International audience | In order to determine the mechanisms of the retention of 60Co, 85Sr and 134Cs in natural silica sand columns, desorption experiments were performed by changes of pH and ionic strength and by injection of natural organic matter (NOM). Injection of KCl (0.1 M) resulted in a high release of 60Co (60-100%) and 85Sr (72-100%) but a smaller release of 134Cs (31-66%). Only limited release of 60Co (66%) and 85Sr (71%) and no release of 134Cs were observed by injection of NOM. The different percentages of desorption were related to the chemical characteristics of the organic colloids previously retained in columns before the desorption step. The results evidenced different sorption processes on energetically heterogeneous surface sites. According to the initial conditions, the binding of the radionuclides to the solid phase resulted from weak and easily reversible sorption processes to strong association probably by inner sphere complexes. The rather weak release of 134Cs by KCl was attributed to the strong retention of 134Cs by clay coatings on the natural silica sand surfaces. © 2005 Elsevier Ltd. All rights reserved.

The toxicity of organic aerosols has been largely ascribed to the generation of reactive oxygen species, which could subsequently induce oxidative stress in biological systems. The reaction of DTT with redox-active species in PM has been generally assumed to be pseudo-first order, with the oxidative potential of PM being represented by the DTT consumption per minute of reaction time per μg of PM. Although catalytic reactive species such as transition metals and quinones are long believed to be the main contributors of DTT responses, the role of non-catalytic DTT reactive species such as organic hydroperoxides (ROOH) and electron-deficient alkenes (e.g., conjugated carbonyls) in DTT consumption has been recently highlighted. Thus, understanding the reaction kinetics and mechanisms of DTT consumption by various PM components is required to interpret the oxidative potential measured by DTT assays more accurately. In this study, we measured the DTT consumptions over time and characterized the reaction products using model compounds and secondary organic aerosols (SOA) with varying initial concentrations. We observed that the DTT consumption rates linearly increased with both initial DTT and sample concentrations. The overall reaction order of DTT with non-catalytic reactive species and SOA in this study is second order. The reactions of DTT with different functional groups have significantly different rate constants. The reaction rate constant of isoprene SOA with DTT is mainly determined by the concentration of ROOH. For toluene SOA, both ROOH and electron-deficient alkenes may dominate its DTT reaction rates. These results provide some insights into the interpretation of DTT-based aerosol oxidative potential and highlight the need to study the toxicity mechanism of ROOH and electron-deficient alkenes in PM for future work.

Perfluorohexane sulfonate (PFHxS) has been newly recommended to be added into the Stockholm Convention on persistent organic pollutants (POPs). As one of the major perfluoroalkyl pollutants, its long half-time in human serum and neurotoxicity are cause for significant concern. Although mechanochemical degradation has been evaluated as a promising ecofriendly technology to treat pollutants, the extraordinary stability of poly- and perfluoroalkyl substances (PFASs) raises harsh requirements for co-milling reagents. In the present study, zero-valent iron (ZVI) and ferrate(VI) were for the first time used as the co-milling reagents to degrade PFHxS. When ZVI and ferrate(VI) were used alone, both the degradation and defluorination efficiencies were low. However, after milling at the optimum ratio (ferrate(VI):ZVI = 1:2) for 4 h, the synergistic effect of ZVI and ferrate(VI) resulted in almost complete degradation (100%) and defluorination (95%). Two points can account for this excellent performance: (1) the mechanochemical energy input in the system initiates and prominently promotes related reactions; and (2) the active species generated from the reactions among ZVI, ferrate(VI) and other high-valent iron species will accelerate the process of electron transfer. The sulfonate group comprises the favorable attack sites, as corroborated by both the identified intermediates and quantum chemical calculations. The homolysis of the C–S bond is not only the triggering step, but also the rate-limiting step. In summary, the present work confirms the feasibility and underlying mechanism of the ZVI–ferrate(VI) co-milling system to defluorinate PFHxS, which might be a promising technology to treat PFASs in solid wastes.

