Formation and biotoxicity of environmentally persistent free radicals in steelworks soil under thermal treatment.

Thermal treatment are commonly used to address organic contaminated soils. In particular, the pyrolysis of organic substances can result in the creation of environmentally persistent free radicals (EPFRs). We investigated a steelworks site in Chongqing (China) to observe changes in EPFRs before and after thermal treatment. Our findings revealed that the EPFRs were carbon-centered radicals with a g-factor < 2.0030 and a spin density ranging from n.d.-5.23 × 1015 spins/mg. The formation of EPFRs was driving by polycyclic aromatic hydrocarbons (PAHs), Mn, Cu, and total organic carbon (TOC). Following the thermal treatment, the spin densities of EPFRs increased by a factor of 0.25 to 1.81, with maximum levels reached at 300 °C. High molecular weight PAHs exhibited high heat capacity, enabling the generation of more EPFRs. The thermal decay of EPFRs occurred in two stages, with the shortest 1/e lifetime lasting up to 16.8 h. Raising the temperature or prolonging time can significantly reduce EPFRs levels. Thermal treatment increased the generation of EPFRs, hydroxyl radicals (•OH) and superoxide radical (•O2-), leading to a decrease in bacterial luminescence. Specifically, •OH contributed to approximately 73% of the B. brilliantus inhibition. Our results highlight that the thermal treatment significantly enhance EPFRs concentrations, and the treated soil remained ecologically risky. The knowledge of the formation of EPFRs and their biotoxicity is shedding new light on the thermal treatment risk management.

Variations of different PAH fractions and bacterial communities during the biological self-purification in the soil vertical profile.

Wild PAH-contaminated sites struggle to provide continuous and stable monitoring, resulting in the potential risks of contaminated soil utilization could not be evaluated effectively. This work provided a 9-months laboratory simulation which was close to the natural ecological process. These results believed that PAH-degrading bacteria (PDB) preferred to degrade organic extracted PAH (PAH_OS) and fresh bound-PAH (79.36-99.97%). The formation and migration efficiency of PAH binding with HA humic acid (HA) (PAH_HA) was lower than that of PAH binding with fulvic acid (FA) and humin (HM) (PAH_FA and PAH_HM), leading to PAH_HA had more persistent retention and influenced bacterial communities in shallow soils. Besides, phylum Proteobacteria gradually dominated the bacterial community and decreased 12.05-20.48% diversity at all depths during the biological self-purification process. Although the effect of this process enhanced the abundance of 28 genes 16 s rRNA and three PAH-degrading genes (PDGs) by 5.91-2047.34 times (phe, nahAc and nidA), the top 30 genera maintained their ecological characteristics. This study provided insights into the important influencing factor and mechanism of the biological self-purification processes and discerned the linkages between bacterial communities and environmental variables in the vertical profile, which is important to the isolation and application of PDB and ecological risk assessment.

Distribution of bound-PAH residues and their correlations with the bacterial community at different depths of soil from an abandoned chemical plant site.

The situ pollutant residue and microbial characteristics in contaminated environments are crucial for ecological restoration and soil utilization. This work reported the variation of polycyclic aromatic hydrocarbon (PAH) residues and the bacterial community at different depths in an aged-abandoned site. These results unveiled that over 90% of low molecular weight (LMW) and medium molecular weight (MMW), 52.84-76.88% of high molecular weight (HMW) bound-PAH (BP) residues were sequestrated in humin (HM). The stresses of PAH and soil depth enhanced the frequency of bacteria associations, especially positive associations. We enriched and cultured PAH degradation bacteria (PDB) from the sampling site mainly consisting of Pseudomonas and Acinetobacter, which were originally 0.39-0.52% abundant in the sampling site. The abundances of PDB and PAH-degradation genes (PDGs) were higher at shallower depths and increased with high PAH concentration. Simultaneously, Pearson correlation analysis and experimental verification found that the process of PAH binding with SOM limited the further increase of PDB and PDGs in PAH-contaminated sites. These findings may illustrate possible ecological risks of contaminated soils and provide guidance for the isolation and application of PDB.

Enhanced transformation capability towards benzo(a)pyrene by Fe(III)-modified manganese oxides.

