Transformation of chlorobenzene by Mn(III) generated in MnO2/organic acid systems.

Chlorobenzene (CB) is a prevalent organic contaminant in water and soil environments. It presents high chemical stability and is resistant to both oxidation and reduction. In this study, we showed that CB was substantially removed by soluble Mn(III) produced during the reductive dissolution of colloidal MnO2 by naturally-occurring organic acids such as formate (FOR), oxalate (OX), and citrate (CIT). The removal rate was dependent on the physicochemical properties of organic acids. With strong electron-donating and coordination ability, OX and CIT promoted MnO2 dissolution and Mn(III) generation compared to FOR, but had adverse effects on the stability and reactivity of Mn(III). As a result, CB removal followed the order: MnO2/CIT > MnO2/FOR > MnO2/OX. Analysis of the transformation products showed that Mn(III) complexes acted as strong electrophiles, attacking the ortho/para carbons of the benzene ring and transforming CB to chlorophenols via an electrophilic substitution mechanism. The theoretical foundation of this proposed reaction mechanism was supplemented by quantum mechanical calculations. Together, the findings of this study provide new insights into the transformation of CB in natural environments and hold the potential to offer a novel strategy for the development of manganese oxide/ligand systems for CB elimination.

Effects of phosphate, silicate, humic acid, and calcium on the release of As(V) co-precipitated with Fe(III) and Fe(II) during aging.

The effects of phosphate (P), silicate (Si), humic acid (HA), and calcium (Ca) on the release of As(V) co-precipitated with Fe(III) and Fe(II) during aging were investigated. As(V) in synthetic groundwater could be efficiently removed by both Fe(III) and Fe(II) processes. The addition of P remarkably decreased As(V) removal efficiency while no obvious release of As(V) during aging was observed. Si and HA reduced As(V) removal to a less extent than P but caused notable As(V) release during aging. FTIR spectra and particle size of the precipitates before and after aging indicated that As(V) release in the presence of Si was due to the serious structural transformation and particle aggregation of the precipitates during aging. While for HA, As(V) release was caused by sorption of HA on the precipitates and dissolution of the precipitates by HA. The addition of Ca partially counteracted the adverse impacts of P, Si, and HA and promoted As(V) removal efficiency but had limited inhibitory effect on As(V) release as it induced more serious particle aggregation during aging. The results demonstrated that the release of As(V) caused by Si and HA should be considered when using Fe coagulation for in-situ treatment of As(V) contaminated groundwater.

Effects of Fe(III) and Cu(II) on the sorption of s-triazine herbicides on clay minerals.

The effects of Fe(III) and Cu(II) on the sorption of atrazine (AT) and prometryn (PY) on clay minerals were investigated both preloaded and in solution. For smectite, Fe(III) preloading greatly enhanced AT and PY sorption at pH 4.0 and 6.0 but diminished AT sorption at pH 8.0. Cu(II) preloading promoted AT and PY sorption under alkaline conditions but suppressed AT sorption at pH 4.0. The adverse effects were not obvious for PY. While for illite and kaolinite, Fe(III) and Cu(II) had little or promotion effects due to the lower contents of them in these two minerals. In the co-sorption studies, for smectite, AT sorption remained at pH 4.0 and increased at pH 6.0 and 8.0, while PY sorption was inhabited over the pH range of 4.0-8.0 in the presence of Fe(III). AT and PY sorption were not affected by Cu(II) except for PY at pH 8.0, in which case, the sorption was promoted. For illite and kaolinite, Fe(III) and Cu(II) generally enhanced AT and PY sorption.

Impact of dissolved O2 on phenol oxidation by δ-MnO2.

