Gamma irradiation of 2-mercaptobenzothiazole aqueous solution in the presence of persulfate.

Recently, water treatment by ionizing radiation has gained increasing attention as a powerful technology for the destruction of refractory pollutants. 2-Mercaptobenzothiazole (MBT) is known as a widespread, toxic and poorly biodegradable pollutant. This paper studied the gamma irradiation of aqueous solutions of MBT. Moreover, the effect of the addition of persulfate (S2O8(2-)) on the radiolytic destruction of MBT was investigated. The main transformation products of the studied compound were detected and the sequence of occurrence of the products was described. The change of biodegradability of MBT solution was also observed. The main results obtained in this study indicated that gamma radiation was effective for removing MBT in aqueous solution. Persulfate addition, which induced the formation of reactive sulfate radicals (SO4(-)), greatly enhanced the degradation of MBT. Benzothiazole was identified as the first radiation product, followed by 2-hydroxybenzothiazole. Decomposition of MBT started with the oxidation of -SH groups to sulfate ions. Possible pathways for MBT decomposition by gamma irradiation were proposed. The BOD/COD ratios of MBT samples were increased after radiation, indicating the improvement of biodegradability and reduction of toxicity.

Radiation induced decomposition of a refractory cefathiamidine intermediate.

Diisopropylthiourea (DPT), an intermediate of a widely used cephalosporin, has been found to be one of the most refractory components in cephalosporin synthesis wastewater. This compound cannot be completely removed by conventional biological processes due to its antimicrobial property. Ionizing radiation has been applied in the decomposition of refractory pollutants in recent years and has proved effective. Therefore, the decomposition of DPT by γ-irradiation was studied. The compound was irradiated at the dose of 150-2000 Gy before a change of concentration and UV absorption of the solutions was detected. Furthermore, the decomposition kinetics and radiation yield (G-value) of DPT was investigated. The results of radiation experiments on DPT-containing aqueous showed that the DPT can be effectively degraded by γ-radiation. DPT concentration decreased with increasing absorbed doses. G-values of radiolytic decomposition for DPT (20 mg/L) were 1.04 and 0.47 for absorbed doses of 150 and 2000 Gy, respectively. The initial concentration and pH of the solutions affected the degradation. As the concentration of substrate increased, the decomposition was reduced. The decrease of removal rate and radiation efficacy under alkaline condition suggested that lower pH values benefit the γ-induced degradation. UV absorption from 190 to 250 nm decreased after radiation while that from 250 to 300 nm increased, indicating the formation of by-products.

Transport and release of electron donors and alkalinity during reductive dechlorination by combined emulsified vegetable oil and colloidal Mg(OH)2: Laboratory sand column and microcosm tests.

Emulsified vegetable oil combined with colloidal Mg(OH)2 (EVO-CM) can slowly release electron donors and OH- into groundwater and is therefore regarded as a promising amendment for enhanced in situ treatment of chlorinated solvents, such as tetrachloroethene (PCE) and trichloroethene (TCE). However, its migration ability in different porous media and the simultaneous release of electron donor and pH buffer during enhanced reductive dechlorination (ERD) have never been evaluated in detail. In this study, EVO-CM with uniform drop size and desirable stability was prepared. Laboratory-scale column tests were conducted to investigate the transport and spatial distribution of the EVO-CM in different porous media. Batch microcosm experiments were carried out to study the dechlorination efficiency under different EVO:Mg(OH)2 ratios. Experimental results indicate that prepared EVO-CM emulsions can be transported effectively through different porous media with grain size ranging from 0.1-1.0 mm. The emulsified vegetable oil (EVO) and colloidal Mg(OH)2 showed synchronous movement through the porous media column systems, providing both electron donor and alkalinity at the same location. The retention degree of EVO-CM is greater in the finer grained media and decreases with increasing distance from the inlet. The injection of EVO-CM lead to a significant mobilization of TCE in the column. The reductive dechlorination of TCE in the microcosms was remarkably enhanced in the presence of EVO-CM. The coaddition of sufficient colloidal Mg(OH)2 effectively limits the deleterious pH decline caused by acid release. The microcosm achieves an optimum dechlorination efficiency when the EVO:Mg(OH)2 ratio is 1:1.

Simulated reactive zone with emulsified vegetable oil for the long-term remediation of Cr(VI)-contaminated aquifer: dynamic evolution of geological parameters and groundwater microbial community.

