An innovative in-situ DRAINage system for advanced groundwater reactive TREATment (in-DRAIN-TREAT).

The removal of groundwater contamination is a complex process due to the hydro-geochemical characteristics of the specific site, related maintenance and the possible presence of several types of pollutants, both organic and inorganic. In recent decades, there has been an increasing drive towards more sustainable treatment for contaminated groundwater as opposed to "intensive" treatments, i.e. with high requirements for onsite infrastructure, energy and resource use. In this study, a new remediation technology is proposed, combining the use of advanced drainage systems with adsorption processes, termed "In-situ reactive DRAINage system for groundwater TREATment" (In-DRAIN-TREAT). By taking advantage of the groundwater natural gradient, In-DRAIN-TREAT collects the contaminated groundwater via a drainage system and treats the polluted water directly into an active cell located downstream, avoiding external energy inputs. Preliminary results indicate the applicability and high efficiency of In-DRAIN-TREAT when compared with a permeable reactive barrier (PRB). In-DRAIN-TREAT is applied to remediate a theoretical aquifer with low permeability, contaminated by a 13 m wide hexavalent chromium (CrVI) plume. This is achieved in less than a year, via a drain DN500, 32 m long, a 30 m3 treatment cell filled with activated carbon and no energy consumption. A comparison with permeable barriers also shows a preliminary 63% volume reduction, with a related 10% decrease of remediation costs.

Experimental and simulation study of the restoration of a thallium (I)-contaminated aquifer by Permeable Adsorptive Barriers (PABs).

Permeable Adsorptive Barriers (PABs), filled with a commercial activated carbon, are tested as a technique for the remediation of a thallium (I)-contaminated aquifer located in the south of Italy. Thallium adsorption capacity of the activated carbon is experimentally determined through dedicated laboratory tests, allowing to obtain the main modelling parameters to describe the adsorption phenomena within the barrier. A 2D numerical model, solved by using a finite element approach via COMSOL Multi-physics®, is used to simulate the contaminant transport within the aquifer and for the PAB design. Investigations are carried out on an innovative barrier configuration, called Discontinuous Permeable Adsorptive Barrier (PAB-D). In addition, an optimization procedure is followed to determine the optimum PAB-D parameters, and to evaluate the total costs of the intervention. A PAB-D made by an array of wells having a diameter of 1.5m and spaced at a distance of 4m from each other, is shown to be the most cost-effective of those tested, and ensures the aquifer restoration within 80years. The simulation outcomes demonstrate that the designed PAB-D is an effective tool for the remediation of the aquifer under analysis, since the contaminant concentration downstream of the barrier is below the thallium regulatory limit for groundwater, also accounting for possible desorption phenomena. Finally, the best PAB-D configuration is compared with a continuous barrier (PAB-C), resulting in a 32% saving of adsorbing material volume, and 36% of the overall costs for the PAB-D.

Adsorption of elemental mercury vapors from synthetic exhaust combustion gas onto HGR carbon.

UNLABELLED: An activated carbon commercially available named HGR, produced by Calgon-Carbon Group, was used to adsorbe metallic mercury. The work is part of a wider research activity by the same group focused on the removal of metallic and divalent mercury from combustion flue gas. With respect to previously published papers, this one is aimed at studying in depth thermodynamic equilibria of metallic mercury adsorption onto a commercial activated carbon. The innovativeness lies in the wider operative conditions explored (temperature and mercury concentrations) and in the evaluation of kinetic and thermodynamic data for a commercially available adsorbing material. In detail, experimental runs were carried out on a laboratory-scale plant, in which Hg° vapors were supplied in a nitrogen gas stream at different temperature and mercury concentration. The gas phase was flowed through a fixed bed of adsorbent material. Adsorbate loading curves for different Hg° concentrations together with adsorption isotherms were achieved as a function of temperature (120, 150, 200°C) and Hg° concentrations (1.0-7.0 mg/m(3)). Experimental runs demonstrated satisfying results of the adsorption process, while Langmuir parameters were evaluated with gas-solid equilibrium data. Especially, they confirmed that adsorption capacity is a favored process in case of lower temperature and they showed that the adsorption heat was -20 kJ/mol. Furthermore, a numerical integration of differential equations that model the adsorption process was proposed. Scanning electron microscopy (SEM) investigation was an useful tool to investigate about fresh and saturated carbon areas. The comparison between them allowed identification of surface sites where mercury is adsorbed; these spots correspond to carbon areas where sulfur concentration is greater. IMPLICATIONS: Mercury compounds can cause severe harm to human health and to the ecosystem. There are a lot of sources that emit mercury species to the atmosphere; the main ones are exhaust gases from coal combustion and municipal solid waste incineration. Furthermore, certain CO2 capture processes, particularly oxyfuel combustion in a pulverized fuel coal-fired power station, produce a raw CO2 product containing several contaminants, mainly water vapor, oxygen, and nitrogen but also mercury, that have to be almost completely removed; otherwise these would represent a strong drawback to the success of the process.