Although redox reactions of organic contaminants with manganese oxides have been extensively studied, the role of dissolved O2 in these processes has largely been overlooked. In this study, the oxidative degradation of phenol by δ-MnO2 was investigated under both oxic and anoxic conditions. Dissolved O2 inhibited phenol degradation due to its promoting role in the reoxidation and precipitation of reduced Mn(ii) to Mn(iii) on the δ-MnO2 surface, resulting in partial transformation of δ-MnO2 to "c-disordered" H+-birnessite at pH 5.5 and feitknechtite, manganite, and hausmannite at pH 7.0 and 8.5. The reformed Mn(iii) phases could reduce phenol oxidation by blocking reactive sites of δ-MnO2. In addition, dissolved O2 caused a higher degree of particle agglomeration and a more severe specific surface area decrease, and hence lower reactivity of δ-MnO2. These findings revealed that after reductive dissolution by phenol and reoxidation by dissolved O2 throughout continuous redox cycling, δ-MnO2 became less reactive rather than being regenerated. These results can provide new insights into the understanding of the oxidation of organic contaminants by manganese oxides in the natural environment.

Sorption of Non-ionic Aromatic Organics to Mineral Micropores: Interactive Effect of Cation Hydration and Mineral Charge Density.

The influence of K+ and Ca2+ on the sorption of non-ionic aromatic contaminants (1,4-dinitrobenzene and p-xylene) on a series of microporous zeolite minerals (HZSM-5) with various surface charge densities was investigated. For zeolites with high or low charge density (>1.78 or <0.16 sites/nm2), K+ and Ca2+ had negligible influence on the sorption of organics, which mainly occurred at the hydrophobic nanosites. For zeolites with charge density in the moderate range (0.16-1.78 sites/nm2), the sorption of organics was strongly dependent upon the cation hydration effect. K+ with a lower hydration free energy greatly favored sorption of organics to the micropores compared to Ca2+. Differential scanning calorimetry and X-ray photoelectron spectroscopy results indicated that K+ can reduce the water affinity and promote specific sorption of organics in the zeolites with moderate charge density. The above mechanisms were successfully applied to explain the retention of 1,4-dinitrobenzene and p-xylene on four natural minerals (smectite, illite, kaolinite, and mordenite). This study shed new insights on how cation hydration influences sorption interactions of non-ionic aromatic contaminants at mineral-water interfaces as a function of the mineral charge density.

Chromium(VI) removal by mechanochemically sulfidated zero valent iron and its effect on dechlorination of trichloroethene as a co-contaminant.

Mechanochemically sulfidated microscale zero valent iron (S-mZVIbm) is a promising groundwater remediation material as it has been proven to be not only efficient in dechlorinating chlorinated compounds but also amenable to up-scaling. Yet, its efficiency in treating metal contaminants remains barely studied. In this study, we investigated the mechanism and efficiencies of Cr(VI) removal by S-mZVIbm and its effect on TCE dechlorination as a co-contaminant. The Cr(VI) removal by S-mZVIbm was mainly a chemisorption process and its kinetics was well fitted by a pseudo-second-order model. Alkaline pH inhibited Cr(VI) removal while dissolved oxygen slightly depressed the Cr(VI) removal. The Cr(VI) removal rapidly formed a non-conductive layer on S-mZVIbm surface to hinder further electron transfer from Fe0 core before H+ was able to accept any electrons to produce H2, which resulted in 100% electron efficiencies of Cr(VI) removal but <1% of Fe0 utilization efficiency. The presence of Cr(VI) also dramatically inhibited the dechlorination of TCE and its electron efficiency as a co-contaminant by passivating the FeS surface. Therefore, Cr(VI) is likely to be an electron sink if present for remediation of other contaminants in groundwater.

Role of dissolved Mn(III) in transformation of organic contaminants: Non-oxidative versus oxidative mechanisms.

Mn(III) is a strong oxidant for one electron transfer, which may be important in the transformation of organic contaminants during water/wastewater treatment and biogeochemical redox processes. This study explored the reaction mechanisms of dissolved Mn(III) with organics. The role of dissolved Mn(III) either as a catalyst or an oxidant in reactions with organics was recognized. Aquo and/or hydroxo (or free) Mn(III), generated from the bisulfite activated permanganate process, facilitated efficient N-dealkylation of atrazine via a ß-elimination mechanism, resulting no net redox reaction. In contrast, free Mn(III) degraded 4-chlorophenol via intramolecular redox processes, the same as hydroxyl radical (OH), resulting in dechlorination,OH substitution, ring-opening and mineralization. Mn(III)-pyrophosphate compounds did not react with atrazine because complexation by pyrophosphate rendered Mn(III) unable to bond with atrazine, thus the electron and proton transfers between the reactants couldn't occur. However, it degraded 4-chlorophenol at a slower rate compared to free Mn(III), due to its reduced oxidation potential. These results showed two distinct mechanisms on the degradation of organic contaminants and the insights may be applied in natural manganese-rich environments and water treatment processes with manganese compounds.

