Estudo do tratamento de águas contaminadas com tricloroetileno, usando ferro zerovalente

A tecnologia de barreiras reactivas é uma alternativa possível de ser implementada para tratamento de águas contaminadas com compostos organoclorados, nomeadamente o tricloroetileno (TCE). O recurso a ferro zerovalente (Fe0) como meio reactivo tem na actualidade inúmeras aplicações, tratando-se de uma reacção de desalogenação por mecanismo de oxidação-redução. Neste trabalho fizeram-se estudos em batch da reacção entre o Fe0 e o TCE de forma a conhecer os parâmetros cinéticos. A natureza e a área da superfície do ferro provaram ser determinantes na velocidade da reacção. Foi possível verificar que para o sistema ferro comercial / TCE a ordem da reacção é inferior a um, e a constante cinética da ordem de 10-2 Lm-2h-1. Para simular uma barreira reactiva, projectaram-se e construíram-se colunas, as quais foram cheias com areia e ferro depois de devidamente misturados, uma vez que se tratou da disposição a que corresponderam melhores eficiências de redução do TCE. Não foi possível estabelecer o mecanismo da reacção, nem conhecer os parâmetros cinéticos, pelas dificuldades experimentais encontradas na análise do TCE e pelo facto de se tratar de uma reacção muito lenta. A cromatografia gasosa com detector de ionização de chama provou ser o método mais apropriado para doseamento do TCE em águas contaminadas, nas condições usadas neste estudo. A elevada volatilização do TCE e a baixa solubilidade em água contribuíram para as dificuldades operacionais encontradas.

Heterogeneous kinetics of the reduction of chromium (VI) by elemental iron

Zero valent iron (ZVI) has been extensively used as a reactive medium for the reduction of Cr(VI) to Cr(III) in reactive permeable barriers. The kinetic rate depends strongly on the superficial oxidation of the iron particles used and the preliminary washing of ZVI increases the rate. The reaction has been primarily modelled using a pseudo-first-order kinetics which is inappropriate for a heterogeneous reaction. We assumed a shrinking particle type model where the kinetic rate is proportional to the available iron surface area, to the initial volume of solution and to the chromium concentration raised to a power ˛ which is the order of the chemical reaction occurring at surface. We assumed α= 2/3 based on the likeness to the shrinking particle models with spherical symmetry. Kinetics studies were performed in order to evaluate the suitability of this approach. The influence of the following parameters was experimentally studied: initial available surface area, chromium concentration, temperature and pH. The assumed order for the reaction was confirmed. In addition, the rate constant was calculated from data obtained in different operating conditions. Digital pictures of iron balls were periodically taken and the image treatment allowed for establishing the time evolution of their size distribution.

Estudo da remediação de um aquífero contaminado com sulfato e metais através de barreira reativa permeável orgânica.

