28 results on '"Baciocchi, R"'
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2. Carbonation of activated serpentine for direct flue gas mineralization
- Author
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Werner, M, Hariharan, S, Bortolan, A, Zingaretti, D, and Baciocchi, R
- Subjects
Settore ICAR/03 - Ingegneria Sanitaria-Ambientale - Published
- 2013
3. Performance and kinetics of CO2 sequestration by direct gas-solid carbonation of APC residues
- Author
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Baciocchi, R, Polettini, A, Pomi, R, Prigiobbe, V, Nikulshina, V, and Steinfeld, A
- Subjects
Settore ICAR/03 - Ingegneria Sanitaria-Ambientale - Published
- 2006
4. Using groundwater monitoring wells for rapid application of soil gas radon deficit technique to evaluate residual LNAPL.
- Author
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Cecconi A, Verginelli I, Baciocchi R, Lanari C, Villani F, and Bonfedi G
- Subjects
- Soil, Water Wells, Radon analysis, Groundwater, Soil Pollutants analysis
- Abstract
The application of the
222 Radon (Rn) deficit technique using subsurface soil gas probes for the identification and quantification of light non-aqueous phase liquids (LNAPL) has provided positive outcomes in recent years. This study presents an alternative method for applying this technique in the headspace of groundwater monitoring wells. The developed protocol, designed for groundwater monitoring wells with a portion of their screen in the vadose zone, is based on the use of portable equipment that allows rapid measurement of the Rn soil gas activity in the vadose zone close to the water table (i.e., smear zone) where LNAPL is typically expected. The paper first describes the step-by-step procedure to be followed for the application of this method. Then, a preliminary assessment of the potential of the method was carried out at two Italian sites characterized by accidental gasoline and diesel spills into the subsurface from underground storage tanks. Although the number of tests conducted does not allow for definitive conclusions, the results obtained suggest that, from a qualitative point of view, Rn monitoring in the headspace of monitoring wells is a promising, fast, and minimally invasive screening method that could also potentially reduce the costs associated with field data acquisition. This method proves to be suitable for detecting the presence of LNAPL in both the mobile and residual phases with results consistent with the other lines of evidence available at the sites, such as groundwater and soil gas monitoring. Future efforts should be directed toward evaluating the accuracy of this method for a quantitative assessment of residual LNAPL saturations., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier B.V.)- Published
- 2023
- Full Text
- View/download PDF
5. Degradation of trichloroethylene vapors by micrometric zero-valent FeCu and FeNi bimetals under partially saturated conditions.
- Author
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Settimi C, Zingaretti D, Verginelli I, and Baciocchi R
- Subjects
- Copper, Solvents, Iron, Trichloroethylene, Water Pollutants, Chemical
- Abstract
The degradation of trichloroethylene (TCE) vapors by zero-valent Iron-Copper (Fe-Cu) and Iron-Nickel (Fe-Ni) bimetals with 1%, 5% and 20% weight content (%wt) of Cu or Ni was tested in anaerobic batch vapor systems carried out at ambient room temperature (20 ± 2 °C) under partially saturated conditions. The concentrations of TCE and byproducts were determined at discrete reaction time intervals (4 h-7 days) by analyzing the headspace vapors. In all the experiments, up to 99.9% degradation of TCE in the gas phase was achieved after 2-4 days with zero-order TCE degradation kinetic constants in the range of 134-332 g m
air -3 d-1 . Fe-Ni showed a higher reactivity towards TCE vapors compared to Fe-Cu, with up to 99.9% TCE dechlorination after 2 days of reaction, i.e., significantly higher than zero-valent iron alone that in previous studies was found to achieve comparable TCE degradation after minimum 2 weeks of reaction. The only detectable byproducts of the reactions were C3 -C6 hydrocarbons. Neither vinyl chloride or dichloroethylene peaks were detected in the tested conditions above their method quantification limits that were in the order of 0.01 g mair -3 . In view of using the tested bimetals in horizontal permeable reactive barriers (HPRBs) placed in the unsaturated zone to treat chlorinated solvent vapors emitted from contaminated groundwater, the experimental results obtained were integrated into a simple analytical model to simulate the reactive transport of vapors through the barrier. It was found that an HPRB of 20 cm could be potentially effective to ensure TCE vapors reduction., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)- Published
