Environmental Science and Pollution Research

Krýsa, Josef; Mantzavinos, Dionissios; Pichat, Pierre; Poulios, Ioannis

doi: 10.1007/s11356-018-3411-2pmid: 30311120

Diban, Nazely; Urtiaga, Ane

doi: 10.1007/s11356-017-1124-6pmid: 29305801

Electrochemical oxidation (ELOX) with boron-doped diamond (BDD) anodes was successfully applied to degrade a model aqueous solution of a mixture of commercial naphthenic acids (NAs). The model mixture was prepared resembling the NA and salt composition of oil sands process-affected water (OSPW) as described in the literature. The initial concentration of NAs between 70 and 120 mg/L did not influence the electrooxidation kinetics. However, increasing the applied current density from 20 to 100 A/m2 and the initial chloride concentration from 15 to 70 and 150 mg/L accelerated the rate of NA degradation. At higher chloride concentration, the formation of indirect oxidative species could contribute to the faster oxidation of NAs. Complete chemical oxygen demand removal at an initial NA concentration of 120 mg/L, 70 mg/L of chloride and applied 50 A/m2 of current density was achieved, and 85% mineralization, defined as the decrease of the total organic carbon (TOC) content, was attained. Moreover, after 6 h of treatment and independently on the experimental conditions, the formation of more toxic species, i.e. perchlorate and organochlorinated compounds, was not detected. Finally, the use of ELOX with BDD anodes produced a 7 to 11-fold reduction of toxicity (IC50 towards Vibrio fischeri) after 2 h of treatment.

Gomez-Herrero, Esther; Tobajas, Montserrat; Polo, Alicia; Rodriguez, Juan; Mohedano, Angel

doi: 10.1007/s11356-017-0867-4pmid: 29318485

The oxidation of imidazolium (1-hexyl-3-methylimidazolium chloride, HmimCl) and pyridinium (1-butyl-4-methylpyridinium chloride, BmpyrCl) ionic liquids (ILs) by Fenton’s reagent has been studied. Complete conversion was achieved for both ILs using the stoichiometric H2O2 dose at 70 °C, reaching final TOC conversion values around 45 and 55% for HmimCl and BmpyrCl, respectively. The decrease in hydrogen peroxide dose to substoichiometric concentrations (20–80% stoichiometric dose) caused a decrease in TOC conversion and COD removal and the appearance of hydroxylated oxidation by-products. Working at these substoichiometric H2O2 doses allowed the depiction of a possible degradation pathway for the oxidation of both imidazolium and pyridinium ILs. The first step of the oxidation process consisted in the hydroxylation of the ionic liquid by the attack of the ·OH radicals, followed by the ring-opening and the formation of short-chain organic acids, which could be partially oxidized up to CO2 and H2O. At H2O2 doses near stoichiometric values (80%), the resulting effluents showed non-ecotoxic behaviour and more biodegradable character (BOD5/COD ratio around 0.38 and 0.58 for HmimCl and BmpyrCl, respectively) due to the formation of short-chain organic acids.

Arslan-Alaton, Idil; Olmez-Hanci, Tugba; Ozturk, Tugce

doi: 10.1007/s11356-017-1182-9pmid: 29322392

The effect of varying inorganic (chloride, nitrate, sulfate, and phosphate) and organic (represented by humic acid) solutes on the removal of aqueous micropollutant bisphenol A (BPA; 8.8 μM; 2 mg/L) with the oxidizing agents hydrogen peroxide (HP; 0.25 mM) and persulfate (PS; 0.25 mM) activated using zero-valent aluminum (ZVA) nanoparticles (1 g/L) was investigated at a pH of 3. In the absence of the solutes, the PS/ZVA treatment system was superior to the HP/ZVA system in terms of BPA removal rates and kinetics. Further, the HP/ZVA process was not affected by nitrate (50 mg/L) addition, whereas chloride (250 mg/L) exhibited no effect on the PS/ZVA process. The negative effect of inorganic anions on BPA removal generally speaking increased with increasing charge in the following order: NO3 − (no inhibition) < Cl− (250 mg/L) = SO4 2− < PO4 3− for HP/ZVA and Cl− (250 mg/L; no inhibition) < NO3 − < SO4 2− < PO4 3− for PS/ZVA. Upon addition of 20 mg/L humic acid representing natural organic matter, BPA removals decreased from 72 and 100% in the absence of solutes to 24 and 57% for HP/ZVA and PS/ZVA treatments, respectively. The solute mixture containing all inorganic and organic solutes together partly suppressed the inhibitory effects of phosphate and humic acid on BPA removals decreasing to 46 and 43% after HP/ZVA and PS/ZVA treatments, respectively. Dissolved organic carbon removals were obtained in the range of 30 and 47% (the HP/ZVA process), as well as 47 and 57% (the PS/ZVA process) for the experiments in the presence of 20 mg/L humic acid and solute mixture, respectively. The relative Vibrio fischeri photoluminescence inhibition decreased particularly for the PS/ZVA treatment system, which exhibited a higher treatment performance than the HP/ZVA treatment system.

