Angela Volpe

Peroxymonosulfate-Co(II) oxidation system for the removal of the non-ionic surfactant Brij 35 from aqueous solution.

The non-ionic surfactant Brij 35 was effectively removed from concentrated aqueous solution by the peroxymonosulfate/Co(II) system, using oxone (2KHSO(5)·KHSO(4)·K(2)SO(4)) as a source of peroxymonosulfate. At pH=2.3 and initial Brij 35 concentration in the range 680-2410 mg L(-1), 86-94% removal was achieved after 24 h, using Co(II)=15 μM and oxone=5.9 mM. The effectiveness of removal did not change when initial pH was in the range 2.3-8.2. After five subsequent additions of Co(II) and oxone to the solution, COD and TOC removals increased up to 64% and 33%, respectively. Radical quenching tests confirmed that sulfate radical was the dominant radical species in the system. The main identified by-products from surfactant degradation were: (a) low molecular weight organic acids; (b) aldehydes and formates with shorter ethoxy chain than Brij 35; (c) alcohol ethoxylates carrying hydroxyl groups bonded to ethoxy chain. By-products identification allowed to hypothesize the pathways of Brij 35 degradation.

OXIDATION OF NONIONIC SURFACTANTS BY FENTON AND H2O2/UV PROCESSES

Abstract The oxidation of 10 nonionic surfactants (6 alcohol ethoxylates and 4 alkylphenol ethoxylates) by Fenton and H2O2/UV processes was investigated in synthetic (deionized water) and real aqueous matrices, i.e. secondary effluent from municipal wastewater treatment plant and groundwater. Batch tests were carried out to assess the optimal dosages of reagents leading to the total removal of surfactants. Regardless to the specific surfactant, both Fenton and H2O2/UV treatments of synthetic solutions containing one single surfactant (C0=14 mg l−1) always caused its rapid and quantitative removal (96–99%) with a corresponding very low (0–18%) TOC decrease. Only for the Fenton treatment, linear relationships were found between the amounts of H2O2 and Fe2+ necessary for surfactant removal and the ethoxy chain length of each surfactant. Conversely, in the case of H2O2/UV treatment the H2O2 dosage causing the quantitative oxidation of the treated surfactant depended on the length of both chains: the ethoxy and the hydrophobic one. Mixtures of the 10 surfactants (1.4 mg l−1 each) were treated in both synthetic and real matrices. These latter were different in the case of Fenton (i.e. municipal secondary effluent) or H2O2/UV (i.e. real groundwater) treatments. Fenton treatment of municipal secondary effluent containing the surfactants mixture led to its total removal when a molar ratio [Total surfactants]/[H2O2]/[Fe2+] equal to 1/17/12 was used. As for H2O2/UV treatment of real groundwater samples, quantitative removal of surfactants mixture was achieved with a molar ratio [Total surfactants]/ [H2O2] equal to 1/7.4. Surfactants mixture removals, if compared in deionized water and in real matrices, showed the same matrix effect during both treatments, i.e. less amounts of reagents were always required in synthetic solutions.

Enhanced bioremediation of methyl tert-butyl ether (MTBE) by microbial consortia obtained from contaminated aquifer material.