Cr(VI), which is highly toxic and soluble, is one of the most challenging groundwater contaminants. Previous work has indicated that emulsified vegetable oil (EVO) is an effective in situ amendment for removing Cr(VI) from groundwater. However, the spatial and temporal changes in geological parameters and microbial community structures throughout the remediation period are poorly understood. In this study, a large laboratory-scale sand-packed chamber (reactive zone of 100 × 50 × 30 cm) was used to simulate the bioremediation of Cr(VI)-contaminated aquifer by EVO over a 512-day period. Various geological parameters and microbial communities were monitored during both the establishment and remediation stages. The results indicate that several biogeochemical reactions occurred in a specific sequence following the injection of EVO, creating an acidic and reducing environment. A shift in the community structure and a decrease in the community diversity were observed. The abundance of microbes involved in the degradation of EVO and reduction of electron acceptors significantly increased. Then, the EVO reactive zone was flushed with Cr(VI)-contaminated groundwater. Biogeochemical reactions were inhibited after the inflow of Cr(VI) and subsequently recovered a month later. The pH of the aquifer returned to the initial neutral condition (approximately 7.2). The EVO reactive zone could remediate Cr(VI)-contaminated groundwater at an efficiency exceeding 97% over 480 days. Biogeochemistry played a major role in the early period (0~75 days). In the later period (240~480 days), the remediation of Cr(VI) in the reactive zone depended mostly on bio-reduction by Cr(VI)-reducing bacteria.

A 2D tank test on remediation of nitrobenzene-contaminated aquifer using in-situ reactive zone with emulsified nanoscale zero-valent iron.

Nitrobenzene (NB) is one of the most challenging pollutants for groundwater remediation due to its great harm and recalcitrance. Emulsified nanoscale zero-valent iron (EZVI) is considered as a promising agent for in-situ remediation of contaminated groundwater for its high reactivity, good durability and low cost. In this paper, 2D tank experiment was conducted to evaluate the effectiveness of enhanced remediation of NB-contaminated groundwater with EZVI. 9 L of EZVI solution was injected into aquifer to establish in-situ reactive zone (IRZ) before 40 d of NB contamination. Results indicate that injection of EZVI leads to 90% reduction of total NB, which is mainly converted to aniline (AN). NB concentration decreases along the flow path in the tank. Fe2+ is generated from Fe0 oxidation. Significant acetate and bicarbonate are released due to emulsified oil decomposition during the whole operation time. Groundwater pH maintains in neutral value (6.6-8.2) owing to the balance between organic acids and OH- released after iron oxidation. Drastic decrease of ORP and DO indicates the transformation from oxidizing to reducing condition, leading to the reduction of oxidative species (e.g. sulfate, nitrate) in subsurface. Calculation of reducing equivalents suggests that microbial breakdown of emulsified oil provides more electrons than Fe0 oxidation does to the system. Both biotic and abiotic processes are involved in the enhanced degradation of NB.

In situ reactive zone with modified Mg(OH)2 for remediation of heavy metal polluted groundwater: Immobilization and interaction of Cr(III), Pb(II) and Cd(II).

Mg(OH)2 dissolves slowly and can provide a long-term source of alkalinity, thus a promising alternative reagent for the in situ remediation of heavy metal polluted groundwater. However, the application of Mg(OH)2 on in situ reactive zone (IRZ) for heavy metal polluted groundwater has never been investigated. In this study, the behaviors of heavy metals in a Mg(OH)2 IRZ were monitored for 45d. The heavy metals show a sequential precipitation by modified Mg(OH)2 due to the difference of Ksp. Column tests were conducted to investigate the temporal and spatial distribution of heavy metals in Mg(OH)2 IRZ and evaluate the stabilization effect for multi-heavy metal polluted groundwater. Experimental results indicate that there exist interactions between different heavy metals, and their zoning distribution is attributed either to the competitive adsorption onto porous media (control column) or to the sequential precipitation of heavy metal ions (IRZ column). In contrast with the control column, heavy metal contaminated area in Mg(OH)2 IRZ significantly shrinks. According to the chemical speciation analysis, when water containing Pb(II), Cd(II) and Cr(III) flows through Mg(OH)2 IRZ, exchangeable fraction of total concentration significantly reduce and the proportion of carbonate and Fe/Mn oxides fraction increase, indicating the decrease of their mobility and toxicity.