Isotopic fractionation associated to nitrate reduction by zero valent iron

One of the methodologies developed in recent years to induce nitrate attenuation is the use of permeable reactive barriers (PRB). This in situ remediation technique involves the interception of groundwater flow to remove contaminants by physical, chemical or biological processes. In the case of nitrate pollution, heterotrophic or autotrophic denitrification can be induced by using organic or inorganic substrates, respectively. On the other hand, several PRB filled with Zero-Valent Iron (ZVI) have been installed to remediate groundwater polluted with chlorinated solvents (Wilkin et al., 2014) or nitrate (Gu et al., 2002)

Photodegradation of polycyclic aromatic hydrocarbons in soils under a climate change base scenario

The photodegradation of polycyclic aromatic hydrocarbons (PAHs) in two typical Mediterranean soils, either coarse- or fine-textured, was here investigated. Soil samples, spiked with the 16 US EPA priority PAHs, were incubated in a climate chamber at stable conditions of temperature (20 degrees C) and light (9.6 W m(-2)) for 28 days, simulating a climate change base scenario. PAH concentrations in soils were analyzed throughout the experiment, and correlated with data obtained by means of Microtox (R) ecotoxicity test. Photodegradation was found to be dependent on exposure time, molecular weight of each hydrocarbon, and soil texture. Fine-textured soil was able to enhance sorption, being PAHs more photodegraded than in coarse-textured soil. According to the EC50 values reported by Microtox (R), a higher detoxification was observed in fine-textured soil, being correlated with the outcomes of the analytical study. Significant photodegradation rates were detected for a number of PAHs, namely phenanthrene, anthracene, benzo(a)pyrene, and indeno(123-cd)pyrene. Benzo(a)pyrene, commonly used as an indicator for PAH pollution, was completely removed after 7 days of light exposure. In addition to the PAH chemical analysis and the ecotoxicity tests, a hydrogen isotope analysis of benzo(a)pyrene was also carried out. The degradation of this specific compound was associated to a high enrichment in H-2, obtaining a maximum delta H-2 isotopic shift of +232 parts per thousand. This strong isotopic effect observed in benzo(a) pyrene suggests that compound-specific isotope analysis (CSIA) may be a powerful tool to monitor in situ degradation of PAHs. Moreover, hydrogen isotopes of benzo(a)pyrene evidenced a degradation process of unknown origin occurring in the darkness. (C) 2016 Elsevier Ltd. All rights reserved

The use of alkaline hydrolysis as a novel strategy for chloroform remediation: feasibility of using urban construction wastes and evaluation of carbon isotopic fractionation

Laboratory and field-scale pilot experiments were performed to evaluate the feasibility of chloroform degradation by alkaline hydrolysis and the potential of δ13C values to assess this induced reaction process at contaminated sites. In batch experiments, alkaline conditions were induced by adding crushed concrete (pH 12.33 ± 0.07), a filtered concrete solution (pH 12.27 ± 0.04), a filtered cement solution (pH 12.66 ± 0.02) and a pH 12 buffer solution (pH 11.92 ± 0.11). The resulting chloroform degradation after 28 days was 94, 96, 99, and 72%, respectively. The experimental data were described using a pseudo-first-order kinetic model, resulting in pseudo-first-order rate constant values of 0.10, 0.12, 0.20, and 0.05 d−1, respectively. Furthermore, the significant chloroform carbon isotopic fractionation associated with alkaline hydrolysis of chloroform (−53 ± 3¿) and its independence from pH in the admittedly limited tested pH range imply a great potential for the use of δ13C values for in situ monitoring of the efficacy of remediation approaches based on alkaline hydrolysis. The carbon isotopic fractionation obtained at the lab scale allowed the calculation of the percentage of chloroform degradation in field-scale pilot experiments where alkaline conditions were induced in two recharge water interception trenches filled with concrete-based construction wastes. A maximum of approximately 30−40% of chloroform degradation was achieved during the two studied recharge periods. Although further research is required, the treatment of chloroform in groundwater through the use of concrete-based construction wastes is proposed. This strategy would also imply the recycling of construction and demolition wastes for use in value-added applications to increase economic and environmental benefits