Increasing attention has been attracted in developing new technologies to remove chlorofene (CF) and dichlorofene (DCF), which were active agents in antimicrobials for general cleaning and disinfecting. This study investigated the significant influences of bicarbonate (HCO3−) on the degradation of CF and DCF in the Cu(II)-mediated Fenton-like system Cu2+/H2O2. Our results indicate that HCO3− may play a dual role to act 1) as a ligand to stabilize Cu(II), forming soluble [CuII(HCO3−)(S)]+ species to catalyze H2O2 producing hydroxyl radical (OH) and superoxide ion (O2−) and 2) as a OH scavenger. Furthermore, the reaction kinetics, mechanisms, and intermediates of CF and DCF were assessed. The apparent rate constants of CF and DCF were enhanced by a factor of 8.5 and 5.5, respectively, in the presence of HCO3− at the optimized concentration of 4 mM. Based on the intermediate identification and frontier electron densities (FEDs) calculations, the associated reaction pathways were tentatively proposed, including C–C scission, single or multiple hydroxylation, and coupling reaction. In addition, significant reduction in the aquatic toxicity of CF and DCF was observed after treatment with Cu2+/H2O2–HCO3- system, evaluated by Ecological Structure Activity Relationships (ECOSAR) program. These findings provide new insights into Cu(II)-mediated reactions to better understand the environmental fate of organic contaminants in carbonate-rich waters.

Low temperatures and frequent soil freeze–thaw in polar environments present challenges for the immobilisation of metals. To address these challenges we investigated the chemical forms of Pb, Zn and Cu in an Antarctic landfill, examined in vitro reaction kinetics of these metals and orthophosphate at 2 and 22 °C for up to 185 days, and subjected the products to freeze–thaw. Reaction products at both temperatures were similar, but the rate of production varied, with Cu-PO₄ phases forming faster, and the Zn- and Pb-PO₄ phases slower at 2 °C. All metal-orthophosphate phases produced were stable during a 2.5 h freeze–thaw cycle to −30 °C. Metal immobilisation using orthophosphate can be successful in polar regions, but treatments will need to consider differing mineral stabilities and reaction rates at low temperatures.

Here we investigate the photodegradation of structurally similar organophosphorus pesticides; methyl-parathion and fenitrothion in water (20 °C) and ice (−15 °C) under environmentally-relevant conditions with the aim of comparing these laboratory findings to limited field observations. Both compounds were found to be photolyzed more efficiently in ice than in aqueous solutions, with quantum yields of degradation being higher in ice than in water (fenitrothion > methyl-parathion). This rather surprising observation was attributed to the concentration effect caused by freezing the aqueous solutions. The major phototransformation products included the corresponding oxons (methyl-paraoxon and fenitroxon) and the nitrophenols (3-methyl-nitrophenol and nitrophenol) in both irradiated water and ice samples. The presence of oxons in ice following irradiation, demonstrates an additional formation mechanism of these toxicologically relevant compounds in cold environments, although further photodegradation of oxons in ice indicates that photochemistry of OPs might be an environmentally important sink in cold environments. Photodegradation of methyl-parathion and fenitrothion in water and ice under environmentally-relevant conditions is described.

The adsorption/transformation of two members (clarithromycin and roxithromycin) of the macrolide (ML) antibacterial agents on the surface of three environmental subsurface sorbents (clay, iron(III) and manganese(IV) oxy-hydroxides) was investigated. The adsorption fitted well to the Freundlich model with a high sorption capacity. Adsorption probably occurred through a surface complexation mechanism and was accompanied by slow degradation of the selected MLs. Transformation proceeded through two parallel pathways: a major pathway was the hydrolysis of the cladinose sugar, and to a lesser extent the hydrolysis of the lactone ring. A minor pathway was the N-dealkylation of the amino sugar. This study indicates that Fe(III) and Mn(IV) oxy-hydroxides in aquatic sediments may play an important role in the natural attenuation of MLs. Such an attenuation route yields a range of intermediates that might retain some of their biological activity. Iron(III) and manganese(IV) oxy-hydroxides in aquatic sediments may play an important role in the natural attenuation of macrolide antibacterial agents.