Ayoub, Hawraa; Roques-Carmes, Thibault; Potier, Olivier; Koubaissy, Bachar; Pontvianne, Steve; Lenouvel, Audrey; Guignard, Cédric; Mousset, Emmanuel; Poirot, Hélène; Toufaily, Joumana; Hamieh, Tayssir

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Foszpańczyk, Magdalena; Drozdek, Emilia; Gmurek, Marta; Ledakowicz, Stanisław

doi: 10.1007/s11356-018-1286-xpmid: 29374377

It is well established that aquatic wildlife in marine and freshwater of the European Union is exposed to natural and synthetic endocrine disruptor compounds (EDCs) which are able to interfere with the hormonal system causing adverse effects on the intact physiology of organisms. The traditional wastewater treatment processes are inefficient on the removal of EDCs in low concentration. Moreover, not only the efficiency of treatment must be considered but also toxicological aspects. Taking into account all these aspects, the main goal of the study was to investigate the photochemical decomposition of hazardous phenolic compounds under simulated as well as natural sunlight from the toxicity point of view. The studies were focused on photodegradation of 2,4-dichlorophenol as well as mixture of phenol, 2-chlorophenol and 2,4-dichlorophenol. Photosensitized oxidation process was carried out in homogeneous and heterogeneous system. V. fischeri luminescence inhibition was used to determine the changes of toxicity in mixture during simulated and natural irradiation. The photodegradation was carried out in three kinds of water matrix; moreover, the influence of presence of inorganic matter on the treatment process was investigated. The experiments with natural sunlight proved applicability of photosensitive chitosan for visible-light water pollutant degradation. The results of toxicity investigation show that using photosensitive chitosan for visible-light, the toxicity of reaction mixture towards V. fischeri has significantly decreased. The EC50 was found to increase over the irradiation time; this increase was not proportional to the transformation of the parent compounds.

Veréb, Gábor; Kovács, Ildikó; Zakar, Mihály; Kertész, Szabolcs; Hodúr, Cecilia; László, Zsuzsanna

doi: 10.1007/s11356-018-1287-9pmid: 29392609

In the present study, oil in water emulsions (c oil = 100 ppm; d oil droplets < 2 μm) was purified with ozonation followed by microfiltration using polyethersulfone (PES) membrane (d pore = 0.2 μm). The effects of pre-ozonation on membrane microfiltration were investigated in detail both in case of ultrapure and model groundwater matrices, applying different durations (0, 5, 10, and 20 min) of pre-ozonation. Simultaneously, the effects of added inorganic water components on the combined method were investigated. Size distribution of oil droplets, zeta potentials, fluxes, and purification efficiencies were measured and fouling mechanisms were described in all cases. It was found that the matrix significantly affected the size distribution and adherence ability of oil droplets onto the membrane surface, therefore fouling mechanisms also were strongly dependent on the matrix. In case of low salt concentration, the total resistance was caused mainly by reversible resistance, which could be significantly reduced (eliminated) by pre-ozonation. In case of model groundwater matrix, nearly twice higher total resistance was measured, and irreversible resistance was dominant, because of the higher adhesion ability of the oil droplets onto the membrane surface. In this case, pre-ozonation resulted in much lower irreversible, but higher reversible resistance. Increased duration of pre-ozonation raised the total resistance and reduced the elimination efficiency (due to fragmented oil droplets and water soluble oxidation by-products) in both cases, therefore short pre-ozonation can be recommended both from economic and performance aspects.

Dominguez, Carmen; Oturan, Nihal; Romero, Arturo; Santos, Aurora; Oturan, Mehmet

doi: 10.1007/s11356-018-1425-4pmid: 29446016

This study is focused on the effective removal of recalcitrant pollutants hexaclorocyclohexanes (HCHs, isomers α, β, γ, and δ) and chlorobenzenes (CBs) present in a real groundwater coming from a landfill of an old lindane factory. Groundwater is characterized by a total organic carbon (TOC) content of 9 mg L−1, pH0 = 7, conductivity = 3.7 mS cm−1, high salt concentration (SO4 2−, HCO3 −, Cl−), and ferrous iron in solution. The experiments were performed using a BDD anode and a carbon felt (CF) cathode at the natural groundwater pH and without addition of supporting electrolyte. The complete depletion of the four HCH isomers and a mineralization degree of 90% were reached at 4-h electrolysis with a current intensity of 400 mA, the residual TOC (0.8 mg L−1) corresponding mainly to formic acid. A parallel series reaction pathway was proposed: HCHs and CBs are transformed into chlorinated and hydroxylated intermediates that are rapidly oxidized to non-toxic carboxylic acids and/or mineralized, leading to a rapid decrease in solution pH.