- 2023
- Full Text
- View/download PDF
6. Influence of advection on the soil gas radon deficit technique for the quantification of LNAPL.
- Author
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Cecconi A, Verginelli I, Barrio-Parra F, De Miguel E, and Baciocchi R
- Abstract
The Radon (Rn) deficit technique is a rapid, low-cost, and non-invasive method to identify and quantify light non-aqueous phase liquids (LNAPL) in the soil. LNAPL saturation is typically estimated from Rn deficit using Rn partition coefficients, assuming equilibrium conditions. This work examines the applicability of this method in the presence of local advective fluxes that can be generated by groundwater fluctuations or biodegradation processes in the source zone. To this end, a one-dimensional analytical model was developed to simulate the steady-state diffusive-advective transport of soil gas Rn in the presence of LNAPL. The analytical solution was first validated against an existing numerical model adapted to include advection. Then a series of simulations to study the effect of advection on Rn profiles were carried out. It was found that in high-permeability soils (such as sandy soils), advective phenomena can significantly affect Rn deficit curves in the subsurface compared with those expected, assuming either equilibrium conditions or a diffusion-dominated transport. Namely, in the presence of pressure gradients generated by groundwater fluctuations, applying the traditional Rn deficit technique (assuming equilibrium conditions) can lead to an underestimation of LNAPL saturation. Furthermore, in the presence of methanogenesis processes (e.g., in the case of a fresh LNAPL of petroleum hydrocarbons), local advective fluxes can be expected above the source zone. In such cases, Rn concentrations above the source zone can be higher than those above background areas without advective phenomena, resulting in Rn deficits higher than 1 (i.e., Rn excess), and thus leading to a wrong interpretation regarding the presence of LNAPL in the subsurface if advection is not considered. Overall, the results obtained suggest that advection should be considered in the presence of pressure gradients in the subsurface to ensure an effective application of the soil gas Rn-deficit technique for quantitative estimation of LNAPL saturation., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)
- Published
- 2023
- Full Text
- View/download PDF
7. Modeling of soil gas radon as an in situ partitioning tracer for quantifying LNAPL contamination.
- Author
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Cecconi A, Verginelli I, and Baciocchi R
- Subjects
- Gasoline, Soil, Radon analysis, Soil Pollutants analysis, Water Pollutants, Chemical analysis
- Abstract
In the last decades radon (Rn) has been widely proposed as a naturally occurring tracer for non-aqueous phase liquids (NAPL) in the soil. This work examines the feasibility of using soil gas data collected at some distance from the source zone for the application of the Rn deficit technique for the identification and quantification of NAPL contamination. To this end, we used a steady-state 1-D analytical solution that is based on a 3-layer model that allows to simulate the transport and distribution of Rn in the source zone, capillary fringe and overlying unsaturated soil. The analytical solution was first validated against a more detailed numerical model available in the literature. Then, a series of simulations were carried out to evaluate the vertical concentration profiles of Rn in soil gas above the source zone and in background location not impacted by NAPL. Simulation results showed that the parameters that most influence the migration and distribution of Rn in the subsurface are the distance of the soil gas probe from the source zone and, to a lower extent, the type of contamination (e.g. diesel or gasoline) and the soil type. On the basis of these results, we developed some easy-to-use nomographs to estimate the residual NAPL phase based on the observed radon deficit in soil gas and on the probe to source distance and soil and NAPL characteristics. According to the obtained results, the radon deficit technique results a feasible method for a qualitative identification of residual NAPL when radon in soil gas is measured at distances lower than 2 m from the contaminated zone. However, for an accurate quantitative estimation of the NAPL phase content, soil gas probes should be preferably located at distances lower than 1 m from the source zone., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)
- Published
- 2022
- Full Text
- View/download PDF
8. Refinement of the gradient method for the estimation of natural source zone depletion at petroleum contaminated sites.
- Author
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Verginelli I and Baciocchi R
- Subjects
- Biodegradation, Environmental, Carbon Dioxide analysis, Diffusion, Hydrocarbons, Oxygen, Soil, Petroleum, Soil Pollutants analysis
- Abstract
Rates of natural source zone depletion (NSZD) are increasingly being used to aid remedial decision making and light non-aqueous phase liquid (LNAPL) longevity estimates at petroleum release sites. Current NSZD estimate methods, based on analyses of carbon dioxide (CO
2 ) and oxygen (O2 ) soil-gas concentration gradients ("gradient method") assume linear concentration profiles with depth. This assumption can underestimate the concentration gradients especially above LNAPL sources that are typically characterized by curvilinear or semi-curvilinear O2 and CO2 concentration profiles. In this work, we proposed a new method that relies on calculating the O2 and CO2 concentration gradient using a first-order reaction model. The method requires an estimate of the diffusive reaction length that can be easily derived from soil-gas concentration data. A simple step-by-step guide for applying the new method is provided. Nomographs were also developed to facilitate method application. Application of the nomographs using field data from published literature showed that NSZD rates could be underestimated by nearly an order of magnitude if reactivity in the vadose zone is not accounted for. The new method helps refine NSZD rates estimation and improve risk-based decision making at certain petroleum contaminated sites., (Copyright © 2021 Elsevier B.V. All rights reserved.)- Published
- 2021
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9. Horizontal permeable reactive barriers with zero-valent iron for preventing upward diffusion of chlorinated solvent vapors in the unsaturated zone.
- Author
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Zingaretti D, Verginelli I, Luisetto I, and Baciocchi R
- Subjects
- Iron, Solvents, Groundwater, Trichloroethylene, Water Pollutants, Chemical analysis
- Abstract
Chlorinated solvents are extensively used in many activities and hence in the past decades impacted a large number of sites. The presence of these contaminants in groundwater is challenging particularly for the management of the vapor intrusion pathway. In this work we examine the potential feasibility of using horizontal permeable reactive barriers (HPRBs) placed in the unsaturated zone to treat chlorinated solvent vapors emitted from groundwater. Zero-valent iron (ZVI) powders, partially saturated with water and characterized by different specific surface areas (SSA), were tested, alone or mixed with sand, in lab-scale batch reactors using TCE as model compound. Depending on the type of iron powder used, a reduction of TCE concentration in the vapor phase from approximately 35% up to 99% was observed after 3 weeks of treatment. The best performance in terms of TCE reduction was obtained using the ZVI characterized by the intermediated values of the specific surface area (SSA). This finding, which is in contrast with the results generally observed in in aqueous solutions, was tentatively attributed to a non-selective higher reactivity of the fine-grained iron samples with water and dissolved oxygen (with a consequent iron passivation) or to the occurrence of a diffusion-limited reaction kinetics. Based on the first-order kinetic degradation rate constants estimated from the experimental data, a horizontal barrier of 1 m containing ZVI or a mixture of ZVI and sand can potentially lead to an attenuation of TCE vapors over 99%., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)
- Published
- 2020
- Full Text
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10. Dehalogenation of trichloroethylene vapors by partially saturated zero-valent iron.