Este trabalho teve como objetivo geral estudar a viabilidade técnica de utilizar bagaço de cana como meio reativo de barreiras reativas permeáveis (BRP) para remoção de sulfato e metais de águas subterrâneas contaminadas. O estudo baseou-se em investigação experimental, por meio de ensaios laboratoriais de coluna, e em modelagem matemática, para a qual utilizaram-se também alguns dados obtidos em um estudo de caso de uma unidade industrial contaminada com sulfato e metais. Neste local contaminado, as características hidrogeológicas e topográficas propiciam a utilização de uma barreira reativa permeável como técnica de remediação. Barreiras reativas permeáveis são uma alternativa para remediação de águas subterrâneas que vem progredindo rapidamente na última década, a partir de ensaios de bancada e coluna em laboratório para implementação em escala real em campo. Três colunas bióticas foram montadas utilizando bagaço de cana como meio reativo e um material de base poroso constituído de areia e cascalho para fornecer adequada condutividade hidráulica, com a proporção de 1:28 em massa seca. Também foi adicionado ao meio reativo um inóculo bacteriano composto por esterco bovino dissolvido. Uma quarta coluna, sem inóculo e contendo um agente biocida, compôs o experimento branco (abiótico). Uma solução sintética foi introduzida nas colunas simulando condições da água subterrânea do estudo de caso, com velocidade de Darcy em torno de 2,0x10-7 m/s composta por sulfato e metais (zinco e níquel) com concentrações de 6.000 mg/L e 15 mg/L, respectivamente. Os resultados das análises da fase líquida das colunas bióticas apresentaram: (i) média da taxa de remoção de sulfato durante todo o tempo do experimento de 49 mg/L/dia; (ii) as concentrações de Zn e Ni diminuíram de 15 mg/L para valores não detectáveis pela técnica analítica utilizada (< 0,01 mg/L); (iii) aumento do pH de 5.5-5.8 para valores entre 6,8-8,0; (iv) redução do valor do potencial de óxido redução (Eh) para valores de até -200mV. Não foram observadas reduções das concentrações de metais e sulfato na fase líquida da coluna abiótica e os valores de pH e Eh permaneceram dentro das faixas iniciais. Análises nas fases sólidas das colunas bióticas por MEV e EDS após o término do experimento identificaram a presença de Ni, Zn, S e Mn, indicando a precipitação desses metais em forma de sulfetos. Estes elementos não foram detectados na fase sólida da coluna abiótica. Assim, pôde-se inferir que toda a remoção de sulfato verificada nas colunas bióticas pode ser atribuída a redução bacteriana de sulfato. A partir das condições experimentais dos ensaios, foi realizada a modelagem e o dimensionamento da BRP. Para a estimativa da cinética de redução de sulfato, aplicou-se a solução analítica de Van Genuchten para transporte de contaminantes com degradação, obtendo-se uma taxa de decaimento de primeira ordem de 0,01 dia-1. A determinação da espessura e tempo de residência da barreira foi realizada considerando que a concentração de sulfato na saída da barreira fosse menor ou igual a 250 mg/L. O resultado do dimensionamento de uma BRP preenchida com bagaço de cana e areia nas proporções de 1:28 em massa seca resultaria em uma BRP de 7,1 m de espessura, com tempo de residência de 950 dias, no local de estudo de caso. Caso fosse utilizado o dobro da proporção de bagaço de cana e areia em massa seca (1:14), a implantação da BRP apresentar-se-ia viável, com espessura aproximada de 4 m. Através destes resultados, pôde ser comprovada a hipótese de que bagaço de cana como substrato e esterco bovino como inóculo compõem um meio reativo viável para a redução de sulfato e precipitação de metais em uma BRP.

Vermiculite bio-barriers for Cu and Zn remediation: an eco-friendly approach for freshwater and sediments protection

The increase in heavy metal contamination in freshwater systems causes serious environmental problems in most industrialized countries, and the effort to find ecofriendly techniques for reducing water and sediment contamination is fundamental for environmental protection. Permeable barriers made of natural clays can be used as low-cost and eco-friendly materials for adsorbing heavy metals from water solution and thus reducing the sediment contamination. This study discusses the application of permeable barriers made of vermiculite clay for heavy metals remediation at the interface between water and sediments and investigates the possibility to increase their efficiency by loading the vermiculite surface with a microbial biofilm of Pseudomonas putida, which is well known to be a heavy metal accumulator. Some batch assays were performed to verify the uptake capacity of two systems and their adsorption kinetics, and the results indicated that the vermiculite bio-barrier system had a higher removal capacity than the vermiculite barrier (?34.4 and 22.8 % for Cu and Zn, respectively). Moreover, the presence of P. putida biofilm strongly contributed to fasten the kinetics of metals adsorption onto vermiculite sheets. In open-system conditions, the presence of a vermiculite barrier at the interface between water and sediment could reduce the sediment contamination up to 20 and 23 % for Cu and Zn, respectively, highlighting the efficiency of these eco-friendly materials for environmental applications. Nevertheless, the contribution of microbial biofilm in open-system setup should be optimized, and some important considerations about biofilm attachment in a continuous-flow system have been discussed.