The effectiveness of biochar as a sorptive material to remove contaminants, particularly heavy metals, from water is dependent on biomass type and pyrolysis condition. Biochars were produced from pulp mill sludge (PMS) and rice straw (RS) with nitrogen (N₂) or carbon dioxide (CO₂) as the purging gas. The sorptive capacity of the biochars for cadmium(II), copper(II), nickel(II) and lead(II) was studied. The heavy metal adsorption capacity was mainly affected by biomass type, with biochars adsorption capacities higher for lead(II) (109.9–256.4 mg g⁻¹) than for nickel(II) (40.2–64.1 mg g⁻¹), cadmium(II) (29.5–42.7 mg g⁻¹) and copper(II) (18.5–39.4 mg g⁻¹) based on the Langmuir adsorption model. The highest lead(II) adsorption capacities for PMS and RS biochars were 256.4 and 133.3 mg g⁻¹, respectively, when generated using N₂ as the purging gas. The corresponding lead(II) adsorption capacities were 250.0 and 109.9 mg g⁻¹, respectively, when generated using CO₂ as the purging gas. According to the intraparticle diffusion model, 30–62% of heavy metal adsorption was achieved in 1 h; film diffusion was the rate-dominating step, whereas pore diffusion was a rate-limiting step. Ion exchange and complexation between heavy metals and biochar surface functional groups such as carbonyl and hydroxyl groups were effective mechanisms for heavy metal sorption from the aqueous solution. We conclude that proper selection of both the feedstock type and the purging gas is important in designing biochars for the effective removal of potentially toxic metals from wastewater.

Carbamazepine (CBZ), a widely detected pharmaceutical in wastewaters, cannot currently be treated by conventional activated sludge technologies, as it is highly resistant to biodegradation. In this study, the degradation kinetics and reaction mechanisms of CBZ by hydroxyl radical (OH) and sulfate radical (▪)–based advanced oxidation processes (AOPs) were investigated with a combined experimental/theoretical approach. We first measured the UV absorption spectrum of CBZ and compared it to the theoretical spectrum. The agreement of two spectra reveals an extended π–conjugation system on CBZ molecular structure. The second–order rate constants of OH and ▪ with CBZ, measured by competition kinetics method, were (4.63 ± 0.01) × 10⁹ M⁻¹ s⁻¹ and (8.27 ± 0.01) × 10⁸ M⁻¹ s⁻¹, respectively at pH 3. The energetics of the initial steps of CBZ reaction with OH and ▪ were also calculated by density functional theory (DFT) at SMD/M05–2X/6–311++G**//M05–2X/6–31 + G**level. Our results reveal that radical addition is the dominant pathway for both OH and ▪. Further, compared to the positive ΔGR0 value for the single electron transfer (SET) reaction pathway between CBZ and OH, the ΔGR0 value for SET reaction between CBZ and ▪ is negative, showing that this reaction route is thermodynamically favorable. Our results demonstrated the remarkable advantages of AOPs for the removal of refractory organic contaminants during wastewater treatment processes. The elucidation of the pathways for the reaction of OH and ▪ with CBZ are beneficial to predict byproducts formation and assess associated ecotoxicity, providing an evaluation mean for the feasibility of AOPs application.

2,6-Dichloro-4-nitrophenol (2,6-DCNP) is an emerging chlorinated nitroaromatic pollutant, and its fate in the environment is an important question. However, microorganisms with the ability to utilize 2,6-DCNP have not been reported. In this study, Cupriavidus sp. CNP-8 having been previously reported to degrade various halogenated nitrophenols, was verified to be also capable of degrading 2,6-DCNP. Biodegradation kinetics assay showed that it degraded 2,6-DCNP with the specific growth rate of 0.124 h⁻¹, half saturation constant of 0.038 mM and inhibition constant of 0.42 mM. Real-time quantitative PCR analyses indicated that the hnp gene cluster was involved in the catabolism of 2,6-DCNP. The hnpA and hnpB gene products were purified to homogeneity by Ni-NTA chromatography. Enzymatic assays showed that HnpAB, a FAD-dependent two-component monooxygenase, converted 2,6-DCNP to 6-chlorohydroxyquinol with a Kₘ of 3.9 ± 1.4 μM and a kcₐₜ/Kₘ of 0.12 ± 0.04 μΜ⁻¹ min⁻¹. As the oxygenase component encoding gene, hnpA is necessary for CNP-8 to grow on 2,6-DCNP by gene knockout and complementation. The phylogenetic analysis showed that the hnp cluster originated from the cluster involved in the catabolism of chlorophenols rather than nitrophenols. To our knowledge, CNP-8 is the first bacterium with the ability to utilize 2,6-DCNP, and this study fills a gap in the microbial degradation mechanism of this pollutant at the molecular, biochemical and genetic levels. Moreover, strain CNP-8 could degrade three chlorinated nitrophenols rapidly from the synthetic wastewater, indicating its potential in the bioremediation of chlorinated nitrophenols polluted environments.