Marco Petrangeli Papini

Laboratory investigation of DNAPL migration in porous media

Laboratory experiments have been carried out with and without groundwater flow in a two-dimensional laboratory-scale tank to assess the influence of layered media and hydraulic gradient on DNAPL infiltration and redistribution processes. Hydrofluoroether has been used as DNAPL and glass beads have been utilized as porous medium. An image analysis procedure has been used to determine saturation distribution during infiltration and redistribution processes. This method allows quantitative time dependent full fields mapping of the DNAPL saturation, as well as the monitoring of DNAPL saturation variation. By means of performed experiments important information were obtained about the migration and redistribution process, the infiltration and migration velocity, the characteristics of migration body. The experimental results show that the hydraulic gradient promotes the infiltration process, increasing the infiltration rate. It hampers DNAPL spread and fingering bringing to a reduction of residual DNAPL and it also promotes the DNAPL redistribution, and it reduces the amount remaining at residual saturation. Furthermore the hydraulic gradient promotes downward and down-gradient migration. DNAPL migration in the direction of water flow, can be considered important due to significant errors in the location of sources in the case of high gradients and high aquifer thicknesses, and for high water flow velocities, such as those which can be expected during pumping actions in water supply or in remediation activities.

Characterization and distribution of petroleum hydrocarbons and heavy metals in groundwater from three Italian tank farms.

The present paper highlights the utility of petroleum chemical fingerprinting in investigating known or suspected tank farm releases. A detailed characterization of groundwater was carried out in three tank farms located in north, central and south Italy. Eighteen parent polycyclic aromatic hydrocarbons (naphthalene through coronene), n-alkanes (n-C(10) through n-C(36)), isoprenoids pristane and phytane, vanadium, nickel and lead were determined. Distribution profiles and diagnostic ratios of specific fuel constituents were studied in order to identify contamination sources. Data analysis shows that in the study sites multiple pollutant sources affecting the tank farms and the surrounding industrial areas are present. Both high concentrations of contaminants coming from fuel releases and noticeable concentrations of biogenic compounds were found. A detailed data analysis suggests the origin and the level of pollution of the three sites. The results demonstrate that threshold concentration approach is not always sufficient and it is necessary to carry out studies of contaminant distribution and their diagnostic ratios in order to perform a successful forensic investigation.

The "Oil-Spill Snorkel": an innovative bioelectrochemical approach to accelerate hydrocarbons biodegradation in marine sediments.

This study presents the proof-of-concept of the “Oil-Spill Snorkel”: a novel bioelectrochemical approach to stimulate the oxidative biodegradation of petroleum hydrocarbons in sediments. The “Oil-Spill Snorkel” consists of a single conductive material (the snorkel) positioned suitably to create an electrochemical connection between the anoxic zone (the contaminated sediment) and the oxic zone (the overlying O2-containing water). The segment of the electrode buried within the sediment plays a role of anode, accepting electrons deriving from the oxidation of contaminants. Electrons flow through the snorkel up to the part exposed to the aerobic environment (the cathode), where they reduce oxygen to form water. Here we report the results of lab-scale microcosms setup with marine sediments and spiked with crude oil. Microcosms containing one or three graphite snorkels and controls (snorkel-free and autoclaved) were monitored for over 400 days. Collectively, the results of this study confirmed that the snorkels accelerate oxidative reactions taking place within the sediment, as documented by a significant 1.7-fold increase (p = 0.023, two-tailed t-test) in the cumulative oxygen uptake and 1.4-fold increase (p = 0.040) in the cumulative CO2 evolution in the microcosms containing three snorkels compared to snorkel-free controls. Accordingly, the initial rate of total petroleum hydrocarbons (TPH) degradation was also substantially enhanced. Indeed, while after 200 days of incubation a negligible degradation of TPH was noticed in snorkel-free controls, a significant reduction of 12 ± 1% (p = 0.004) and 21 ± 1% (p = 0.001) was observed in microcosms containing one and three snorkels, respectively. Although, the “Oil-Spill Snorkel” potentially represents a groundbreaking alternative to more expensive remediation options, further research efforts are needed to clarify factors and conditions affecting the snorkel-driven biodegradation processes and to identify suitable configurations for field applications.