Selecting oxidation process for treating water contaminated with a mixture of chlorinated VOCs

Chlorinated volatile organic compounds are some of the most prevalent contaminants in the environment. In situ chemical oxidation (ISCO) is a frequently used approach for the remediation of groundwater contaminated with these compounds (Huling @ Pivetz, 2006). Compound-Specific Isotope Analysis (CSIA) can be used to evaluate the effectiveness of ISCO approaches since it is useful to discern contaminant degradation from non-degradative processes such as dilution or mixing

Control of the effectiveness of source removal and ZVI barrier treatment in a DNAPLs contaminated site using CSIA

The study site is polluted with dense non aqueoys phase liquids (DNAPLs): Tetrachiorethyiene (PCE), trichoreothyiene (TCE) and dichoroethene (cis-DCE)

The use of alkaline hydrolysis as a novel strategy for chloroform remediation: The feasibility of using construction wastes and evaluation of carbon isotopic fractionation

Laboratory and field-scale pilot experiments were performed to evaluate the feasibility of chloroform degradation by alkaline hydrolysis and the potential of δ13C values to assess this induced reaction process at contaminated sites. In batch experiments, alkaline conditions were induced by adding crushed concrete (pH 12.33 ± 0.07), a filtered concrete solution (pH 12.27 ± 0.04), a filtered cement solution (pH 12.66 ± 0.02) and a pH 12 buffer solution (pH 11.92 ± 0.11). The resulting chloroform degradation after 28 days was 94, 96, 99, and 72%, respectively. The experimental data were described using a pseudo-first-order kinetic model, resulting in pseudo-first-order rate constant values of 0.10, 0.12, 0.20, and 0.05 d-1, respectively. Furthermore, the significant chloroform carbon isotopic fractionation associated with alkaline hydrolysis of chloroform (-53 ± 3‰) and its independence from pH in the admittedly limited tested pH range imply a great potential for the use of δ13C values for in situ monitoring of the efficacy of remediation approaches based on alkaline hydrolysis. The carbon isotopic fractionation obtained at the lab scale allowed the calculation of the percentage of chloroform degradation in field-scale pilot experiments where alkaline conditions were induced in two recharge water interception trenches filled with concrete-based construction wastes. A maximum of approximately 30-40% of chloroform degradation was achieved during the two studied recharge periods. Although further research is required, the treatment of chloroform in groundwater through the use of concrete-based construction wastes is proposed. This strategy would also imply the recycling of construction and demolition wastes for use in value-added applications to increase economic and environmental benefits. © 2014 American Chemical Society

C, Cl and H compound-specific isotope analysis to assess natural versus Fe(0) barrier-induced degradation of chlorinated ethenes at a contaminated site

Compound-specific isotopic analysis of multiple elements (C, Cl, H) was tested to better assess the effect of a zero-valent iron-permeable reactive barrier (ZVI-PRB) installation at a site contaminated with tetrachloroethene (PCE) and trichloroethene (TCE). The focus was on (1) using 13C to evaluate natural chlorinated ethene biodegradation and the ZVI-PRB efficiency; (2) using dual element 13C-37Cl isotopic analysis to distinguish biotic from abiotic degradation of cis-dichloroethene (cis-DCE); and (3) using 13C-37Cl-2H isotopic analysis of cis-DCE and TCE to elucidate different contaminant sources. Both biodegradation and degradation by ZVI-PRB were indicated by the metabolites that were detected and the 13C data, with a quantitative estimate of the ZVI-PRB efficiency of less than 10% for PCE. Dual ele- ment 13C-37Cl isotopic plots confirmed that biodegradation was the main process at the site including the ZVI-PRB area. Based on the carbon isotope data, approximately 45% and 71% of PCE and TCE, respec- tively, were estimated to be removed by biodegradation. 2H combined with 13C and 37Cl seems to have identified two discrete sources contributing to the contaminant plume, indicating the potential of 2 H to discriminate whether a compound is of industrial origin, or whether a compound is formed as a daughter product during degradation

