This research was aimed to investigate the enhancement of electrokinetic (EK) remediation arsenate-contaminated soil by permeable reaction barrier (PRB). All experiments, which experimental parameters included the position, materials, and quantity of PRB, processing fluid types, potential gradients, and treatment time, were conducted in two types of EK systems. One was Pyrex glass cylindrical cells with dimension of 4.2 cm (£r) ¡Ñ 12 cm (L) and the other was a small pilot-scale modulus with dimension of 36cm (L) ¡Ñ18cm (W) ¡Ñ18cm cm (H). The PRBs were composed of four kinds of reaction materials, which included commercial zero valent iron (Fe(0)C), manufactured zero valent iron (Fe(0)M), commercial hydrous ferric oxide (FeOOHC), and manufactured hydrous ferric oxide (FeOOHM), mixed with ottawa sand in a ratio of 1:2,respectively, and installed in the anode, middle, and cathode side of the EK systems. For 5-day EK cylindrical cell tests, the results showed that the PRB installation would result in a lower electroosmosis permeability (Ke) and a higher removal efficiency of arsenate. The arsenate removal efficiency of EK system with PRB was in the range of 43.89-70.25%, which was 1.5~2.6 times greater than that without PRB, and the value of Ke was in the range of 4.30-12.61¡Ñ10-6 cm2/V-s. The soil pH after EK/PRB treatment was much closer to natural and more arsenate was collected in the anode reservoir. Moreover, the remediation performance of FeOOHC as PRB materials was much better than other materials. For EK pilot-scale modulus tests, it was shown that the removal efficiency of arsenate was effectively enhanced as improved experimental parameters and, however, led to increase the treatment cost. In EK modulus without PRB, the removal efficiency of arsenate, elctroosmosis permeability, and energy consumption were 27.76%, 3.30-5.39¡Ñ10-6 cm2/V-s, and 1724.81 kWh/m3, respectively. Furthermore, the treatment cost was NT 9583/m3. As increasing treatment time, graphite electrode, potential gradient, and quantity of PRB materials, the removal efficiency of arsenate increased to as high as 45.11-71.22% and the treatment cost also increased up to NT 24,800-57,730/m3. As investigated the binding form of arsenate with soil after EK/PRB treatment, it was found that the arsenate ¡Vsoil binding forms of Fe-Mn oxide bound, organically bound, and residual in the soil section behind the PRB were much easier transformed to the forms of exchangeable and carbonate bound. The transformation rate reached as high as 72.5% and it increased with treatment time. However, the Fe-Mn oxide bound was still the main binding form, 61.6-81.6%, in the soil section prior to the PRB. The removal mechanism of arsenate contaminated soil remediation was dominated by electromigration, electrolysis, and electroosmosis in EK system without PRB. And, in EK/PRB system, the removal of arsenate from soil was mainly resulted from adsorption rather than redox reaction by PRB. To sum up, the PRB can effectively enhance the electrokinetic remediation of arsenate contaminated soil by choosing the right PRB materials and operation parameters.

The main objective of this study was to evaluate the feasibility of using nanoscale zero-valent iron (nZVI) as the source of hydrogen to enhance in situ anaerobic biodegradation of trichloroethylene (TCE). In the first part of this study, microcosms were constructed to evaluate the effects of different controlling factors [e.g., different redox conditions (aerobic and anaerobic conditions), different microorganisms (in situ microorganisms, activated sludge, and anaerobic sludge), and different sources of substrates and electron donors (phenol, cane molasses, hydrogen, and nZVI)] on TCE biodegradation. In the second part of this study, batch experiments were conducted to evaluate the feasibility of hydrogen production by nZVI and bimetallic particles. Results from the microcosm study indicate that in-situ microorganisms were capable of degrading TCE under aerobic and anaerobic conditions. Results also show that TCE removal was more effective by activated sludge and anaerobic sludge. Aerobic biodegradation of TCE was enhanced by the addition of phenol and cane molasses. Under anaerobic conditions, TCE removal could be improved when cane molasses and hydrogen were