Nanoparticles based Permeable Reactive Barriers as an Eco-efficient Technology for nitrate remediation in soil and groundwater

The need to increase agricultural yield led, among others, to an increase in the consumption of nitrogen based fertilizers. As a consequence, there are excessive concentrations of nitrates, the most abundant of the reactive nitrogen (Nr) species, in several areas of the world. The demographic changes and projected population growth for the next decades, and the economic shifts which are already shaping the near future are powerful drivers for a further intensification in the use of fertilizers, with a predicted increase of the nitrogen loads in soils. Nitrate easily diffuses in the subsurface environments, portraying high mobility in soils. Moreover, the presence of high nitrate loads in water has the potential to cause an array of health dysfunctions, such as methemoglobinemia and several cancers. Permeable Reactive Barriers (PRB) placed strategically relatively to the nitrate source constitute an effective technology to tackle nitrate pollution. Ergo, PRB avoid various adverse impacts resulting from the displacement of reactive nitrogen downstream along water bodies. A four stages literature review was carried out in 34 databases. Initially, a set of pertinent key words were identified to perform the initial databases searches. Then, the synonyms of those initial key words were used to carry out a second set of databases searches. The third stage comprised the identification of other additional relevant terms from the research papers identified in the previous two stages. Again, databases searches were performed with this third set of key words. The final step consisted of the identification of relevant papers from the bibliography of the relevant papers identified in the previous three stages of the literature review process. The set of papers identified as relevant for in-depth analysis were assessed considering a set of relevant characterization variables.

Permeable Reactive Barriers using nanoparticles to remediate nitrate pollution

Nitrat e (NO3 - ) i s per vasi ve i n t he bi ospher e[ 1, 2]. Cont emporar y agri cult ural pr acti ces are a mong t he maj or ant hr opogeni c sources of r eacti ve nitrogen speci es, wher e nitrat ei s t he most abundant of t hese [ 2]. Excessi ve a mount s of r eacti ve nitrogen i n soil s and gr oundwat er ar e creati ng si gnifi cant t hr eat s t o hu man healt h and saf et y [ 3] as well as a host of undesirabl e environment al i mpact s [ 2]; it i s curr ently consi der ed t he second most r el evant environment al i ssue, aft er car bon di oxide e mi ssi ons. Nowadays, a mong t he most r el evant and pr omi si ng appr oaches t o r educe nitrat e concentrati on i n wat er, na mel y gr oundwat er, ar e denitrifi cati on- based pr ocesses [ 4]. Per meabl e r eacti ve barri ers ( PRB) have been pr oven eff ecti ve i n r educi ng vari ous cont ami nant s i n copi ous a mount s, parti cul arl y i n shall ow gr oundwat er [ 5]. However t he possi bl e added eff ecti veness of usi ng nanoparti cl es i n t hese structur es t o obt ai n nitrogen gas from nitrat es requires f urt her i nvesti gati on.

Nanosized iron based permeable reactive barriers for nitrate removal - Systematic review

It is unquestionable that an effective decision concerning the usage of a certain environmental clean-up technology should be conveniently supported. Significant amount of scientific work focussing on the reduction of nitrate concentration in drinking water by both metallic iron and nanomaterials and their usage in permeable reactive barriers has been worldwide published over the last two decades. This work aims to present in a systematic review of the most relevant research done on the removal of nitrate from groundwater using nanosized iron based permeable reactive barriers. The research was based on scientific papers published between 2004 and June 2014. It was performed using 16 combinations of keywords in 34 databases, according to PRISMA statement guidelines. Independent reviewers validated the selection criteria. From the 4161 records filtered, 45 met the selection criteria and were selected to be included in this review. This study's outcomes show that the permeable reactive barriers are, indeed, a suitable technology for denitrification and with good performance record but the long-term impact of the use of nanosized zero valent iron in this remediation process, in both on the environment and on the human health, is far to be conveniently known. As a consequence, further work is required on this matter, so that nanosized iron based permeable reactive barriers for the removal of nitrate from drinking water can be genuinely considered an eco-efficient technology.