- Author
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Zingaretti D, Verginelli I, and Baciocchi R
- Abstract
The reduction of trichloroethylene (TCE) in gas phase by different types of granular zero-valent iron (Fe
0 ) was examined in anaerobic batch vapor systems performed at room temperature. Concentrations of TCE and byproducts were determined at discrete time intervals by analysis of the headspace vapors. Depending on the type of iron used, reductions of TCE gas concentration from 35% up to 99% were observed for treatments of 6 weeks. In line with other experimental studies performed with aqueous solutions, the particle size was found to play a key role in the reactivity of the iron. Namely an increase of the TCE removal up to almost 3 times was observed using iron powders with particle size lower than 425 μm compared to iron powders with particle size lower than 850 μm. The manufacturing process of the iron powder was instead found to play only a limited role. Namely, no significant differences were observed in the TCE reduction by Fe0 obtained using an iron powder attained by water atomization and sieving compared to the removal achieved using an iron powder subjected to a further annealing processes to reduce the content of oxides. Conversely, the pretreatment of the iron powder with HCl was found to enhance the reactivity of the iron. In particular, by washing the iron powder of 425 μm with HCl acid 0.1 M the reduction of TCE after 6 weeks of treatment increase from approximately 80% for the as received material to >99% for the pretreated iron powder. We also performed tests at different humidity of the iron observing that not statistical differences were obtained using a water content of 10% or 50% by weight. In all the experiments, the only detectable byproducts of the reactions were C4-C6 alkenes and alkanes that can be attributed to a hydrogenation of the CCl bond., (Copyright © 2018 Elsevier B.V. All rights reserved.)- Published
- 2019
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11. Soluble organic substances extracted from compost as amendments for Fenton-like oxidation of contaminated sites.
- Author
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Zingaretti D, Lombardi F, and Baciocchi R
- Abstract
The Fenton process is a well known treatment that proved to be effective for the remediation of sites contaminated by a wide range of organic pollutants. Its application to soil-water systems typically requires the addition of a stabilizer, in order to increase the H
2 O2 lifetime and thus the radius of influence of the treatment, and a chelating agent, aimed to extract and maintain in solution the iron present in the soil. However, as the use of these compounds has been debated for their environmental impact, efforts have been placed to test new "greener" amendments. Namely, in line with the concept of circular economy introduced by the European Council, in this study we have tested the use of humic acids extracted from compost as amendment in a Fenton-like process. These substances are of potential interest as can form complexes with metal ions and act as sorbents for hydrophobic organic compounds. Fenton-like lab-scale tests with the extracted humic acids were performed on a soil-water system artificially contaminated by chlorophenol. The obtained results were compared with those achieved applying commercial humic acids or traditional amendments (i.e. KH2 PO4 or EDTA) used as reference. The humic acids extracted from compost allowed to achieve a H2 O2 lifetime close to the one obtained with traditional stabilizing agent; besides, humic acids proved also effective in removing chlorophenol, with performance close to the one achieved using a traditional chelating agent. These findings hence suggest that the use of the humic acids extracted from wastes in a Fenton-like process could allow to replace at the same time the H2 O2 stabilizer and the chelating agent., (Copyright © 2017 Elsevier B.V. All rights reserved.)- Published
- 2018
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12. Using dynamic flux chambers to estimate the natural attenuation rates in the subsurface at petroleum contaminated sites.
- Author
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Verginelli I, Pecoraro R, and Baciocchi R
- Abstract
In this work, we introduce a screening method for the evaluation of the natural attenuation rates in the subsurface at sites contaminated by petroleum hydrocarbons. The method is based on the combination of the data obtained from standard source characterization with dynamic flux chambers measurements. The natural attenuation rates are calculated as difference between the flux of contaminants estimated with a non-reactive diffusive model starting from the concentrations of the contaminants detected in the source (soil and/or groundwater) and the effective emission rate of the contaminants measured using dynamic flux chambers installed at ground level. The reliability of this approach was tested in a contaminated site characterized by the presence of BTEX in soil and groundwater. Namely, the BTEX emission rates from the subsurface were measured in 4 seasonal campaigns using dynamic flux chambers installed in 14 sampling points. The comparison of measured fluxes with those predicted using a non-reactive diffusive model, starting from the source concentrations, showed that, in line with other recent studies, the modelling approach can overestimate the expected outdoor concentration of petroleum hydrocarbons even up to 4 orders of magnitude. On the other hand, by coupling the measured data with the fluxes estimated with the diffusive non-reactive model, it was possible to perform a mass balance to evaluate the natural attenuation loss rates of petroleum hydrocarbons during the migration from the source to ground level. Based on this comparison, the estimated BTEX loss rates in the test site were up to almost 0.5kg/year/m
2 . These rates are in line with the values reported in the recent literature for natural source zone depletion. In short, the method presented in this work can represent an easy-to-use and cost-effective option that can provide a further line of evidence of natural attenuation rates expected at contaminated sites., (Copyright © 2017 Elsevier B.V. All rights reserved.)- Published
- 2018
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13. Analytical model for the design of in situ horizontal permeable reactive barriers (HPRBs) for the mitigation of chlorinated solvent vapors in the unsaturated zone.