supplied. In addition, anaerobic TCE degradation was more effective with the presence of hydrogen. Results of microcosms conducted with the addition of nZVI reveal that TCE was degraded completely in both live and autoclaved microcosms. This indicates that chemical reductive dechlorination seemed to dominate the removal of TCE in microcosms. Therefore, further studies with higher TCE concentrations or lower nZVI doses need to be conducted to determine the effects of the produced hydrogen on TCE biodegradation. Results from the hydrogen production experiments indicate that efficiency of hydrogen production by nZVI ranged from 30% to 76%. Higher dose of nZVI addition resulted in higher amount of hydrogen production. The total amounts of hydrogen production were correlated with the doses of nZVI. In addition, rates and efficiency of hydrogen production by bimetallic particles were better than those of nZVI. Results of the batch experiments reveal that nZVI and bimetallic particles had good efficiency on hydrogen production. This indicates that nZVI and bimetallic particles have high potential to be used as hydrogen producers. In this study, a simple system consisted of only water and nZVI or bimetallic particles was applied to produce hydrogen. Although TCE in microcosms with nZVI addition was totally consumed by nZVI, results of microcosms with hydrogen addition demonstrated that hydrogen was able to improve the efficiency of anaerobic TCE biodegradation. Thus, it may be feasible to use nZVI as the source of hydrogen to enhance in situ anaerobic biodegradation of TCE. The advantages of using nZVI as the source of hydrogen include: (1) rapid removal of significant contaminant concentrations in the early stage of nZVI injection; (2) creation of a more reducing environment; (3) safer than liquid hydrogen, which is stored in steel containers; and (4) direct hydrogen supply without transfer of biological mechanisms compared to commercial hydrogen release compounds and other organic substrates. Results of this study suggest that biological reductive dechlorination of TCE can be enhanced if proper doses of nZVI are supplied in situ. Knowledge and comprehension obtained in this study will be helpful in designing an enhanced in situ anaerobic bioremediation system for a TCE-contaminated site.

Many water treatment technologies for arsenic removal that are used today produce arsenic-bearing solid residuals (ABSR), which are disposed in mixed solid waste landfills. It is now well established that many of these residuals will release arsenic into the environment to a much greater extent than predicted by standard regulatory leaching tests and, consequently, require stabilization to ensure benign behaviour after disposal. Conventional waste stabilization technologies, such as cement encapsulation and vitrification, are not suitable for ABSR applications due to their lack of effectiveness or high cost, thus creating a need for a more effective and low-cost treatment technology for ABSR. Arsenic Crystallization Technology (ACT) is a proposed arsenic stabilization method that involves in converting the ABSR into arsenic-bearing minerals that resemble natural materials and have high arsenic capacity, long term stability, and low solubility compared to untreated ABSR. Three arsenic minerals, scorodite, arsenate apatite and ferrous arsenate, have been investigated in this research for their potential application as ACT for ABSR stabilization. Among the three minerals, ferrous arsenate is demonstrated to be the most suitable arsenate mineral for safe arsenic disposal due to its low arsenic solubility and ease of synthesis. An innovative treatment procedure has been developed in this research for stabilization of ABSR to a stable phase of ferrous arsenate using zero-valent iron (ZVI) as the reducing agent. The procedure works at ambient temperature and pressure, and neutral pH. In addition, a modified four-step sequential extraction method has been developed as a means to determine the proportions of various arsenic phases in the stabilized as well as untreated ABSR matrices. This extraction method, as well as traditional leach and solubility tests, show that arsenic stability in the solid phase is dramatically increased after formation of crystalline ferrous arsenate.