Compound Specific Isotope Analysis ((13)C, (37)Cl,( 2)H) to trace induced attenuation of chlorinated organic contaminants in groundwater

[cat] El chloroform (CF), el tetracloroetè (PCE) i el tricloretè (TCE) són hidrocarburs clor-alifàtics densos usats extensament com a solvents industrials. Aquests compostos s’han alliberat al medi degut a un tractament inadequat dels seus residus. En aquesta tesi, l’efecte d’una barrera permeable reactiva de ferro zero valent (BPR-FZV) instal•lada en un emplaçament contaminat majoritàriament amb PCE, TCE i cis-dicloretè (cis-DCE, subproducte de TCE) ha estat avaluada. A més a més, s’ha proposat i desenvolupat una nova estratègia per a degradar el CF, el qual és un compost recalcitrant, consistent en la inducció de la hidròlisi alcalina del CF mitjançant residus de construcció basats en formigó. L’ànàlisi isotòpic de compost específic (AICE) és una eina valuosa per al monitoreig d’un sistema de tractament medi ambiental, basant-se en el fraccionament isotòpic d’un element durant les reaccions de transformació. L’objectiu general d’aquesta tesi és l’ús de l’anàlisi isotòpic de compost específic de 13C, 37Cl i 2H com una eina per a controlar els dos processos d’atenuació 1) la degradació dels eten-clorats mitjançant una BPR-FZV instal•lada en el camp; i, 2) la nova tècnica de remediació de CF proposada basada en l’ús de residus reciclats de la construcció per tal d’induir la hidròlisi alcalina del CF. En general, mitjançant la combinació dels isòtops de C, Cl i H, aquesta tesi aporta noves eines per discriminar la degradació dels compostos organoclorats d’estudi mitjançant FZV, respecte la biodegradació en el camp, així com també per a identificar fonts de contaminació d’origen industrial o de productes formats, entre d’altres aportacions. A més a més, el nou mètode proposat per a degradar el CF basat en la seva hidròlisi alcalina mitjançant l’ús de residus de construcció reciclats ha demostrat ser eficient en la degradació d’aquest contaminant, així com també, mitjançant l’ús de isòtops de carboni, ha demostrat funcionar en experiments pilot monitorejats a escala de camp.[eng] Chloroform (CF), tetrachloroethene (PCE) and trichloroethene (TCE) are dense chloro-aliphatic hydrocarbons (CAH) extensively used as industrial solvents. These compounds have been largely released to the environment due to poor waste management. In this thesis, the effect of a ZVI-PRB installed at a field site contaminated mainly with PCE, TCE and cis-DCE was evaluated. Moreover, a novel strategy to degrade the recalcitrant CF -alkaline hydrolysis induced by concrete-based recycled construction wastes- was proposed and developed in order to test its efficiency in degrading this pollutant. Compound specific isotope analysis (CSIA) is a valuable tool for monitoring an environmental treatment in the field, based on the isotope fractionation of an element during transformation reactions. Therefore, the general aim of this thesis is to use compound specific isotope analysis of 13C, 37Cl and 2H as a tool to assess both induced attenuation processes 1) chlorinated ethenes degradation by a ZVI-PRB installed at the field sited; and, 2) the proposed new remediation technique based on the use of concrete-based recycled construction wastes to degrade chloroform (CF) by alkaline hydrolysis applied at a site contaminated by this pollutant. First, laboratory experiments were conducted to study both ZVI and concrete effects on the chlorinated ethenes and the chloroform, respectively. ZVI experiments yielded carbon isotope fractionation values of the chlorinated ethenes degradation by the specific ZVI used in the field application, as well as, the first chlorine isotope fractionation values of TCE and cis-DCE associated to this reaction. Two promising approaches to discriminate the abiotic ZVI degradation versus biotic degradation present at the field site were brought forward 1) the dual isotope C-Cl approach, which distinguished slopes 4 times lower than for biodegradation of cis-DCE by the commercially available Dehalococcoides-containing culture mixed culture KB-1; and 2) the product-specific carbon isotope fractionation that showed a 10‰ difference between those products coming from β-dichloroelimination and hydrogenolysis reactions. Concrete experiments with CF achieved a 95% CF degradation after 28 d, accompanied by a significant carbon isotope fractionation. The carbon isotopic fractionation associated with alkaline hydrolysis of CF was -53±3‰. The obtained laboratory data permitted the assessment of the respective induced degradation treatments applied at the field site. At the site with the ZVI-PRB treatment, both, occurrence of biodegradation and degradation by ZVI-PRB were evidenced by means of detected metabolites and 13C data, with quantitative estimates of ZVI-PRB efficiency of less than 10% and 2% for PCE and cis-DCE, respectively. Dual element 13C-37Cl isotope plots confirmed that the effect of the ZVI-PRB was masked by biodegradation. Based on carbon isotopes data, 49% and almost 100% of PCE and TCE, respectively, were estimated to be removed by biodegradation. Finally the combination of 2H with 13C and 37Cl discriminated two different sources of contamination spilled from the same industry. This indicates the potential of δ2H to discriminate if a compound is of industrial origin, or whether it is formed as a daughter product during degradation. Regarding CF hydrolysis, field-scale pilot experiments were used to test the efficiency of the concrete-base recycled construction wastes to induce alkaline hydrolysis. The carbon isotopic fractionation obtained at the lab scale allowed the calculation of the percentage of chloroform degradation in the field-scale pilot experiments where alkaline conditions were induced in two recharge water interception trenches filled with concrete-based construction wastes. A maximum of approximately 30-40% of chloroform degradation was achieved. Although further research is required, the treatment of chloroform in groundwater through the use of concrete-based construction wastes is proposed. This strategy would also imply the recycling of construction and demolition wastes for use in value-added applications to increase economic and environmental benefits