- Author
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Verginelli I, Capobianco O, Hartog N, and Baciocchi R
- Subjects
- Diffusion, Gases, Halogenation, Hydrocarbons, Chlorinated, Hydrogen-Ion Concentration, Oxidation-Reduction, Porosity, Potassium Permanganate, Silicon Dioxide, Soil chemistry, Solvents chemistry, Tetrachloroethylene chemistry, Trichloroethylene chemistry, Water Pollution, Chemical prevention & control, Environmental Restoration and Remediation methods, Hydrology methods, Models, Theoretical, Water Pollutants, Chemical
- Abstract
In this work we introduce a 1-D analytical solution that can be used for the design of horizontal permeable reactive barriers (HPRBs) as a vapor mitigation system at sites contaminated by chlorinated solvents. The developed model incorporates a transient diffusion-dominated transport with a second-order reaction rate constant. Furthermore, the model accounts for the HPRB lifetime as a function of the oxidant consumption by reaction with upward vapors and its progressive dissolution and leaching by infiltrating water. Simulation results by this new model closely replicate previous lab-scale tests carried out on trichloroethylene (TCE) using a HPRB containing a mixture of potassium permanganate, water and sand. In view of field applications, design criteria, in terms of the minimum HPRB thickness required to attenuate vapors at acceptable risk-based levels and the expected HPRB lifetime, are determined from site-specific conditions such as vapor source concentration, water infiltration rate and HPRB mixture. The results clearly show the field-scale feasibility of this alternative vapor mitigation system for the treatment of chlorinated solvents. Depending on the oxidation kinetic of the target contaminant, a 1m thick HPRB can ensure an attenuation of vapor concentrations of orders of magnitude up to 20years, even for vapor source concentrations up to 10g/m
3 . A demonstrative application for representative contaminated site conditions also shows the feasibility of this mitigation system from an economical point of view with capital costs potentially somewhat lower than those of other remediation options, such as soil vapor extraction systems. Overall, based on the experimental and theoretical evaluation thus far, field-scale tests are warranted to verify the potential and cost-effectiveness of HPRBs for vapor mitigation control under various conditions of application., (Copyright © 2017 Elsevier B.V. All rights reserved.)- Published
- 2017
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14. Role of the source to building lateral separation distance in petroleum vapor intrusion.
- Author
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Verginelli I, Capobianco O, and Baciocchi R
- Subjects
- Aerobiosis, Air Pollutants, Benzene, Biodegradation, Environmental, Gases, Groundwater chemistry, Hydrocarbons analysis, Hydrocarbons metabolism, Models, Theoretical, Oxygen metabolism, Soil chemistry, Soil Microbiology, Volatilization, Petroleum analysis, Soil Pollutants analysis, Water Pollutants, Chemical
- Abstract
The adoption of source to building separation distances to screen sites that need further field investigation is becoming a common practice for the evaluation of the vapor intrusion pathway at sites contaminated by petroleum hydrocarbons. Namely, for the source to building vertical distance, the screening criteria for petroleum vapor intrusion have been deeply investigated in the recent literature and fully addressed in the recent guidelines issued by ITRC and U.S.EPA. Conversely, due to the lack of field and modeling studies, the source to building lateral distance received relatively low attention. To address this issue, in this work we present a steady-state vapor intrusion analytical model incorporating a piecewise first-order aerobic biodegradation limited by oxygen availability that accounts for lateral source to building separation. The developed model can be used to evaluate the role and relevance of lateral vapor attenuation as well as to provide a site-specific assessment of the lateral screening distances needed to attenuate vapor concentrations to risk-based values. The simulation outcomes showed to be consistent with field data and 3-D numerical modeling results reported in previous studies and, for shallow sources, with the screening criteria recommended by U.S.EPA for the vertical separation distance. Indeed, although petroleum vapors can cover maximum lateral distances up to 25-30m, as highlighted by the comparison of model outputs with field evidences of vapor migration in the subsurface, simulation results by this new model indicated that, regardless of the source concentration and depth, 6m and 7m lateral distances are sufficient to attenuate petroleum vapors below risk-based values for groundwater and soil sources, respectively. However, for deep sources (>5m) and for low to moderate source concentrations (benzene concentrations lower than 5mg/L in groundwater and 0.5mg/kg in soil) the above criteria were found extremely conservative as the model results indicated that for such scenarios the lateral screening distance may be set equal to zero., (Copyright © 2016 Elsevier B.V. All rights reserved.)
- Published
- 2016
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15. The fate of MtBE during Fenton-like treatments through laboratory scale column tests.