Equilibrium and dynamic study on hexavalent chromium adsorption onto activated carbon.

In this work, the results of equilibrium and dynamic adsorption tests of hexavalent chromium, Cr (VI), on activated carbon are presented. Adsorption isotherms were determined at different levels of pH and temperature. Dynamic tests were carried out in terms of breakthrough curves of lab-scale fixed bed column at different pH, inlet concentration and flow rate. Both the adsorption isotherms and the breakthrough curves showed non-linear and unconventional trends. The experimental results revealed that chromium speciation played a key role in the adsorption process, also for the occurrence of Cr(VI)-to-Cr(III) reduction reactions. Equilibrium tests were interpreted in light of a multi-component Langmuir model supported by ion speciation analysis. For the interpretation of the adsorption dynamic tests, a mass transfer model was proposed. Dynamic tests at pH 11 were well described considering the external mass transfer as the rate controlling step. Differently, for dynamic tests at pH 6 the same model provided a satisfying description of the experimental breakthrough curves only until a sorbent coverage around 1.6mgg(-1). Above this level, a marked reduction of the breakthrough curve slope was observed in response to a transition to an inter-particle adsorption mechanism.

Permeable Adsorptive Barrier (PAB) for the remediation of groundwater simultaneously contaminated by some chlorinated organic compounds.

In this paper, a Permeable Reactive Barrier (PRB) made with activated carbon, namely a Permeable Adsorptive Barrier (PAB), is put forward as an effective technique for the remediation of aquifers simultaneously contaminated by some chlorinated organic compounds. A design procedure, based on a computer code and including different routines, is presented as a tool to accurately describe mass transport within the aquifer and adsorption/desorption phenomena occurring inside the barrier. The remediation of a contaminated aquifer near a solid waste landfill in the district of Napoli (Italy), where Tetrachloroethylene (PCE) and Trichloroethylene (TCE) are simultaneously present, is considered as a case study. A complete hydrological and geotechnical site characterization, as well as a number of dedicated adsorption laboratory tests for the determination of activated carbon PCE/TCE adsorption capacity in binary systems, are carried out to support the barrier design. By means of a series of numerical simulations it is possible to determine the optimal barrier location, orientation and dimensions. PABs appear to be an effective remediation tool for the in-situ treatment of an aquifer contaminated by PCE and TCE simultaneously, as the concentration of both compounds flowing out of the barrier is everywhere lower than the regulatory limits on groundwater quality.

Remediation of an aquifer polluted with dissolved tetrachloroethylene by an array of wells filled with activated carbon.

In this work, an array of deep passive wells filled with activated carbon, namely a Discontinuous Permeable Adsorptive Barrier (PAB-D), has been proposed for the remediation of an aquifer contaminated by tetrachloroethylene (PCE). The dynamics of the aquifer in the particular PAB-D configuration chosen, including the contaminant transport in the aquifer and the adsorption onto the barrier material, has been accurately performed by means of a computer code which allows describing all the phenomena occurring in the aquifer, simultaneously. A PAB-D design procedure is presented and the main dimensions of the barrier (number and position of passive wells) have been evaluated. Numerical simulations have been carried out over a long time span to follow the contaminant plume and to assess the effectiveness of the remediation method proposed. The model results show that this PAB-D design allows for a complete remediation of the aquifer under a natural hydraulic gradient, the PCE concentrations flowing out of the barrier being always lower than the corresponding Italian regulation limit. Finally, the results have been compared with those obtained for the design of a more traditional continuous barrier (PAB-C) for the same remediation process.

Mercury adsorption on granular activated carbon in aqueous solutions containing nitrates and chlorides.

Adsorption is an effective process to remove mercury from polluted waters. In spite of the great number of experiments on this subject, the assessment of the optimal working conditions for industrial processes is suffering the lack of reliable models to describe the main adsorption mechanisms. This paper presents a critical analysis of mercury adsorption on an activated carbon, based on the use of chemical speciation analysis to find out correlations between mercury adsorption and concentration of dissolved species. To support this analysis, a comprehensive experimental study on mercury adsorption at different mercury concentrations, temperatures and pH was carried out in model aqueous solutions. This study pointed out that mercury capture occurs mainly through adsorption of cationic species, the adsorption of anions being significant only for basic pH. Furthermore, it was shown that HgOH(+) and Hg(2+) are captured to a higher extent than HgCl(+), but their adsorption is more sensitive to solution pH. Tests on the effect of temperature in a range from 10 to 55 °C showed a peculiar non-monotonic trend for mercury solution containing chlorides. The chemical speciation and the assumption of adsorption exothermicity allow describing this experimental finding without considering the occurrence of different adsorption mechanisms at different temperature.

A procedure to design a Permeable Adsorptive Barrier (PAB) for contaminated groundwater remediation.