Performance of a novel microwave-based treatment technology for atrazine removal and destruction: Sorbent reusability and chemical stability, and effect of water matrices.

Transition metal-exchanged dealuminated Y zeolites were used to adsorb atrazine from aqueous solutions, followed by regeneration of the sorbents and destruction of the sorbed atrazine with microwave irradiation. Exchange of copper and iron into the zeolite's micropores significantly enhanced its sorption capacity and selectivity toward atrazine, and increased the microwave-induced degradation rate of the sorbed atrazine by 3-4-folds. Both the copper- and iron-exchanged zeolites could be regenerated and reused multiple times, while the catalytic activity of the latter was more robust due to the much greater chemical stability of Fe(3+) species in the micropores. The presence of humic acid, and common cations and anions had little impact on the sorption of atrazine on the transition metal-exchanged zeolites. In the treatment of atrazine spiked in natural surface water and groundwater samples, sorptive removal of atrazine was found to be impacted by the level of dissolved organic carbon, probably through competition for the micropore spaces and pore blocking, while the water matrices exhibited no strong effect on the microwave-induced degradation of sorbed atrazine. Overall, iron-exchanged dealuminated Y zeolites show great potential for removal and destruction of atrazine from contaminated surface water and groundwater in practical implementation of the novel treatment technology.

Arsenic pollution of agricultural soils by concentrated animal feeding operations (CAFOs).

Animal wastes from concentrated animal feeding operations (CAFOs) can cause soil arsenic pollution due to the widespread use of organoarsenic feed additives. This study investigated the arsenic pollution of surface soils in a typical CAFO zone, in comparison with that of agricultural soils in the Pearl River Delta, China. The mean soil arsenic contents in the CAFO zone were elevated compared to those in the local background and agricultural soils of the Pearl River Delta region. Chemical speciation analysis showed that the soils in the CAFO zone were clearly contaminated by the organoarsenic feed additive, p-arsanilic acid (ASA). Transformation of ASA to inorganic arsenic (arsenite and arsenate) in the surface soils was also observed. Although the potential ecological risk posed by the arsenic in the surface soils was relatively low in the CAFO zone, continuous discharge of organoarsenic feed additives could cause accumulation of arsenic and thus deserves significant attention.

Catalytic effect of transition metals on microwave-induced degradation of atrazine in mineral micropores.

With their high catalytic activity for redox reactions, transition metal ions (Cu(2+) and Fe(3+)) were exchanged into the micropores of dealuminated Y zeolites to prepare effective microporous mineral sorbents for sorption and microwave-induced degradation of atrazine. Due to its ability to complex with atrazine, loading of copper greatly increased the sorption of atrazine. Atrazine sorption on iron-exchanged zeolites was also significantly enhanced, which was attributed to the hydrolysis of Fe(3+) polycations in mineral micropores and electrostatic interactions of protonated atrazine molecules with the negatively charged pore wall surface. Copper and iron species in the micropores also significantly accelerated degradation of the sorbed atrazine (and its degradation intermediates) under microwave irradiation. The catalytic effect was attributed to the easy reducibility and high oxidation activity of Cu(2+) and Fe(3+) species stabilized in the micropores of the zeolites. It was postulated that the surface species of transition metals (monomeric Cu(2+), Cu(2+)-O-Cu(2+) complexes, FeO(+), and dinuclear Fe-O-Fe-like species) in the mineral micropores were thermally activated under microwave irradiation, and subsequently formed highly reactive sites catalyzing oxidative degradation of atrazine. The transition metal-exchanged zeolites, particularly the iron-exchanged ones, were relatively stable when leached under acidic conditions, which suggests that they are reusable in sorption and microwave-induced degradation. These findings offer valuable insights on designing of effective mineral sorbents that can selectively uptake atrazine from aqueous solutions and catalyze its degradation under microwave irradiation.