- Author
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Piscitelli D, Zingaretti D, Verginelli I, Gavasci R, and Baciocchi R
- Subjects
- Calcium Chelating Agents chemistry, Carbon Dioxide chemistry, Edetic Acid chemistry, Hydrogen Peroxide chemistry, Iron chemistry, Laboratories, Oxidants chemistry, Oxidation-Reduction, Soil chemistry, Methyl Ethers chemistry, Soil Pollutants chemistry, Water Pollutants, Chemical chemistry
- Abstract
In Situ Chemical Oxidation (ISCO) based on the Fenton's process is a proven technology for the treatment of groundwater contaminated by organic compounds. Nevertheless, the application of this treatment process to methyl tert-butyl ether (MtBE) is questioned, as there are concerns about its capacity to achieve complete mineralization. Many existing studies have focused on water contaminated by MtBE and are thus not representative of in situ treatments since they do not consider the presence of soil. In this work, the effectiveness of a Fenton-like process for MtBE treatment was proven in soil column tests performed at operating conditions (i.e., oxidant and contaminant concentration and flow rates) resembling those typically used for in situ applications. No MtBE by-products were detected in any of the tested conditions, thus suggesting that the tert-butyl group of MtBE was completely degraded. A mass balance based on the CO2 produced was used as evidence that most of the MtBE removed was actually mineralized. Finally, the obtained results show that preconditioning of soil with a chelating agent (EDTA) significantly enhanced MtBE oxidation., (Copyright © 2015 Elsevier B.V. All rights reserved.)
- Published
- 2015
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16. Effects of thin-film accelerated carbonation on steel slag leaching.
- Author
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Baciocchi R, Costa G, Polettini A, and Pomi R
- Subjects
- Carbon Sequestration, Models, Theoretical, Carbon Dioxide chemistry, Industrial Waste analysis, Metals analysis, Stainless Steel, Waste Management methods
- Abstract
This paper discusses the effects of accelerated carbonation on the leaching behaviour of two types of stainless steel slags (electric arc furnace and argon oxygen decarburisation slag). The release of major elements and toxic metals both at the natural pH and at varying pH conditions was addressed. Geochemical modelling of the eluates was used to theoretically describe leaching and derive information about mineralogical changes induced by carbonation. Among the investigated elements, Ca and Si were most appreciably affected by carbonation. A very clear effect of carbonation on leaching was observed for silicate phases; geochemical modelling indicated that the Ca/Si ratio of Ca-controlling minerals shifted from ∼ 1 for the untreated slag to 0.5-0.67 for the carbonated samples, thus showing that the carbonation process left some residual Ca-depleted silicate phases while the extracted Ca precipitated in the form of carbonate minerals. For toxic metals the changes in leaching induced by carbonation appeared to be mainly related to the resulting pH changes, which were as high as ∼ 2 orders of magnitude upon carbonation. Depending on the specific shape of the respective solubility curves, the extent of leaching of toxic metals from the slag was differently affected by carbonation., (Copyright © 2014 Elsevier B.V. All rights reserved.)
- Published
- 2015
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17. Thin-film versus slurry-phase carbonation of steel slag: CO₂ uptake and effects on mineralogy.
- Author
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Baciocchi R, Costa G, Di Gianfilippo M, Polettini A, Pomi R, and Stramazzo A
- Subjects
- Carbonates, Carbon Dioxide chemistry, Industrial Waste, Refuse Disposal methods, Steel
- Abstract
The results of direct aqueous accelerated carbonation of three types of steel manufacturing residues, including an electric arc furnace (EAF) slag and two basic oxygen furnace (BOF) slags, are reported. Batch accelerated carbonation tests were conducted at different temperatures and CO2 pressures applying the thin-film route (liquid to solid, L/S, ratio=0.3L/kg) or the slurry-phase route (L/S ratio=5L/kg). The CO2 uptake strongly depended on both the slag characteristics and the process route; maximum yields of 280 (EAF), 325 (BOF1) and 403 (BOF2) gCO2/kg slag were achieved in slurry phase at T=100°C and pCO2=10 bar. Differently from previous studies, additional carbonates (other than Ca-based phases) were retrieved in the carbonated BOF slags, indicating that also Mg-, Fe- and Mn-containing phases partially reacted with CO2 under the tested conditions. The results hence show that the effects of accelerated carbonation in terms of CO2 uptake capacity, yield of mineral conversion into carbonates and mineralogy of the treated product, strongly rely on several factors. These include, above all, the mineralogy of the original material and the operating conditions adopted, which thus need specific case-by-case optimization to maximize the CO2 sequestration yield., (Copyright © 2014 Elsevier B.V. All rights reserved.)
- Published
- 2015
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18. Pilot-scale ISCO treatment of a MtBE contaminated site using a Fenton-like process.