A microcosm study was carried out to evaluate the potential for biodegradation of methyl tert-butyl ether (MTBE) impacting groundwater at a former oil refinery site located in Naples (SW Italy). A screening of aerobic, anaerobic and co-metabolic aerobic conditions was carried out by triplicate batch reactors, using contaminated soil and groundwater from the study site. All microcosms were amended with ammonium and phosphate salts and, if aerobic, they were supplied with excess oxygen throughout the static incubation period of 6 months. Propane, pentane and n-hexane were selected as the primary substrates for co-metabolic treatments. After the initial lag phase (40-60d), quantitative MTBE decay was repeatedly observed in the aerobic set amended only with nitrogen and phosphorus and further fed with MTBE, thus suggesting that the indigenous soil bacteria have the ability to degrade MTBE. All other treatments, i.e., anaerobic and co-metabolic aerobic, resulted unsuccessful after incubation extending up to 190d. Bacterial consortia in the active microcosms were later enriched and further studied through second and third generation batch reactors with no soil, operated under continuous mixing for 5-7 months. MTBE degradation rate progressively increased with reactor operating time, following a zero order kinetics in the concentration range 1-10mgL(-1) and leading to a residual concentration of less than 10microgL(-1). The calculated maximum biodegradation rate was 20mg(MTBE)g(VSS)(-1)h(-1). An accumulation of nitrite ions also occurred after long operating times, thus inhibiting MTBE degradation. This effect was minimized by replacing ammonium with nitrate. Identified degradation intermediates were tert-butyl alcohol and tert-butyl formate. Fluorescent in situ hybridization was applied for a preliminary microbiological screening of the consortia, suggesting that the detected cocci (about 0.5 and 1.5microm diameter, respectively) and long bacilli with a narrow diameter might be as yet undescribed species.

Degradation of chlorobenzene by Fenton-like processes using zero-valent iron in the presence of Fe3+ and Cu2+.

Batch and column tests were conducted to compare the efficiencies of three Fenton‐like systems in the degradation of chlorobenzene. In the investigated systems, iron powder was the source of Fe2+ ions, and either Fe3+ or Cu2+ were added in order to enhance the degradation process. Optimum pH and concentrations of Fe3+, Cu2+ and hydrogen peroxide were assessed by treating synthetic chlorobenzene solutions both in batch and in column mode, thus achieving the minimum residual concentration of chlorobenzene. Optimum conditions assessed by means of column tests were then applied to column treatment of real chlorobenzene‐contaminated groundwater. Results showed that, when the TOC content of water was above 12 mg L−1, the performance of the Fe0/H2O2 system was enhanced by the addition of Fe3+, leading to 10–20 µg L−1 of residual chlorobenzene.

Simultaneous Cr(VI) reduction and non-ionic surfactant oxidation by peroxymonosulphate and iron powder

Some industrial wastewaters contain both hexavalent chromium and surfactants. In this work, their removal from aqueous solution by zero-valent iron (ZVI) and peroxymonosulphate (PMS) was studied using Brij 35 as a representative non-ionic surfactant. The performance of the ZVI/PMS system in the simultaneous removal of both pollutants was compared to that achieved with control solutions containing either Cr(VI) or Brij 35 separately. Reactions were carried out over 24h at initial pH=2.3 with variable initial amounts of Cr(VI) and Brij 35. The results showed that surfactant removal was enhanced in the system also containing Cr(VI). Surfactant degradation followed zero-order kinetics and produced formic acid as the main by-product, together with hydroxylated aldehydes, formates and alcohols that were identified by LC/MS. The presence of surfactant similarly enhanced Cr(VI) reduction, which also followed zero-order kinetics. Chromium removal was quantitative only when the initial chromium concentration was lower than 140 mg L(-1). Reduced chromium was mainly in the solution phase together with dissolved iron. Precipitation with NaOH was therefore required to definitively remove dissolved metals from the investigated system.

Conservative technologies for environmental protection based on the use of reactive polymers

Abstract Biodegradation of organic pollutants is based on ‘destructive’ technologies leading to the formation of low-molecular-weight compounds and carbon dioxide or methane depending on the process red-ox conditions. This is not possible for persistent pollutants (e.g., heavy metals, biorefractory organics, complex organometals) independent of the origin and structure of the chemical substrate. Reference compounds can only be recovered and eventually recycled to the production lines of origin and/or to related industrial activities. However, the quality of the recovered products must justify the recycling operation. Sorption techniques (ion exchange, carbon adsorption) and membrane technology as typical ‘conservative’ unit operations allow for removal of pollutants to the strictest limits imposed by enforced legislation and simultaneous recovery and recycling. We discuss two examples of conservative environmental technologies, based on ion exchange and the use of reactive polymers. The first relates to metal-laden effluents from the tannery industry, and the second to the management of residues (clarifier sludge) from the drinking water industry. Both processes are aimed at the minimization of environmental impact resulting from the production lines (Cr(III)- and Al(III)-containing wastes, respectively) and the recovery of valuable by-products with the related economic revenues associated with their commercial value.

