Phenanthrene degradation in Arthrobacter sp. P1-1: initial 1,2-, 3,4- and 9,10-dioxygenation, and meta- and ortho-cleavages of naphthalene-1,2-diol after its formation from naphthalene-1,2-dicarboxylic acid and hydroxyl naphthoic acids

Arthrobacter sp. P1-1, isolated from a polycyclic aromatic hydrocarbon (PAH)-contaminated site in Hilo, HI, USA, can decompose phenanthrene (40 mg l⁻¹) completely within 7 days. A detailed phenanthrene metabolism map was constructed based on metabolite analysis and replacement cultures. Initial dioxygenation occurs on 1,2-, 3,4-, and 9,10-C of phenanthrene, dominantly on 3,4-C positions. Rapid accumulation of 5,6- and 7,8-benzocoumarin suggests that phenanthrene-1,2- and -3,4-diols mainly undergo meta-cleavage. However, a trace amount of o-carboxyvinylnaphthoates and diphenic acid indicates a limited extent of ortho-cleavage of the diols. Naphthalene-1,2-diol, as a common and converged metabolite, was formed from 1-[(E)-2-carboxyvinyl]-2-naphthoic acid, naphthalene-1,2-dicarboxylic acid, and 1-hydroxy-2-naphthoic acid in separate culture tests. Naphthalene-1,2-diol is then degraded in a dominant phthalic acid pathway and a minor salicylic acid pathway. Several metabolites of phthalic acid were found, while no salicylic acid metabolites were detected. The strain P1-1 likely has a very diverse set of PAH-degrading enzymes or the enzymes having relaxed substrate-specificity.     

Equilibrium sorption of phenanthrene by soil humic acids

This study investigated the effect of chemical heterogeneity of humic acids (HAs) on the equilibrium sorption of phenanthrene by HA extracts. Six HA samples were extracted from three different soils with 0.5 M NaOH and 0.1 M Na₄P₂O₇ and were characterized with elemental analysis, infrared spectrometry, and solid-state ¹³C nuclear magnetic resonance (NMR) spectrometry. The equilibrium sorption measurements were carried out with a batch technique and using the six HA solids as the sorbents and phenanthrene as the sorbate. The measured sorption isotherm data were fitted to the Freundlich equation. The results showed that, for the same soil, (i) the total HA mass extracted with Na₄P₂O₇ was 13.7–22.6% less than that extracted with NaOH, (ii) the Na₄P₂O₇-extracted HA had higher O/C atomic ratio, greater content of polar organic carbons (POC), and lower aliphatic carbon content than the NaOH-extracted HA, and (iii) the Na₄P₂O₇-extracted HA exhibited greater sorption isotherm linearity and but not dramatic difference in sorption capacities than the NaOH extracted HA. The differences in the HA properties resulting from the two different extraction methods may be because NaOH can hydrolyze insoluble HA fractions such as fatty acid like macromolecules bound on soils whereas Na₄P₂O₇ could not. As a result, the HAs extracted with the two different methods had different polarity and functionality which affected their sorption property for phenanthrene.     

Acute toxic effects of phenanthrene on Chinese mitten crab Eriocheir sinensis北大核心CSCD

Phenanthrene is a persistent organic pollutant frequently found in aquatic environments. This paper aimed to assess the acute effects (96 h) of phenanthrene on Chinese mitten crab (Eriocheir sinensis), a key economic aquatic animal in China. An acute semi-static toxic test was carried out to expose E. sinensis to water-borne phenanthrene with different concentrations (1.00, 1.63, 2.65, 4.31 and 7.00 mg L-1) for 96 hours. Mortality and toxic reactions were used as effect criteria. Furthermore, the oxidative stress relative biomarkers (activities of CAT, SOD, GST and content of MDA in hepatopancreas and gills) were measured for E. sinensis exposed to four lower concentrations of phenanthrene (1.00, 1.63, 2.65 and 4.31 mg L-1). The median lethal concentration (LC50) for 24,48 and 96 hour phenanthrene exposure was 16.7, 2.96 and 2.14 mg L-1, respectively; and the safe concentration (SC) of phenanthrene on E. sinensis was 0.214 mg L-1. Phenanthrene significantly increased the activity of CAT in hepatopancreas and gills, and showed a significant dose-effect relationship in hepatopancreas. Bell-shape response patterns were found in the activities of GST and SOD in the hepatopancreas and gills, with significant increases of hepatopancreas GST at 1.00 and 1.63 mg L-1 (P < 0.05), and a significant decrease at 4.31mg L-1 (P < 0.05). Phenanthrene significantly increased the contents of gills MDA at 2.65mg L-1 and hepatopancreas MDA at all four concentrations of phenanthrene. Phenanthrene, especially of high concentration, is highly toxic on E. sinensis, causing lipid peroxidative damage and even acute mortality. Meanwhile, E. sinensis can adapt to lower concentrations of phenanthrene by increasing the activities of SOD, CAT and GST. Because the CAT and GST activities of the gill and hepatopancreas are very sensitive to the presence of high-concentration phenanthrene, they can be used as highly sensitive biomarkers for phenanthrene polluted water.