- Author
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Innocenti I, Verginelli I, Massetti F, Piscitelli D, Gavasci R, and Baciocchi R
- Subjects
- Methyl Ethers analysis, Models, Chemical, Pilot Projects, Water Pollutants, Chemical analysis, Environmental Restoration and Remediation methods, Groundwater chemistry, Hydrogen Peroxide chemistry, Iron chemistry, Methyl Ethers chemistry, Water Pollutants, Chemical chemistry
- Abstract
This paper reports about a pilot-scale feasibility study of In-Situ Chemical Oxidation (ISCO) application based on the use of stabilized hydrogen peroxide catalyzed by naturally occurring iron minerals (Fenton-like process) to a site formerly used for fuel storage and contaminated by MtBE. The stratigraphy of the site consists of a 2-3 meter backfill layer followed by a 3-4 meter low permeability layer, that confines the main aquifer, affected by a widespread MtBE groundwater contamination with concentrations up to 4000 μg/L, also with the presence of petroleum hydrocarbons. The design of the pilot-scale treatment was based on the integration of the results obtained from experimental and numerical modeling accounting for the technological and regulatory constraints existing in the site to be remediated. In particular, lab-scale batch tests allowed the selection of the most suitable operating conditions. Then, this information was implemented in a numerical software that allowed to define the injection and monitoring layout and to predict the propagation of hydrogen peroxide in groundwater. The pilot-scale field results confirmed the effective propagation of hydrogen peroxide in nearly all the target area (around 75 m(2) using 3 injection wells). As far as the MtBE removal is concerned, the ISCO application allowed us to meet the clean-up goals in an area of 60 m(2). Besides, the concentration of TBA, i.e. a potential by-product of MtBE oxidation, was actually reduced after the ISCO treatment. The results of the pilot-scale test suggest that ISCO may be a suitable option for the remediation of the groundwater plume contaminated by MtBE, providing the background data for the design and cost-estimate of the full-scale treatment., (Copyright © 2014 Elsevier B.V. All rights reserved.)
- Published
- 2014
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19. Modeling of vapor intrusion from hydrocarbon-contaminated sources accounting for aerobic and anaerobic biodegradation.
- Author
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Verginelli I and Baciocchi R
- Subjects
- Biodegradation, Environmental, Gasoline analysis, Hydrocarbons analysis, Hydrocarbons metabolism, Methane chemistry, Oxygen Consumption, Soil Pollutants analysis, Soil Pollutants metabolism, Toluene, Hydrocarbons chemistry, Models, Chemical, Soil Pollutants chemistry
- Abstract
A one-dimensional steady state vapor intrusion model including both anaerobic and oxygen-limited aerobic biodegradation was developed. The aerobic and anaerobic layer thickness are calculated by stoichiometrically coupling the reactive transport of vapors with oxygen transport and consumption. The model accounts for the different oxygen demand in the subsurface required to sustain the aerobic biodegradation of the compound(s) of concern and for the baseline soil oxygen respiration. In the case of anaerobic reaction under methanogenic conditions, the model accounts for the generation of methane which leads to a further oxygen demand, due to methane oxidation, in the aerobic zone. The model was solved analytically and applied, using representative parameter ranges and values, to identify under which site conditions the attenuation of hydrocarbons migrating into indoor environments is likely to be significant. Simulations were performed assuming a soil contaminated by toluene only, by a BTEX mixture, by Fresh Gasoline and by Weathered Gasoline. The obtained results have shown that for several site conditions oxygen concentration below the building is sufficient to sustain aerobic biodegradation. For these scenarios the aerobic biodegradation is the primary mechanism of attenuation, i.e. anaerobic contribution is negligible and a model accounting just for aerobic biodegradation can be used. On the contrary, in all cases where oxygen is not sufficient to sustain aerobic biodegradation alone (e.g. highly contaminated sources), anaerobic biodegradation can significantly contribute to the overall attenuation depending on the site specific conditions., (Copyright © 2011 Elsevier B.V. All rights reserved.)
- Published
- 2011
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20. Biological treatment of PAH-contaminated sediments in a Sequencing Batch Reactor.
- Author
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Chiavola A, Baciocchi R, and Gavasci R
- Subjects
- Oxygen analysis, Bioreactors, Geologic Sediments chemistry, Polycyclic Compounds analysis
- Abstract
The technical feasibility of a sequential batch process for the biological treatment of sediments contaminated by polycyclic aromatic hydrocarbons (PAHs) was evaluated through an experimental study. A bench-scale Sediment Slurry Sequencing Batch Reactor (SS-SBR) was fed with river sediments contaminated by a PAH mixture made by fluorene, anthracene, pyrene and crysene. The process performance was evaluated under different operating conditions, obtained by modifying the influent organic load, the feed composition and the hydraulic residence time. Measurements of the Oxygen Uptake Rates (OURs) provided useful insights on the biological kinetics occurring in the SS-SBR, suggesting the minimum applied cycle time-length of 7 days could be eventually halved, as also confirmed by the trend observed in the volatile solid and total organic carbon data. The removal efficiencies gradually improved during the SS-SBR operation, achieving at the end of the study rather constant removal rates above 80% for both 3-rings PAHs (fluorene and anthracene) and 4-ring PAHs (pyrene and crysene) for an inlet total PAH concentration of 70 mg/kg as dry weight (dw)., (Copyright © 2010 Elsevier B.V. All rights reserved.)
- Published
- 2010
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21. Human health risk assessment: models for predicting the effective exposure duration of on-site receptors exposed to contaminated groundwater.