Vela, Nuria; Calín, May; Yáñez-Gascón, María; Garrido, Isabel; Pérez-Lucas, Gabriel; Fenoll, José; Navarro, Simón

doi: 10.1007/s11356-018-1716-9pmid: 29558788

Endocrine disruptors (EDs) are xenobiotics that interfere with the synthesis, secretion, transport, binding, action, and elimination of the natural hormones. In this paper, the photodegradation of six EDs in municipal wastewater treatment plant effluents at pilot plant scale is reported. The EDs were bisphenol A, bisphenol B, diamyl phthalate, butyl benzylphthalate, methyl p-hydroxybenzoate, and ethyl 4-hydroxybenzoate. ZnO as photocatalyst in tandem with Na2S2O8 as electron acceptor under natural sunlight were used. The process was previously optimized under laboratory conditions through a photoreactor under artificial UVA irradiation studying the role of some key operating parameters (catalyst loading, effect of electron acceptor, and pH). Results carried out at pilot plant scale show that addition of ZnO in tandem with Na2S2O8 strongly enhances degradation rates compared with photolytic test. At the end of the irradiation time (240 min), the remaining amounts of EDs ranged from 24% (butyl benzylphthalate) to 0% (< LOQ bisphenol B). The degradation rates were in the order: bisphenols > parabens > phthalates. After the photoperiod, 83% of the initial dissolved organic carbon was removed and toxicity decreased to acceptable values (11% inhibition to Vibrio fisheri). The photodegradation process was found to follow pseudo-first-order kinetic model with DT50 ranging from 5 min (bisphenol B) to 102 min (butyl benzylphthalate). Thereby, photocatalytic oxidation using ZnO is an area of environmental interest for the treatment of polluted water, particularly relevant for Mediterranean countries, where solar irradiation is highly available.

García-Garay, Juan; Franco-Herrera, Andrés; Machuca-Martinez, Fiderman

doi: 10.1007/s11356-018-2308-4pmid: 29804250

The ballasting and de-ballasting of ships are two necessary operations with ballast water that provide stability for safe navigation. Empty ships must ballast tanks with water, which contains living organisms and subsequently carries them away from their original distribution. De-ballasting represents an input of still viable zooplankton, phytoplankton, and microorganisms in the destination port, leading to the introduction of alien species, and consequently, the introduction of organisms will alter the local biodiversity. Ballast water treatment is necessary to comply with the International Maritime Organization (IMO) for the maximum viable organisms permitted. It is known that UVC eliminates microorganisms, but there are few studies on the other taxonomical groups, such as phytoplankton and zooplankton. The advance oxidation processes (AOPs) with UV-C can be a good alternative to manage the problem of ballast water, primarily for microorganisms. However, for larger organisms, there is more resistance, and, a stage with filtration (by physical filtration or hydrocyclone) is usually required. The filter can fail, or certain zooplankton organisms can escape across the filter and go to the AOPs or UVC reactor. According to the taxonomic group, there can be a different sensitivity to the treatment, and one could survive and generate a risk. The AOPs tested were natural solar radiation (RAD), UV/H2O2, UV/TiO2, UV/TiO2/H2O2, and UV/TiO2/H2O2/RAD. Natural sea water was pumped and treated with the AOPs. The vital zooplankton organisms counted were polychaetes, cladocerans, ostracods, nauplii and calanoid, cyclopoid, and harpacticoid copepods. For the phytoplankton, the abundance was estimated, and the photosystem II efficiency was determined. To evaluate the phytoplankton regrowth after the treatments, the treated water was stored and populations counted for 20 days. The most effective treatment for the zooplankton groups was UVC/H2O2. Regarding the sensitivity, the cyclopoid copepods were the most resistant. The nauplii and polychaetes were more likely to be killed by the AOPs, greatly decreasing the risk from nauplii due to their abundance and ease of passing through the filters with their smaller size. Phytoplankton regrowth was observed in all treatments, and it even reached abundance values higher than in the intake water. For instance, additional dark conditions and retreatment on days 3 or 5 are suggested for any treatment.