Climate change impact on the PAH photodegradation in soils: Characterization and metabolites identification

Polycyclic aromatic hydrocarbons (PAHs) are airborne pollutants that are deposited on soils. As climate change is already altering temperature and solar radiation, the global warming is suggested to impact the environmental fate of PAHs. This study was aimed at evaluating the effect of climate change on the PAH photodegradation in soils. Samples ofMediterranean soilswere subjected to different temperature and light radiation conditions in a climate chamber. Two climate scenarios were considered according to IPCC projections: 1) a base (B) scenario, being temperature and light intensity 20 °C and 9.6W/m2, respectively, and 2) a climate change (CC) scenario,working at 24 °C and 24W/m2, respectively. As expected, low molecularweight PAHswere rapidly volatilizedwhen increasing both temperature and light intensity. In contrast, medium and high molecular weight PAHs presented different photodegradation rates in soils with different texture, which was likely related to the amount of photocatalysts contained in both soils. In turn, the hydrogen isotopic composition of some of the PAHs under study was also investigated to verify any degradation process. Hydrogen isotopes confirmed that benzo(a)pyrene is degraded in both B and CC scenarios, not only under light but also in the darkness, revealing unknown degradation processes occurring when light is lacking. Potential generation pathways of PAH photodegradation by-products were also suggested, being a higher number of metabolites formed in the CC scenario. Consequently, in a more or less near future, although humans might be less exposed to PAHs, they could be exposed to new metabolites of these pollutants, which might be even more toxic