- Author
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Baciocchi R, Berardi S, and Verginelli I
- Subjects
- Decontamination, Humans, Risk Assessment methods, Water Pollutants, Chemical, Environmental Exposure, Environmental Health methods, Environmental Restoration and Remediation adverse effects, Models, Theoretical
- Abstract
Clean-up of contaminated sites is usually based on a risk-based approach for the definition of the remediation goals, which relies on the well known ASTM-RBCA standard procedure. In this procedure, migration of contaminants is described through simple analytical models and the source contaminants' concentration is supposed to be constant throughout the entire exposure period, i.e. 25-30 years. The latter assumption may often result over-protective of human health, leading to unrealistically low remediation goals. The aim of this work is to propose an alternative model taking in account the source depletion, while keeping the original simplicity and analytical form of the ASTM-RBCA approach. The results obtained by the application of this model are compared with those provided by the traditional ASTM-RBCA approach, by a model based on the source depletion algorithm of the RBCA ToolKit software and by a numerical model, allowing to assess its feasibility for inclusion in risk analysis procedures. The results discussed in this work are limited to on-site exposure to contaminated water by ingestion, but the approach proposed can be extended to other exposure pathways., (Copyright 2010 Elsevier B.V. All rights reserved.)
- Published
- 2010
- Full Text
- View/download PDF
22. Influence of the operating conditions on highly oxidative radicals generation in Fenton's systems.
- Author
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Ciotti C, Baciocchi R, and Tuhkanen T
- Subjects
- Time Factors, Chemistry Techniques, Analytical methods, Hydrogen Peroxide chemistry, Iron chemistry, Oxides analysis, Oxides chemistry
- Abstract
In this work, an indirect method for estimating the total amount and concentration of oxidative radicals in aqueous and slurry-phase Fenton's systems was developed. This method, based on the use of benzoic acid as probe compound, was applied for evaluating the effect of the operating conditions on the radicals amount produced, their production efficiency (i.e. moles of radicals generated per mole H2O2 and their concentration. A Rotatable Central Composite design (RCC) was used to select the operating conditions in order to get a statistically meaningful data set. Hydrogen peroxide and ferrous ion concentrations ranged between 0.2-1mM and 0.2-0.5mM, respectively; humic acid concentration between 0 and 15mg/L, whereas the soil/water weight ratio in slurry-phase systems between 1:10 and 9:10. The probe compound concentration was 9 or 0.1mM in experiments aimed to evaluate the total amount or concentration of oxidative radicals, respectively. The obtained results indicated that the amount of radicals generated in both aqueous and soil slurry Fenton's system increased with higher H2O2 concentration and, more specifically, that their production efficiency increased with increasing Fe(II):H2O2 molar ratio. Addition of dissolved organic compounds as humic acid did not notably affect the oxidative radicals amount and concentration. On the contrary, a one order of magnitude reduction in both radicals amount generated and concentration was observed when soil was added to the reaction environment.
- Published
- 2009
- Full Text
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23. Modeling of chlorophenols competitive adsorption on soils by means of the ideal adsorbed solution theory.
- Author
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Baciocchi R, Boni MR, and Lavecchia R
- Subjects
- Adsorption, Forecasting, Temperature, Chlorophenols chemistry, Models, Theoretical, Soil Pollutants
- Abstract
The adsorption of 3-chlorophenol (3-CP) and 3,5-dichlorophenol (3,5-CP) on two Italian soils was studied at 20 degrees C. Experiments on the pure components showed that 3,5-CP was more strongly adsorbed than 3-CP, and that the adsorption capacity could be related to the organic carbon fraction of the soil. Competitive adsorption data were described by the fully predictive ideal adsorbed solution (IAS) theory. To this end, the Langmuir parameters determined from pure component adsorption data were used. Results showed that at low 3,5-CP concentration (up to 5-10 mM) the model describes satisfactorily the binary system behavior, whereas at higher concentrations predictions fail, suggesting that non ideality effects in the adsorbed phase should be accounted for.
- Published
- 2005
- Full Text
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24. Application of H2O2 lifetime as an indicator of TCE Fenton-like oxidation in soils.
- Author
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Baciocchi R, Boni MR, and D'Aprile L
- Subjects
- Oxidation-Reduction, Environmental Monitoring methods, Hydrogen Peroxide analysis, Hydrogen Peroxide chemistry, Oxidants chemistry, Soil analysis, Trichloroethylene chemistry
- Abstract
Hydrogen peroxide decomposition and trichloroethylene (TCE) oxidation kinetics were studied through batch slurry experiments, performed on two TCE contaminated soils (a sandy soil and a clay soil), characterized by different texture and organic fraction; besides, experiments were also performed on sandy soil columns, in order to more closely reproduce the typical conditions of an in situ treatment. The results of the batch tests indicated that hydrogen peroxide lifetime was correlated to the oxidation efficiency; namely, complete TCE oxidation was achieved only for the conditions characterized by longer hydrogen peroxide lifetime, that was obtained by addition of a proper stabilizer (KH(2)PO(4)). The soil properties were also observed to influence both hydrogen peroxide decomposition and TCE oxidation kinetics, probably as a consequence of the different TOC content. The soil column experiments, performed on 10, 20, and 30 cm long columns, indicated that hydrogen peroxide decomposition, which was almost complete at 30 cm depth, was on the contrary negligible when the stabilizer was added. In agreement with this observation, the performance of TCE oxidation were greatly improved in the latter case. Based upon the collected results, it can be concluded that hydrogen peroxide experiments may be useful, at least in the first screening phase of the design activity, for selecting, among the different operating conditions, those that may be potentially more effective for the oxidation treatment.
