Ecotoxicity of parathion during its dissipation mirrored by soil enzyme activity, microbial biomass and basal respiration.

The application of parathion (PTH) in agriculture can result in its entry into the soil and threaten the soil environment. Monitoring the PTH residues and assessing toxicity on soil health are of paramount importance to the public. Herein, the dissipation of PTH and concomitant influence on microbial activities [FDA hydrolase (FDA‒H), microbial biomass carbon (MBC) and basal respiration (BR)] in coastal solonchaks were investigated. Results showed that the dissipation of PTH in tested soil declined linearly, and the half-lives varied from 5.6 to 56.8 days, depending on pollutant concentrations. The FDA‒H activity and MBC were negatively affected by PTH pollution and exhibited a significantly positive correlation. Two‒way ANOVA analysis demonstrated that microbial activities were affected not only by PTH dose and incubation time but also by their interactions. The integrated biomarker response (IBR/n) index values on day 120 were between 1.02 and 2.89, larger than those on day 1 during PTH dissipation. This implied that the soil quality did not recover though there was no PTH residue in the soil at the end of the experiment. These findings suggested that microbial activities integrated with IBR/n index could elucidate the hazardous impacts of PTH dissipation on biochemical cycling and microorganisms in soil.

Kinetics and catalytic efficiency of soil fluorescein diacetate hydrolase under the pesticide parathion stress.

Fluorescein diacetate hydrolase (FDA-H) is an accurate biochemical method measuring the total microbial activity in soil, which indicates soil quality under ambient environmental changes such as pesticide parathion (PTH). However, the influence of PTH on the kinetics of FDA-H is still unknown. In this study, fifteen farmland soils were exposed to acute PTH pollution to investigate how the kinetic characteristics of FDA-H change with PTH concentration. Results showed that PTH strongly inhibited the FDA-H activities. The values of maximum reaction velocity (Vmax) ranged from 0.29 to 2.18 × 10-2 mM g-1 soil h-1 and declined by 42.30%-71.01% under PTH stress. The Michaelis constant (Km) values ranged between 2.90 and 14.17 × 10-2 mM and exhibited three forms including unchanged, increased (38.16-242.65%) and decreased (13.41-39.23%) when exposed to PTH. Based on the changes in two kinetic parameters, the inhibition of PTH on FDA-H was classified as three types, i.e., noncompetitive, linear mixed and uncompetitive inhibition. The competitive inhibition constant (Kic) and noncompetitive constant (Kiu) ranged from 0.064 to 0.447 mM and 0.209 to 0.723 mM, respectively, which were larger than the Km in values. The catalytic efficiency (Vmax/Km) of FDA-H is a sensitive integrated parameter to evaluate the PTH toxicity due to the higher inhibition ratio than the Vmax. The PTH toxicity to FDA-H decreased with increase of soil organic matter and total nitrogen contents. This implied that the PTH toxicity could be alleviated by an increasing content of soil organic matter due to its buffering capacity to PTH. Besides, soils with a higher content of total nitrogen could provide stable environment for FDA-H to maintain its functionality under PTH pollution. Thus, the results of this study have great implications to the risk assessment of parathion in soils.

Interaction of benzo[a]pyrene with Cu(II)-montmorillonite: Generation and toxicity of environmentally persistent free radicals and reactive oxygen species.