Invariant barriers to reactive front propagation in fluid flows

We present theory and experiments on the dynamics of reaction fronts in two-dimensional, vortex-dominated flows, for both time-independent and periodically driven cases. We find that the front propagation process is controlled by one-sided barriers that are either fixed in the laboratory frame (time-independent flows) or oscillate periodically (periodically driven flows). We call these barriers burning invariant manifolds (BIMs), since their role in front propagation is analogous to that of invariant manifolds in the transport and mixing of passive impurities under advection. Theoretically, the BIMs emerge from a dynamical systems approach when the advection-reaction-diffusion dynamics is recast as an ODE for front element dynamics. Experimentally, we measure the location of BIMs for several laboratory flows and confirm their role as barriers to front propagation.

An in-situ permeable reactive barrier for the treatment of hexavalent chromium and trichloroethylene in ground water /

"Project Officer, Robert W. Puls, Subsurface Protection and Remediation Division."

Improving performance of a permeable reactive barrier in the degradation of trichloroethylene using ultrasound

The impact of ultrasound on improving the performance of a granular iron Permeable Reactive Barrier (PRB) in the degradation of Trichloroethylene (TCE) was evaluated. Two treatment columns made of clear Plexiglas with a height of 1ft and a diameter of 2 inches and filled with granular iron were used. One was fitted with 25Khz ultrasound probes. A solution of TCE was run through at constant flow rate. Samples obtained from the column at different residence times before and after sonication were analyzed for concentrations of TCE and used to generate concentration profiles to obtain rate constants, which were compared. An improvement of 23.4% in the reaction rate of TCE degradation was observed after sonication of the iron media suggesting that ultrasound may contribute to improving the performance of PRBs in the degradation of TCE in contaminated groundwater.

Investigating barriers in HIV-testing oncology patients. The IBITOP study: phase I.

BACKGROUND: Since the advent of combined antiretroviral therapy (ART), the incidence of non-AIDS-defining cancers (non-ADCs) among HIV-positive patients is rising. We previously described HIV testing rates of <5% in our oncology centre, against a local HIV prevalence of 0.4% (1). We have since worked with the Service of Oncology to identify, how HIV testing can be optimized, we have conducted a study on investigating barriers in HIV-testing oncology patients (IBITOP) among treating oncologists and their patients. METHODS: After an initial two-month pilot study to examine feasibility (2), we conducted the first phase of the IBITOP study between 1st July and 31st October 2013. Patients of unknown HIV status, newly diagnosed with solid-organ non-AIDS-defining cancer, and treated at Lausanne University Hospital were invited to participate. Patients were offered HIV testing as a part of their initial oncology work-up. Oncologist testing proposals and patient acceptance were the primary endpoints. RESULTS: Of 235 patients with a new oncology diagnosis, 10 were excluded (7 with ADCs and 3 of known HIV-positive status). Mean age was 62 years; 48% were men and 71% were Swiss. Of 225 patients, 75 (33%) were offered HIV testing. Of these, 56 (75%) accepted, of whom 52 (93%) were tested. A further ten patients were tested (without documentation of being offered a test), which gave a total testing rate of 28% (62/225). Among the 19 patients who declined testing, reasons cited included self-perceived absence of HIV risk, previous testing and palliative care. Of the 140 patients not offered HIV testing and not tested, reasons were documented for 35 (25%), the most common being previous testing and follow-up elsewhere. None of the 62 patients HIV tested had a reactive test. CONCLUSIONS: In this study, one third of patients seen were offered testing and the HIV testing rate was fivefold higher than that of previously observed in this service. Most patients accepted testing when offered. As HIV-positive status impacts on the medical management of cancer patients, we recommend that HIV screening should be performed in settings, where HIV prevalence is >0.1%. Phase II of the IBITOP study is now underway to explore barriers to HIV screening among oncologists and patients following the updated national HIV testing guidelines which recommend testing in non-ADC patients undergoing chemotherapy.