Impact of surface chemistry on microwave-induced degradation of atrazine in mineral micropores.

Surface chemistry determines the interactions of sorbate and solvent molecules with the pore wall surfaces of microporous minerals, and affects the transmission and absorption of microwave radiation for a given solvent-sorbate-sorbent system. The sorption and microwave-induced degradation of atrazine in the micropores of nine Y zeolites with different densities (0.16-2.62 site/nm(2)) and types (Mg(2+), Ca(2+), H(+), Na(+), and NH(4)(+)) of surface cations were studied. The influence of the content of cosorbed water in the mineral micropores on atrazine degradation rate was also examined. The results indicate the presence of surface cations at around 0.23 site/nm(2) on the pore wall surface was optimal for atrazine degradation, probably due to formation of insufficient number of "hot spots" with too few cations but excessive competition for microwave energy with too many hydrated cations. Atrazine degraded faster in the presence of cations with lower hydration free energies, which could be attributed to less microwave energy consumption to desorb the bounded water molecules. Reducing the content of coadsorbed water in the micropores also increased atrazine degration rate because of less competition for microwave energy from water. Such mechanistic understanding can guide the design and selection of microporous minerals in the practical application of microwave-induced degradation.

Microwave-induced degradation of atrazine sorbed in mineral micropores.

The herbicide atrazine is a common pollutant in reservoirs and other sources of drinking water worldwide. The adsorption of atrazine from water onto zeolites CBV-720 and 4A, mesoporous silica MCM-41, quartz sand, and diatomite, and its microwave-induced degradation when sorbed on these minerals, were studied. Dealuminated HY zeolite CBV-720 exhibited the highest atrazine sorption capacity among the mineral sorbents because of its high micropore volume, suitable pore sizes, and surface hydrophobicity. Atrazine sorbed on the minerals degraded under microwave irradiation due to interfacial selective heating by the microwave, while atrazine in aqueous solution and associated with PTFE powder was not affected. Atrazine degraded rapidly in the micropores of CBV-720 under microwave irradiation and its degradation intermediates also decomposed with further irradiation, suggesting atrazine could be fully mineralized. Two new degradation intermediates of atrazine, 3,5-diamino-1,2,4-triazole and guanidine, were first identified in this study. The evolution of degradation intermediates and changes in infrared spectra of CBV-720 after microwave irradiation consistently indicate the creation of microscale hot spots in the micropores and the degradation of atrazine following a pyrolysis mechanism. These results indicate that microporous mineral sorption coupled with microwave-induced degradation could serve as an efficient treatment technology for removing atrazine from drinking water.

Impact of mineral micropores on transport and fate of organic contaminants: a review.

Nanometer-scale pores are abundant in porous geological media (soils, sediments, and aquifer materials), and may account for over >90% of total mineral surface areas. Sorption of organic contaminants in mineral micropores (<2 nm) plays a key role in controlling their fate and transport when the porous geological media have very low organic carbon contents (<0.1%). Significant adsorption of hydrophobic organic contaminants could only occur in the hydrophobic micropore spaces because of the strong competition from water. The rate of desorption from micropores is very slow due to hindered diffusion, resulting in distinct two-stage desorption behavior for microporous solids. Size exclusion effect prevents micropore-sorbed contaminants from being accessed by microorganisms and their extracellular enzymes, thus reducing their bioavailability and biodegradation rates. Results from recent studies indicate that sorption in micropores can also inhibit abiotic degradation of reactive contaminants by protecting them in confined spaces with little reactive water, slowing down hydrolysis and other water-mediated transformations. As a result of the inhibitory effect on abiotic and biotic transformations, and the slow desorption due to hindered diffusion, sorption in hydrophobic micropores of porous geological media can cause preservation of anthropogenic organic contaminants in the subsurface and may increase their persistence to the time scale of geological ages under appropriate conditions. From a practical perspective, understanding the role of mineral micropores is important in assessing the long-term ecotoxicological risk of organic contaminants in the subsurface and designing remediation strategies.