This paper presents the interaction of benzo[a]pyrene (B[a]P) with Cu(II)-montmorillonite to investigate the formation, evolution and potential toxicity of environmentally persistent free radicals (EPFRs) under dark and visible light irradiation conditions. Degradation of B[a]P and the generated transformative products on clay mineral are monitored by gas chromatography-mass spectrometry (GC-MS) technique. Hydroxyl-B[a]P and B[a]P-diones are observed during the transformation of B[a]P under dark condition. B[a]P-3,6-dione and B[a]P-6,12-dione are the main products under visible light irradiation. B[a]P transformation is accompanied by the formation of EPFRs, which are quantified by electron paramagnetic resonance (EPR) spectroscopy. With increasing reaction time, the concentrations of the produced EPFRs are initially increased and then gradually decrease to an undetectable level. The deconvolution results of EPR spectra reveal formation of three types of organic radicals (carbon-centered radicals, oxygen-centered radicals, and carbon-centered radicals with a conjugated oxygen), which also co-exist. Correspondingly, visible-light irradiation promotes the formation and the decay of these EPFRs. The produced B[a]P-type EPFRs induce the generation of reactive oxygen species (ROS), such as superoxide (O2-) and hydroxide radicals (OH), which may cause oxidative stress to cells and tissues of organisms. The toxicity of degradation products is evaluated by the livability of human gastric epithelial GES-1cells. The toxicity is initially increased and then decreases with the elapsed reaction time, which correlates with the evolution of EPFRs concentrations. The present work provides direct evidence that the formation of EPFRs in interaction of PAHs with metal-contaminated clays may result in negative effects to human health.

Impacts of Pantoea agglomerans strain and cation-modified clay minerals on the adsorption and biodegradation of phenanthrene.

Interactions between microorganisms and minerals have the potential contribution to remove polycyclic aromatic hydrocarbons (PAHs) in model systems. In this study, phenanthrene (PHE) was used as a probe molecule to explore the potential adsorption and biotransformation processes in the presence of microorganisms and various reference clays, such as montmorillonite (M), kaolinite (K), and pyrophyllite (P). Equilibrium adsorption experiments and scanning electron microscopy (SEM) technique were used to investigate the sorption of Pantoea agglomerans strains on clay minerals saturated with cations (Na+ and Fe3+). The adsorption isotherms of PHE and Pantoea agglomerans strains on cation-modified clay minerals fitted to Langmuir equation, and their adsorbed amounts both followed the sequence: montmorillonite > kaolinite > pyrophyllite. For six types of cation-modified minerals, the behavior of PHE adsorbed and Pantoea agglomerans adhered onto mentioned minerals was in the order of Na(I)-M > Fe(Ⅲ)-M, Na(I)-K > Fe(Ⅲ)-K and Fe(Ⅲ)-P > Na(I)-P, respectively. The biodegradation results showed that cation-modified clay minerals could enhance the biodegradation of PHE, ascribing to their large specific surface area, and cation exchange capability, as well as the difference in zeta potential between minerals and Pantoea agglomerans strains. Comparison of biodegradation rates displayed that PHE was degraded the highest in the presence of Na-M (93.285%). In addition, the obtained results suggested that the adhesion of bacteria onto cation-exchanged clay minerals was beneficial to the biodegradation of PHE. Anthracen-9-ylmethanol and 3,4-dimethyl-2-(3-methylbutanoyl)benzoic acid were detected as the main intermediate compounds, which can be further biodegraded into small molecules. The overall results obtained in this study are of valuable significance for the understanding of the behavior of PHE in soil and associated environment.

Environmentally Persistent Free Radicals in Soils of Past Coking Sites: Distribution and Stabilization.

This study presents the existence of environmentally persistent free radicals (EPFRs) in soils of past coking sites, mainly contaminated by polycyclic aromatic hydrocarbons (PAHs). Measurements of EPFRs were conducted by electron paramagnetic resonance (EPR) technique with numerous soil samples, which were collected from different distances (0-1000 m) and different depths (0-30 cm) of three contaminant sources. EPR signals with ∼3 × 1017 radicals/g of the soil samples were obtained, which are very similar to that generated in PAHs contaminated clays, that is, g = 2.0028-2.0036. Concentrations of PAHs and soil components were determined to understand their role in producing EPFRs. PAHs, clay, and iron predominately contributed to generating EPRFs. Meanwhile, organic matter negatively influenced the production of EPRFs. The effects of environmental factors (moisture and oxic/anoxic) were also studied to probe the persistency of EPFRs under various simulated conditions. The EPFRs are stable under relatively dry and oxic conditions. Under anoxic conditions without O2 and H2O, the spin densities decrease initially, followed by gradual increase before attaining constant values in two months period time. The present work implies that continuous formation of EPFRs induced by PAHs is largely responsible for the presence of relatively stable radicals in soils of coking sites.