Phosphorus (P) is one of the essential nutrients for living organisms; however, excess P in aquatic systems often causes environmental and ecological problems including eutrophication. Removal of P from domestic wastewater, industrial wastewater, and agricultural organic-waste systems is required to minimize loading of P to receiving water bodies. A variety of sorbents or filter materials have previously been evaluated for P removal, including natural materials, industrial byproducts, and synthetic products. Among these materials industrial byproducts were reported as most effective. However, only a few of these studies were based on field experiments. Pharmaceutically active compounds (PhACs) and acesulfame-K (an artificial sweetener) are emerging contaminants observed in wastewater. The removal of PhACs in conventional wastewater treatment systems has been studied; however, few studies on alternative treatment systems are available. Studies related to the removal of acesulfame-K are even more limited. This thesis was focused on evaluation of basic oxygen furnace slag (BOFS), a byproduct from the steel manufacturing industry, as a potential reactive media for P removal from surface water and wastewater. The removal of PhACs and acesulfame-K in wastewater treatment systems containing BOFS as a treatment component was also evaluated. The effectiveness of BOFS for removing P from lake water was evaluated in a three year pilot-scale hypolimnetic withdrawal P treatment system at Lake Wilcox, Richmond Hill, Ontario. Phosphate concentrations of the hypolimnion water ranged from 0.3 to 0.5 mg L-1. About 83-100% P was removed during the experiment. The reactive mixtures were changed each year to improve the performance of the treatment system. Elevated pH (9-12) at the effluent of the treatment system was adjusted by sparging CO2(g) to near neutral pH. Elevated Al was removed through this pH adjustment. Elevated concentrations of V were removed in a column containing 5 wt% zero valent iron (ZVI) mixed with sand (0.5 m3) at the end of the BOFS based column. Removal of P in the BOFS based media is attributed to adsorption and co-precipitation at the outer layer of BOFS. Geochemical modeling results showed supersaturation with respect to hydroxyapatite, ß-tricalciumphosphate, aragonite, and calcite. Solid phase analyzes of the BOFS based reactive media collected after completion of the year 2 experiment (spent media) through combination of scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), and X-ray absorption near edge structure spectroscopy (XANES) support the presence of calcium phosphate minerals on the outer layer of the spent media. A multistep wastewater treatment experiment was carried out in an indoor facility at the Center for Alternative Wastewater Treatment, Fleming College, Lindsay, Ontario, Canada. This experiment evaluated the removal of P, ammonia, cBOD5, COD, E. coli, total coliform, and trace metals in a series of treatment cells including a mixing cell, a vertical subsurface flow aerobic cell, a vertical subsurface flow P treatment cell containing BOFS, and a horizontal subsurface flow anaerobic cell. About 97-99% removal of P, NH3, cBOD5, E. coli, and total coliform; and ~72% removal of COD were achieved in the treatment system. The mixing cell and the aerated cell reduced the concentrations of P, ammonia, cBOD5, E. coli, and total coliform significantly and the P treatment cell provided additional treatment. However, the primary objective of the P treatment cell was to reduce P concentrations to the acceptable range according to the water quality guidelines. The P treatment cell had successfully fulfilled this objective. Elevated concentration of Al and V were also observed in the P treatment cell effluent. The concentration of Al decreased to below the guideline value of 0.075 mg L-1 after introducing a pH adjustment unit between the P treatment cell and the anaerobic cell. The concentration of V was decreased in the anaerobic cell effluent. However, the effluent concentration of V was much higher than the guideline value. Geochemical speciation modeling results showed supersaturation with respect to hydroxyapatite, ß-tricalciumphosphate, aragonite and calcite along the flow path. Accumulation of P on the outer layer of the spent BOFS media was identified by energy dispersive X-ray spectroscopy (EDX). Although X-ray photoelectron spectroscopy (XPS) can provide information to a depth of 5-7 nm from the outer layer of the spent media, both Ca and P were positively identified in some of the samples. Accumulation of P at the edge of the grains of the spent media was clearly identified on the element map of polished cross-sections and corresponding FTIR spectra. The phosphate and carbonate functional groups were identified by the distribution of different vibrational frequencies through FTIR spectroscopy. The presence of calcite and hydroxyapatite were inferred based on the wave numbers assigned for these minerals in the literature. Finally, X-ray absorption near edge structure spectroscopy (XANES) on the outer layer samples from the spent BOFS media and corresponding linear combination fitting analysis indicated the presence of ß-tricalciumphosphate, hydroxyapatite, and calcium phosphate dibasic. Based on the observations from the indoor wastewater treatment experiment, a multistep demonstration-scale outdoor wastewater treatment experiment was conducted to investigate the applicability of the integration of the P treatment technology and engineered wetland technology at a relatively large scale prior to a full-scale field installation. The anaerobic treatment cell was not included in this outdoor system because this unit did not efficiently remove ammonia and metals (e.g. V) from the Cell 4 effluent in the indoor system. A 10 cm layer of zero valent iron was placed at the bottom part of the down flowing P treatment cell to address the elevated V in the P treatment cell effluent observed in the indoor system and also to treat PhACs in the effluent. More than 99% removal of P, E. coli, and total coliform; >82, >98, and >76% removal of ammonia, cBOD5, and COD were achieved in this treatment system. The effluent pH (10.88±1.47) was neutralized and the concentration of V remained < 0.006 mg L-1. The Al concentration was adjusted to <0.075 mg L-1 with the neutralization of pH. Geochemical speciation modeling results showed the supersaturation of hydroxyapatite, ß-tricalciumphosphate, octatricalciumphosphate, aragonite, and calcite. The FTIR and XANES spectra showed the presence of calcium phosphate minerals on the outer layer of the spent media. Removal of the PhACs, including caffeine, ibuprofen, carbamazepine, naproxen, and sulfamethoxazole, and acesulfame-K was monitored in the demonstration-scale outdoor wastewater treatment system, which consisted of five different treatment cells including a horizontal subsurface flow constructed wetland, a vertical subsurface flow aerated cell, a vertical subsurface flow BOFS cell, and a pH neutralization unit. Significant removal of caffeine (>75%) and ibuprofen (50-75%), and moderate removal of sulfamethoxazole and naproxen (25-50%) were observed. The removal of carbamazepine was less effective with <25% removal observed. Acesulfame-K was also persistent along the flow path with <25% removal. This study demonstrated that removal of P from lake water and wastewater in excess of 95% could be achieved using BOFS as a reactive media. Integration of this media into an engineered wetland system enhances its performance in removing nutrients and other wastewater contaminants.