Manganese oxides (Mn oxides) are ubiquitous and may coexist with Fe(III) ions in soil environments. In this study, acid birnessite, alkaline birnessite, cryptomelane, pyrolusite, manganite, and their Fe(III)-modified analogues were synthesized and used for benzo(a)pyrene transformation. Fe-modified Mn oxides show a markedly enhanced transformation capability towards benzo(a)pyrene. Specifically, the benzo(a)pyrene transformation rate constants k for Bir-H, Bir-OH, Cry, Pyr, and Man were 0.49, 0.080, 0.0071, 0.0055, and 0.0022 h-1, respectively. After Fe(III) modification, the transformation rate constants were increased to 22, 2.7, 0.25, 0.0072 and 0.0098 h-1, respectively. Fe(III)-modified layered birnessites exhibited better activity than Fe(III)-modified tunnel Mn oxides, which was attributed to their high Fe(III) contents and abundant active free radicals. Fe(III) was found to accept electrons from benzo(a)pyrene, thereby accelerating the benzo(a)pyrene transformation. Moreover, modification with Fe(III) increased the surface adsorbed water and oxygen, and promoted the generation of active free radicals. Finally, the physicochemical and biochemical properties of transformation products showed the environmental benefits of this process. Overall, the results indicate that the occurrence of Fe(III) ions could promote the removal of PAHs in Mn oxides-rich soils, and this study provides a credible understanding of PAH fates in natural soils.

Humidity induces the formation of radicals and enhances photodegradation of chlorinated-PAHs on Fe(III)-montmorillonite.

Chlorinated-PAHs (ClPAHs) are widely detected in the soil surface and atmospheric particles. However, the underlying mechanisms of their photodegradation are not well understood. In the present study, the formation of radicals on ClPAHs-contaminated clay minerals was quantitatively monitored via electron paramagnetic resonance (EPR) spectroscopy, and the impact of relative humidity (RH) was systematically explored. ClPAHs removal (> 75%) was attributed to electron transfer and •OH attack. The degradation easiness of ClPAHs follows: 2-ClNAP >2-ClANT >9-ClPHE >1-ClPYR. Light irradiation significantly improved the generation of reactive oxygen species (ROS, such as •OH and •O2-), and further generate a series of hydroxylated products of ClPAHs. Persistent free radicals (PFRs) were only detected on clay minerals contaminated with 2-ClANT and 1-ClPYR. RH 10-80%, the concentration of •OH and •O2- increased by 1.07 and 62.79 times respectively, which facilitated transformation of PFRs and ClPAHs degradation. The results of quantum chemical calculations indicate that the initial reaction of ClPAHs photodegradation is mediated by the substitution of •OH for chlorine groups. The present work implies that higher humidity may decrease the generation of PFRs on clay minerals and help mitigate the threats of PFRs and ClPAHs to human health.

Formation of environmentally persistent free radicals from photodegradation of triclosan by metal oxides/silica suspensions and particles.

Metal oxides play an essential role in the photocatalysis of contaminants and substantially increase in the environment by the engineering production. However, whether emerging contaminants will be produced during photocatalysis of contaminants remains unclear. Here, triclosan (TCS) photodegradation in metal oxides/silica suspensions and particles, simulated as the states of metal oxides in water and soil environments, were studied. The photodegradation results confirmed that metal oxides exhibited a double-effect. They promoted TCS photodegradation by generating reactive oxidizing species (ROS) in metal oxides/silica suspensions and inhibited the photodegradation by competing with TCS for irradiation in metal oxides/silica particles. In this study, the critical discovery was the formation of emerging contaminants, environmentally persistent free radicals (EPFRs), and EPFRs yields were promoted by metal oxides (Al2O3, ZnO, TiO2). They were more stable in metal oxides than silica, and the half-lives ranged from 6.7 h to 90.9 d. Although CuO did not increase EPFRs yields compared to silica, the half-lives of EPFRs were also longer. In addition, this study found that EPFRs yields were dependent on the metal oxides concentrations. Our results provided a new insight into the negative environmental impacts of metal oxides and improved our understanding of the formation and fate of EPFRs by metal oxides in soil and aquatic environments.