Influence of metal speciation in landfill leachates on kaolinite sorption

The sorption onto kaolinite of Pb, Cd, Ni and Cu from a landfill leachate was studied in relation to the metal speciation in the liquid phase. Metal speciation was determined by two different experimental procedures based on the exchangeability on a cation chelating resin (Chelex100) and on the separation by dialysis with membranes at different molecular weight (MW) cut off. The speciation procedures were applied on the leachate before and after equilibration with clay, in order to determine the contribution of the different fractions to the total sorption. As determined by the MW-based procedure, large fractions of dissolved metals were associated to substances with high MW (>1000 and >12000 daltons), even if these substances represent only 18% of the total organic content (as determined by chemical oxygen demand, COD). These high-MW fractions contribute to metal sorption onto kaolinite, as also confirmed by the concurrent removal of COD and phenolic substances. As determined by the exchange-based procedure, the main contribution to metal sorption derived from free/labile (rapidly exchangeable) or slowly exchangeable fractions. However, Pb and Cd were also removed from the stable/inert (not exchangeable) fraction. Because metal sorption is partially due to species that are not exchangeable on Chelex100 and partially to species that have MW more than 1000 daltons, these experimental evidences strongly support that free metals are not the only species participating in the sorption onto kaolinite and that some metal species are adsorbed without previous dissociation.

Use of a reactive transport model to describe reductive dechlorination (RD) as a remediation design tool: application at a CAH-contaminated site.

In this paper, a numerical model is presented that is capable of describing the complex set of biochemical processes that occur in chlorinated aliphatic hydrocarbon (CAH)-contaminated groundwater when an exogenous electron donor is added. The reactive pattern is based on the degradation pathways of both chlorinated ethanes and ethenes, and it includes electron donor production (H2 and acetate) from the fermentation of an organic substrate as well as rate-limiting processes related to electron acceptor competition. Coupling of the kinetic model to a convection–dispersion module is described. The calibration phase was carried out using data obtained at a real CAH-contaminated site in the north of Italy. Model simulations of different application scenarios are presented to draw general conclusions on the effectiveness of reductive dechlorination (RD) as a possible cleanup strategy. Early outcomes indicate that cleanup targets can only be achieved if source longevity is reduced. Therefore, metabolic RD is expected to produce beneficial effects because it is known to induce bioenhanced degradation and transformation of CAHs.

Improved electrical wiring of microbes: anthraquinone-modified electrodes for biosensing of chlorinated hydrocarbons.

The present study reports the development of a novel bioelectrochemical sensor for trichloroethene (TCE), a common subsurface contaminant, based on the measurement of the electrical current resulting from the microbially catalysed reduction of TCE at anthraquinone (AQ)-modified electrodes. Firstly, we describe the development and electrochemical characterisation of AQ-modified electrodes, prepared via spontaneous or electrochemical reduction of AQ diazonium derivatives. Finally, the proof-of-principle of the bioelectrochemical sensor for TCE was evaluated, using a TCE-dechlorinating microbial culture as the biosensing element. The response of the bioelectrochemical sensor was measured either as the peak current in cyclic voltammetry or the steady-state current in chronoamperometry; in both cases, it was found to be proportional to TCE concentrations in the range 0-100 μmol/L. On the other hand, the microorganisms in contact with the electrode surface caused severe fouling problems which drastically reduced the life-time of the sensor.

Biotransformation of β-hexachlorocyclohexane by the saprotrophic soil fungus Penicillium griseofulvum.

β-Hexachlorocyclohexane (β-HCH) is a persistent organic pollutant (POP) of global concern with potentially toxic effects on humans and ecosystems. Fungal tolerance and biotransformation of toxic substances hold considerable promise in environmental remediation technologies as many fungi can tolerate extreme environmental conditions and possess efficient extracellular degradative enzymes with relatively non-specific activities. In this research, we have investigated the potential of a saprotrophic soil fungus, Penicillium griseofulvum Dierckx, isolated from soils with high concentrations of isomers of hexachlorocyclohexane, to biotransform β-HCH, the most recalcitrant isomer to microbial activity. The growth kinetics of the fungus were characterized after growth in stirred liquid Czapek-Dox medium. It was found that P. griseofulvum was able to grow in the presence of 1 mg L(-1) β-HCH and in stressful nutritional conditions at different concentrations of sucrose in the medium (0 and 5 g L(-1)). The effects of β-HCH and the toluene, used as a solvent for β-HCH addition, on P. griseofulvum were investigated by means of a Phenotype MicroArray™ technique, which suggested the activation of certain metabolic pathways as a response to oxidative stress due to the presence of the xenobiotics. Gas chromatographic analysis of β-HCH concentration confirmed biodegradation of the isomer with a minimum value of β-HCH residual concentration of 18.6%. The formation of benzoic acid derivatives as dead-end products of β-HCH biotransformation was observed and this could arise from a possible biodegradation pathway for β-HCH with important connections to fungal secondary metabolism.