No description available.

Chromium (VI) is a pervasive groundwater contaminant that poses a considerable threat to human health. Remediation techniques have focused on the reduction of the highly mobile Cr(VI) to the sparingly soluble, and less toxic, Cr(III) species. Traditionally, remediation performance has been evaluated through the measurement of Cr(VI) concentrations; however, this method is both costly and time-consuming, and provides little information regarding the mechanism of Cr(VI) removal. More recently, Cr isotope analysis has been proposed as a tool for tracking Cr(VI) migration in groundwater. Redox processes have been shown to produce significant Cr isotope fractionation, where enrichment in the ⁵³Cr/⁵²Cr ratio in the remaining Cr(VI) pool is indicative of a mass-transfer process. This thesis describes laboratory batch and column experiments that evaluate the Cr isotope fractionation associated with the reduction of Cr(VI) by various materials and under various conditions. Laboratory batch experiments were conducted to characterize the isotope fractionation during Cr(VI) reduction by granular zero-valent iron (ZVI) and organic carbon (OC). A decrease in Cr(VI) concentrations was accompanied by an increase in δ⁵³Cr values for the ZVI experiments. Data were fitted to a Rayleigh-type curve, which produced a fractionation factor α = 0.9994, suggesting a sorption-dominated removal mechanism. Scanning electron microscopy (SEM), X-ray absorption near-edge structure (XANES) spectroscopy, and X-ray photoelectron spectroscopy (XPS) indicated the presence of Cr(III) on the solid material, suggesting that reduction of Cr(VI) occurred. A series of batch experiments determined that reaction rate, experimental design, and pre-treatment of the ZVI had little to no effect on the Cr isotope fractionation. The interpretation of isotope results for the organic carbon experiments was complicated by the presence of both Cr(VI) and Cr(III) co-existing in solution, suggesting that further testing is required. A laboratory column experiment was conducted to evaluate isotopic fractionation of Cr during Cr(VI) reduction by OC under saturated flow conditions. Although decreasing dissolved Cr(VI) concentrations also were accompanied by an increase in δ⁵³Cr values, the isotope ratio values did not fit a Rayleigh-type fractionation curve. Instead, the data followed a linear regression equation yielding α = 0.9979. Solid-phase analysis indicated the presence of Cr(III) on the surface of the OC. Both the results of the solid-phase Cr and isotope analyses suggest a combination of Cr(VI) reduction mechanisms, including reduction in solution, and sorption prior to reduction. The linear characteristic of the δ⁵³Cr data may reflect the contribution of transport on Cr isotope fractionation.

No description available.