Olive husk: an alternative sorbent for removing heavy metals from aqueous streams.

Sorption properties of olive husk were investigated under equilibrium (batch tests) and dynamic (column tests) conditions in order to assess the possibility of using such a waste material for removing heavy metals from aqueous streams. Husk samples were contacted, at 25°C, with aqueous solutions of nitric salts of Pb, Cd, Cu, and Zn. Sorption isotherms obtained from equilibrium data were fitted and interpreted by the Freundlich model. Metals-saturated husk samples resulting from column tests were air-dried and incinerated to simulate combustion in order to assess the fate of sorbed metals. The results demonstrated that, under both equilibrium and dynamic conditions, metal sorption capacity of the husk was in the sequence Pb>Cd>Cu>Zn. For all the metals, calculated Freundlich constants decreased by increasing initial metal concentration or decreasing solution pH. In dynamic tests, a significant reduction of sorption capacity was recorded (except for copper) when a metal was fed simultaneously to the others: Pb (77%); Cd (93%); Zn (68%). Combustion tests carried out on metals-saturated husk samples showed that the average losses of lead and cadmium, as volatile species, were always three to four times greater than the losses of copper and zinc, in both single-metal- and multimetal-saturated samples.

Sorption properties of an amorphous hydroxo titanate towards Pb2+, Ni2+, and Cu2+ ions in aqueous solution

ABSTRACT Titanates may be selectively used as inorganic adsorbents for heavy metal ions owing to their stability and fast adsorption kinetics. Nevertheless, the synthesis of such materials usually requires extreme reaction conditions. In this work, a new titanium-based material was rapidly synthesized under mild laboratory conditions. The obtained amorphous hydroxo titanate was tested for heavy metal sorption through kinetic and equilibrium batch tests, which indicated that the new material had high adsorption rates and adsorption capacities towards Cu2+, Ni2+ and Pb2 ions. Adsorption kinetics were pseudo-second order, and equilibrium data fitted the Langmuir isotherm model. The calculated maximum adsorption capacities of Cu2+, Ni2+ and Pb2+ in deionized water were around 1 mmol g−1, and they decreased for Cu2+ and Ni2+ in the presence of Na+, Ca2+ and Mg2+ ions, whereas the alkali metal ions did not influence Pb2+ uptake. The efficiency of adsorption and recovery of lead ions were evaluated through column dynamic tests, by feeding the column with groundwater and tap water spiked with Pb2+. The high performance of the hydroxo titanate over several cycles of retention and elution suggested that the product is potentially useful for the solid phase extraction of lead at trace levels in natural water samples, with potential use in metal pre-concentration for analytical applications.

Fingerprinting Hydrocarbons in a Contaminated Soil from an Italian Natural Reserve and Assessment of the Performance of a Low-Impact Bioremediation Approach

An environmentally friendly procedure suitable to restore a protected area was evaluated at laboratory scale. Soil contaminated by high molecular weight (C > 10) aliphatic hydrocarbons and by chromium was withdrawn from the study site and a qualitative study of soil hydrocarbon components was first performed in order to assess the potential source of contamination. To this aim, a number of characteristic diagnostic ratios of hydrocarbon components were derived by processing chromatographic data, and were used as indicators for distinguishing anthropogenic from natural hydrocarbons. Then, the efficiency of landfarming for soil remediation was tested by comparing the effect of a few selected amendments and by monitoring the fate of chromium. Soil microbial abundance and activity were also evaluated. Results showed that soil hydrocarbons were mainly of anthropogenic origin and land treatment allowed effective degradation by native microbial populations even in the absence of amendments. The investigated procedures had no effect on the mobilisation of chromium that remained in its stable form of Cr(III). Conventional land treatment may therefore be an effective and safe procedure for the removal of hydrocarbons even in the presence of chromium, and may be applied to areas where low-impact procedures are strictly required.