- Published
- 2004
- Full Text
- View/download PDF
25. General model for the achiral chromatography of enantiomers forming dimers: application to binaphthol.
- Author
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Baciocchi R, Mazzotti M, and Morbidelli MC
- Subjects
- Adsorption, Dimerization, Stereoisomerism, Models, Chemical, Naphthols chemistry
- Abstract
This works deals with the development of a model for the description of the chromatographic behavior of enantiomers forming dimers on achiral stationary phases. The model describes the formation of both homochiral and heterochiral dimers by introducing two equilibrium constants, K(homo) and K(hetero), which have to be independently estimated. The adsorption of both monomeric and dimeric species is described by a bi-Langmuir isotherm. Both adsorption and dimerization equilibrium models are implemented in a standard equilibrium-dispersive model of the chromatographic column. The isotherm parameters are determined by fitting of pulses constituted either of the pure enantiomers or of non racemic mixtures of both enantiomers. The validity of the model is then assessed by application to the binaphthol case.
- Published
- 2004
- Full Text
- View/download PDF
26. Hydrogen peroxide lifetime as an indicator of the efficiency of 3-chlorophenol Fenton's and Fenton-like oxidation in soils.
- Author
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Baciocchi R, Boni MR, and D'Aprile L
- Subjects
- Environmental Pollution prevention & control, Oxidation-Reduction, Chlorophenols chemistry, Hydrogen Peroxide chemistry, Iron chemistry, Oxidants chemistry, Soil Pollutants analysis
- Abstract
In this work the possibility of using the hydrogen peroxide lifetime as indicator of the oxidation efficiency of Fenton's and Fenton-like processes for soil treatment was explored. A reactivity scale, in terms of the oxidizing power in the different tested operating conditions (pH, iron sulfate concentration and stabilizer concentration) was built for each soil as a function of the hydrogen peroxide lifetime. Its validity was then confirmed through 3-chlorophenol Fenton's and Fenton-like slurry-phase oxidation experiments. The proposed reactivity scale proved to be effective for comparing the different operating conditions for the same soil, but failed when used to compare the oxidation performances for different soils, since the different adsorptive behavior of the tested soils may have influenced the contaminant removal rate.
- Published
- 2003
- Full Text
- View/download PDF
27. Separation of binaphthol enantiomers through achiral chromatography.
- Author
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Baciocchi R, Zenoni G, Mazzotti M, and Morbidelli M
- Subjects
- Adsorption, Dimerization, Spectrophotometry, Ultraviolet, Stereoisomerism, Chromatography, Liquid methods, Naphthols isolation & purification
- Abstract
Chromatography is a key technique for the analytical, preparative, and production scale separation of enantiomers, particularly in the pharmaceutical and fine chemicals industries. Although it is common belief that this separation can be accomplished only using a chiral stationary phase, it has been recently shown that under certain circumstances a non-racemic mixture of specific chiral compounds can be separated in two fractions which differ in enantiomeric excess (e.e.) also on an achiral stationary phase. In this work we show that in the case of the enantiomers of binaphthol in chloroform achiral chromatography on LiChrospher 100 NH2 furnishes two fractions constituted of the pure enantiomer present in excess and of the racemic mixture, respectively. This is demonstrated by on-line monitoring the concentration of both enantiomers at the outlet of a chromatographic column fed with a non-racemic pulse of the two enantiomers by using a UV detector and a polarimeter in series. Furthermore, we provide experimental evidence of the presence of homo- and hetero-dimers in solution through NMR experiments and develop a consistent physico-chemical model of the solution itself and of the competitive achiral adsorption equilibria. When combined with a standard rate model of the chromatographic column this not only confirms the possibility of achieving 100% e.e. through achiral chromatography, but also allows for a qualitative and quantitative description of all the experimentally observed phenomena. Among these, the effect of the enantiomeric excess and of the overall concentration of the injected pulse on the chromatographic behaviour are worth mentioning.
- Published
- 2002
- Full Text
- View/download PDF
28. Fast determination of phenols in contaminated soils.
- Author
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Baciocchi R, Attinà M, Lombardi G, and Boni MR
- Subjects
- Reproducibility of Results, Chromatography, Gas methods, Phenols analysis, Soil Pollutants analysis
- Abstract
An extraction method for the determination of phenols in contaminated soils, based on the application of solid-phase microextraction (SPME) coupled with GC-flame ionization detection analysis, was developed and tested. This method was developed using a natural soil spiked with phenol to a concentration level typical of an acute contamination event that can occur in an industrial site. The effects of the extraction parameters (pH, extraction time and salt concentration) on the extraction efficiency were studied and the method was then applied to determine the pollutant concentration at the beginning and during the biological treatment of a soil, contaminated with phenol and 3-chlorophenol, respectively. The SPME results were validated by comparison with those obtained with an US Environmental Protection Agency certified extraction method. The SPME method was also successfully applied to the determination of the adsorption behavior of 3-chlorophenol on a natural clay soil and was shown to be suitable for different matrices and phenolic compounds. Application of SPME technique results in a sharp reduction of the extraction times with negligible solvent consumption.
- Published
- 2001
- Full Text
- View/download PDF
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