This thesis comprises three projects focused on the use of the combination of catalytic copper and iodonium salts towards the functionalisation of alkenes. Chapter 2 details the development of an enantioselective and regiodivergent allylic amide arylation procedure using a specific copper(II)-bisoxazoline pre-catalyst and hexafluorophosphate diaryliodonium salts. The regioselectivity of the process was discovered to be controlled by the electronic properties of the iodane employed, allowing enamide production to be biased with electron-poor iodonium salts and oxazines to be produced with electron-rich analogues. An overall scope of 38 compounds was collaboratively elaborated, with 20 synthesised personally. All products were generated in useful yields and high levels of enantioselectivity. Chapter 3 describes efforts towards the application of a copper-catalysed oxy-alkenylation procedure to the production of the macrolidal natural product (-)-lyngbyaloside B. It is proposed that an elaborate homoallylic carbamate may be coupled with a complex polyoxygenated alkenyl(aryl)iodonium salt as a fragment coupling for polyketide synthesis. Following extensive investigations, it was discovered that the challenging vinyl-iodonium salt could be synthesised in good yields and then coupled with the desired homoallylic carbamate, albeit in limited yield and low d.r. Chapter 4 presents initial studies towards a computational understanding of the copper-catalysed arylation of alkenes with iodonium salts. Evidence is presented to suggest that two functionalisation modes are energetically accessible, allowing the production of regioisomeric arylated products.

abstract: The advantages and challenges of combining zero-valent iron (ZVI) and microbial reduction of trichloroethene (TCE) and perchlorate (ClO4-) in contaminated soil and groundwater are not well understood. The objective of this work was to identify the benefits and limitations of simultaneous application of ZVI and bioaugmentation for detoxification of TCE and ClO4- using conditions relevant to a specific contaminated site. We studied conditions representing a ZVI-injection zone and a downstream zone influenced Fe (II) produced, for simultaneous ZVI and microbial reductive dechlorination applications using bench scale semi-batch microcosm experiments. 16.5 g L-1 ZVI effectively reduced TCE to ethene and ethane but ClO4- was barely reduced. Microbial reductive dechlorination was limited by both ZVI as well as Fe (II) derived from oxidation of ZVI. In the case of TCE, rapid abiotic TCE reduction made the TCE unavailable for the dechlorinating bacteria. In the case of perchlorate, ZVI inhibited the indigenous perchlorate-reducing bacteria present in the soil and groundwater. Further, H2 generated by ZVI reactions stimulated competing microbial processes like sulfate reduction and methanogenesis. In the microcosms representing the ZVI downstream zone (Fe (II) only), we detected accumulation of cis-dichloroethene (cis-DCE) and vinyl chloride (VC) after 56 days. Some ethene also formed under these conditions. In the absence of ZVI or Fe (II), we detected complete TCE dechlorination to ethene and faster rates of ClO4- reduction. The results illustrate potential limitations of combining ZVI with microbial reduction of chlorinated compounds and show the potential that each technology has when applied separately. / Dissertation/Thesis / Masters Thesis Civil, Environmental and Sustainable Engineering 2017

In this Thesis either advanced oxidation or reductive processes are investigated for the degradation of two pesticides considered persistent in the environment: amicarbazone (AMZ) and chlorpyrifos (CP). In chapter I, different advanced oxidation processes (AOPs) driven by sulfate (SO4o-) and hydroxyl radicals (oOH) were applied to the degradation of AMZ. In the first study, several persulfate (PS) activated reactions were explored for AMZ degradation, namely activation with UVA radiation, Fe(II) and H2O2, as well as the combination of UVA radiation with Fe(II), Fe(III) and Fe(III)-complexes. Here, the influence of different reaction variables, such as solution pH, reactants and pesticide initial concentrations, addition of a second oxidant (H2O2) and the addition of different iron catalysts were also investigated. Control experiments regarding the photolysis of iron species in the absence of PS captured our interest and, with the aim of exploring more deeply this process on AMZ degradation, a second investigation was carried out. In this second study, a Doehlert experimental design was applied to investigate the simultaneous effects of two variables on AMZ degradation: pH and Fe(III):carboxylate ratio, where the carboxylate could be oxalate, citrate or tartrate. A response surface model for the observed degradation rate (kobs) as a function of pH and Fe(III):carboxylate ratio was obtained. The processes explored in both aforementioned