Polyhydroxyalkanoate (PHB) as a slow-release electron donor for advanced in situ bioremediation of chlorinated solvent-contaminated aquifers.

During the last two decades permeable reactive barriers (PRBs) established as robust alternatives to traditional pump & treat approaches for groundwater remediation. Zero-valent iron (ZVI) is currently the most frequently employed reactive media, especially for treating plumes polluted by chlorinated hydrocarbons. However PRB-ZVI technology is affected by some problems such as the long-term performance decrease, loss of porosity and no applicability to some important compounds, such as 1,2-dichloroetane (1,2-DCA). In this study we wanted to investigate whether the coupling of ZVI with a long-lasting slow-release substrate (i.e. poly-hydroxybutyrate, PHB) could be a strategy to enhance the degradation performance of ZVI barriers towards chlorinated ethanes especially stimulating biological reductive dechlorination downgradient the PRB. Results here presented clearly demonstrate the feasibility of the proposed approach and the possibility that a biodegradable polymer, usually produced for different commercial sectors, could be advantageously used in the groundwater remediation market.

The bioelectric well: a novel approach for in situ treatment of hydrocarbon-contaminated groundwater

Groundwater contamination by petroleum hydrocarbons (PHs) is a widespread problem which poses serious environmental and health concerns. Recently, microbial electrochemical technologies (MET) have attracted considerable attention for remediation applications, having the potential to overcome some of the limiting factors of conventional in situ bioremediation systems. So far, field‐scale application of MET has been largely hindered by the limited availability of scalable system configurations. Here, we describe the ‘bioelectric well’ a bioelectrochemical reactor configuration, which can be installed directly within groundwater wells and can be applied for in situ treatment of organic contaminants, such as PHs. A laboratory‐scale prototype of the bioelectric well has been set up and operated in continuous‐flow regime with phenol as the model contaminant. The best performance was obtained when the system was inoculated with refinery sludge and the anode potentiostatically controlled at +0.2 V versus SHE. Under this condition, the influent phenol (25 mg l−1) was nearly completely (99.5 ± 0.4%) removed, with an average degradation rate of 59 ± 3 mg l−1 d and a coulombic efficiency of 104 ± 4%. Microbial community analysis revealed a remarkable enrichment of Geobacter species on the surface of the graphite anode, clearly pointing to a direct involvement of this electro‐active bacterium in the current‐generating and phenol‐oxidizing process.

Polyhydroxyalkanoate as a slow-release carbon source for in situ bioremediation of contaminated aquifers: From laboratory investigation to pilot-scale testing in the field.

A pilot-scale study aiming to evaluate the potential use of poly-3-hydroxy-butyrate (PHB) as an electron donor source for in situ bioremediation of chlorinated hydrocarbons in groundwater was conducted. Compared with commercially available electron donors, PHB offers a restricted fermentation pathway (i.e., through acetic acid and molecular hydrogen) by avoiding the formation of any residual carbon that could potentially spoil groundwater quality. The pilot study was carried out at an industrial site in Italy, heavily contaminated by different chlorinated aliphatic hydrocarbons (CAHs). Prior to field testing, PHB was experimentally verified as a suitable electron donor for biological reductive dechlorination processes at the investigated site by microcosm studies carried out on site aquifer material and measuring the quantitative transformation of detected CAHs to ethene. Owing to the complex geological characteristics of the aquifer, the use of a groundwater circulation well (GCW) was identified as a potential strategy to enable effective delivery and distribution of electron donors in less permeable layers and to mobilise contaminants. A 3-screened, 30-m-deep GCW coupled with an external treatment unit was installed at the site. The effect of PHB fermentation products on the in situ reductive dechlorination processes were evaluated by quantitative real-time polymerase chain reaction (qPCR). The results from the first 4 months of operation clearly demonstrated that the PHB fermentation products were effectively delivered to the aquifer and positively influenced the biological dechlorination activity. Indeed, an increased abundance of Dehalococcoides mccartyi (up to 6.6 fold) and reduced CAH concentrations at the installed monitoring wells were observed.