum proportion, whereas BSB-PBR carried C. vulgaris microalgae cultivated in controlled environment. The batch analysis for AB-PRB showed maximum removal efficiency of 95.7% and 98.0% for NO3- and PO43-, at pH-6, whereas 84.0% for Cr(VI) at pH-4. However, continuous flow study showed decreasing trend in removal efficiency of NO3-, PO43- and Cr(VI) with increasing flow rate from 10 ml min-1 to 30 ml min-1. Further, in BSB-PBR, maximum removal of 98.2% was achieved for Cr(VI) of 1.0 mg L-1 initial concentration at 3.3 days of hydraulic retention time (HRT). This study provides a novel integrated remediation approach for efficient removal of unlike contaminants.