studies revealed to be effective for AMZ removal, although nothing is known yet about their effectiveness regarding toxicity removal. Given that, a third study was carried out, where the toxicity of AMZ solutions, before and after submission to the processes studied was evaluated towards five microorganisms: Vibrio fischeri (acute toxicity), Tetrahymena thermophile, Chlorella vulgaris (chronic toxicity), Escherichia coli and Bacilus subtilis (antimicrobial activity). The last investigation detailed in chapter I is related with the application of zero-valent-metals on PS activation, which is a subject that links this chapter with the following one. For that, zero-valent-iron (ZVI) was investigated as a PS activator and the influence of variables that help to assess the environmental applicability of this process. In general, organochlorine pesticides reveal a higher resistance to oxidation than reduction, the latter process preferred when the aim is to degrade that important class of contaminants. Therefore, in chapter II the reductive degradation of CP by means of zero-valent-metals and bimetallic particles was investigated. ZVI has been extensively applied for that purpose. However, besides iron, other zero-valent metals can be potential reactive materials for reductive degradation and hence, in this study, the effectiveness of Zn0 and Cu0 was also explored in comparison to that widely reported for ZVI. Furthermore, two different ways of enhancing metals reactivity were here explored: i) by coating ZVI or Zn0 with a more noble metal (Cu), in order to analyze the copper catalytic effect on the bimetallic system; ii) by different surface pretreatments. / Na presente Tese de Doutorado foram abordados tanto processos oxidativos avançados (POA), como processos redutivos por metais de valência zero, na degradação de dois pesticidas considerados persistentes no meio ambiente: amicarbazona (AMZ) e clorpirifós (CP). No capítulo I são apresentados os estudos realizados com diversos POA, mediados por radicais sulfato (SO4o-) e hidroxila (oOH), aplicados da AMZ. Num primeiro estudo foi explorada a ativação do oxidante persulfato (PS), de diferentes formas, tais como radiação UVA, H2O2 e Fe(II), assim como a combinação de radiação UVA com Fe(II), Fe(III) e complexos de Fe(III). Aqui também foram investigados os efeitos de diversas variáveis reacionais, tais como pH, concentração inicial de reagentes e de pesticida, adição de um segundo oxidante (H2O2) e adição de diferentes espécies de ferro. Os testes realizados, para efeito de controle, referentes à irradiação das espécies de Fe(III) na ausência de PS, despertaram o interesse para um estudo mais aprofundado sobre o efeito da fotólise destas espécies na degradação da AMZ, surgindo assim o segundo trabalho. Neste utilizou-se um projeto experimental de Doehlert, para avaliar o efeito de duas variáveis em simultâneo quanto à degradação da AMZ: pH e proporção Fe(III): ligante, sendo o ligante um dos seguintes carboxilatos: oxalato, citrato ou tartarato. Um modelo de superfície de resposta, que correlaciona a taxa de degradação observada (kobs) em função do pH e proporção Fe(III):ligante foi obtido para cada um dos complexos de Fe(III) estudados. Os processos explorados, tanto no primeiro como no segundo estudo, se mostraram eficazes na remoção da AMZ, porém nada se sabe acerca da remoção da toxicidade. Para tal, foi desenvolvido um terceiro estudo dedicado à avaliação da toxicidade da solução de AMZ, antes e após a aplicação de cada um dos processos anteriormente abordados, contra cinco micro-organismos: Vibrio fischeri (toxicidade aguda); Tetrahymena thermophila, Chlorella vulgaris (toxicidade crônica); Escherichia coli e Bacilus subtilis (atividade antimicrobiana). O último estudo abordado no capitulo I é referente à aplicação de metais de valência zero também nos POA, correlacionado assim o capítulo I e o capítulo II. Como tal, foi feito um estudo de ativação de PS por meio de ferro de valência zero (Fe0), em que se investigou a influência de diversas variáveis por forma a inferir sobre a aplicabilidade prática deste processo. Pesticidas organoclorados apresentam maior resistência à degradação por processos oxidativos do que redutivos, sendo preferível o último na degradação desta importante classe de contaminantes. Como tal, o capítulo II se refere à degradação redutiva, por meio de diferentes metais de valência zero e partículas bimetálicas, do pesticida organoclorado CP. Além do amplamente explorado Fe0, outros metais podem ser aplicados neste processo, pelo que, neste estudo, explorou-se a potencialidade de Zn0 e Cu0 comparativamente ao primeiro. Ainda neste estudo foram investigadas duas formas de aumentar a reatividade dos metais: i) no caso do Fe0 e Zn0, revestindo com um metal mais nobre (Cu), por forma a observar o efeito catalisador do último no sistema bimetálico; ii) realizando um pré-tratamento à superfície dos metais.