Methods to Increase Durability of Reactive ("D" Cracking) Coarse Aggregate in Portland Cement Concrete, MLR-73-01, 1973

The coarse aggregates used for Portland Cement concrete in southwest Iowa have exhibited a poor serviceability. This early failure is attributed to a characteristic commonly referred as "D" cracking. "D" line cracking is a discolored area of concrete caused by many fine, parallel hairline cracks. "D" line cracking is primarily caused by the movement of water in and through coarse aggregate with a unique pore structure. The presence of the water in the aggregates at the time of freezing causes the "D" cracking to occur and early failure. By making the pore structure less permeable to moisture, it is thought the durability factor of the concrete should increase. By drying the aggregate before mixing and then mixing with the cement, the particles of cement should enter the outer pore structure, and upon hydration make the pore structure less permeable to moisture.

Ympäristöteknologioiden verifioinnin mahdollisuudet pilaantuneiden maiden laadukkaan käsittelyn edistämisessä

EU on käynnistämässä ympäristöteknologioiden verifiointijärjestelmää, jonka avulla voidaan tarjota käyttäjille ja sijoittajille riippumatonta tietoa innovatiivisten teknologioiden toimivuudesta ja suorituskyvystä ja parantaa niiden markkina-asemaa. Verifioinnilla tarkoitetaan kolmannen osapuolen suorittamaa prosessia tai mekanismia, jonka avulla tuotteen toiminta ja suorituskyky voidaan todentaa. Kansallinen ympäristöteknologioiden verifiointijärjestelmä on käytössä mm. Yhdysvalloissa ja Kanadassa. Euroopassa järjestelmä otettaneen käyttöön vuonna 2011–2012. Suomessa tehdään nykyisin noin 300 pilaantuneen maan puhdistushanketta koskevaa lupa- ja ilmoituspäätöstä vuosittain. Noin 85 prosentissa kohteista käytetään kunnostusmenetelmänä massanvaihtoa. Massanvaihto tulee ainakin toistaiseksi säilymään yleisimpänä kunnostusmenetelmänä, mutta mm. in situ -menetelmien käytön arvioidaan lisääntyvän. Tämän diplomityön tavoitteena oli arvioida voidaanko verifiointia hyödyntää pilaantuneiden maiden laadukkaan käsittelyn edistämisessä ja voiko verifiointi nopeuttaa innovatiivisten kunnostusmenetelmien markkinoillepääsyä. Aihetta tarkasteltiin mm. kahden erityyppisen pilaantuneen maan ja pohjaveden kunnostusmenetelmän, reaktiivisten seinämien (in situ) ja bitumistabiloinnin (ex situ) kautta. Pilaantuneiden maiden kunnostusmenetelmien toimivuus riippuu monista eri tekijöistä, joista osaa ei voida hallita tai mallintaa luotettavasti. Verifiointi soveltuukin parhaiten laitteiden tai PIMA-menetelmiä yksinkertaisempien puhdistusmenetelmien suorituskyvyn todentamiseen. Verifiointi saattaa kuitenkin hyvin toimia PIMA-kunnostuksen kohdalla esimerkiksi tiedollisena ohjauskeinona. Reaktiivisten seinämien ja bitumistabiloinnin verifioinnin työvaiheet ovat hyvin samankaltaiset, suurimpana erona seinämien kohdalla tulee kuvata myös kohde johon seinämä on asennettu. Reaktiivisten seinämien toiminta on riippuvaista monista ympäristötekijöistä, toisin kuin erillisellä laitteistolla suoritettavan bitumistabiloinnin. Tulosten perusteella voidaan yleistää, että verifiointi soveltuu paremmin ex situ -, kuin in situ -kunnostusmenetelmille.