A procedure to optimize the design of a Permeable Adsorptive Barrier (PAB) for the remediation of a contaminated aquifer is presented in this paper. A computer code, including different routines that describe the groundwater contaminant transport and the pollutant capture by adsorption in unsteady conditions over the barrier solid surface, has been developed. The complete characterization of the chemical-physical interactions between adsorbing solids and the contaminated water, required by the computer code, has been obtained by experimental measurements. A case study in which the procedure developed has been applied to a tetrachloroethylene (PCE)-contaminated aquifer near a solid waste landfill, in the district of Napoli (Italy), is also presented and the main dimensions of the barrier (length and width) have been evaluated. Model results show that PAB is effective for the remediation of a PCE-contaminated aquifer, since the concentration of PCE flowing out of the barrier is everywhere always lower than the concentration limit provided for in the Italian regulations on groundwater quality.

A descriptive model for metallic ions adsorption from aqueous solutions onto activated carbons.

The design of adsorber units is mainly dependent on the equilibrium adsorption capacity of the sorbent in the working conditions. At the moment, these data are available in a limited number of experimental conditions and, for the case of activated carbon, there are no predictive models to assess the adsorption capacity as a function of the process parameters. This makes the adsorber design a complex and approximated task. In this work, a model for the description of metallic ions adsorption onto activated carbon is presented. The model starts from an evaluation of ion speciation and it considers the approach of the multi-component Langmuir model to correlate the metal uptake to the ion concentration in solution. The model has been used to analyse available experimental data on the adsorption of As(V), Cd(II), Cr(III) and Cr(VI) ions on activated carbon. A good matching between experimental results and model predictions has been obtained for all the investigated conditions.

Groundwater protection from cadmium contamination by permeable reactive barriers.

This work studies the reliability of an activated carbon permeable reactive barrier in removing cadmium from a contaminated shallow aquifer. Laboratory tests have been performed to characterize the equilibrium and kinetic adsorption properties of the activated carbon in cadmium-containing aqueous solutions. A 2D numerical model has been used to describe pollutant transport within a groundwater and the pollutant adsorption on the permeable adsorbing barrier (PRB). In particular, it has been considered the case of a permeable adsorbing barrier (PAB) used to protect a river from a Cd(II) contaminated groundwater. Numerical results show that the PAB can achieve a long-term efficiency by preventing river pollution for several months.

Experimental and modelling analysis of As(V) ions adsorption on granular activated carbon.

In this work the adsorption of pentavalent arsenic on a granular activated carbon (GAC) has been experimentally studied. The effects of arsenic concentration, pH, temperature and salinity on equilibrium adsorption capacity have been investigated. Experimental results show that the adsorption capacity is the highest at neutral pH conditions, low salinity levels and high temperatures. A model for the description of the arsenic adsorption mechanism is reported. This is based on the multicomponent Langmuir adsorption theory applied to the ionic species in solution. The model points out that the adsorption capacity is proportional to the concentration of arsenic anions in solution and decreases by increasing the concentration of competitive ions such as hydroxides and chlorides, allowing a correct interpretation of the pH and salinity effects on the adsorption capacity. Finally, one of the main goals of the proposed model is to preserve the exothermicity of the adsorption phenomena despite the observed trend of experimental results: the increase of adsorption capacity with temperature appears to be related to a higher arsenic dissociation.

Removal of chromium ions from [corrected] aqueous solutions by adsorption on activated carbon and char.

Adsorption isotherms of chromium ions in aqueous solution have been experimentally measured on a granular activated carbon (GAC) and on a char of South African coal (CSAC). Experimental results show that the adsorption capacity for the GAC strongly depends on solution pH and salinity, with maximum values around 7mg/g at neutral pH and low salinity levels. On the contrary, the CSAC shows a smaller adsorption capacity, near 0.3mg/g, which slightly decreases by increasing pH and salinity levels. Chromium adsorption mainly depends on the availability of chromium ions in solution and on the occurrence of redox reactions between the surface groups and the Cr(VI) which lead to the formation of Cr(III). The reduction of Cr(VI) and the following sorption of Cr(III) cations appears as the leading mechanism for chromium uptake on the CSAC. A similar behaviour can be observed for the GAC at pH below 3. On the contrary, at pH>7, the multicomponent competitive adsorption of Cr(VI), OH(-) and Cl(-) has to be considered.

Capture of mercury ions by natural and industrial materials.

In this paper the technical feasibility of various adsorbents for mercury removal from contaminated waters has been studied. Adsorption isotherms of mercury ions in aqueous solution have been experimentally measured on a granular activated carbon (Aquacarb 207EA), a char, a pozzolana and a yellow tuff. The experimental evidences show that the mercury capture capacity of yellow tuff and char is of few tenths of milligrams per gram of sorbent while for the pozzolana and the activated carbon this value is of the order of 1mg/g of sorbent. Moreover, for a mercury concentration as high as 3000 microg/l the pozzolana shows the highest adsorption capacity. This result seems to be quite interesting, especially in consideration of the extremely low cost of this natural sorbent.