Xiyun Cai

Aquatic Photochemistry of Fluoroquinolone Antibiotics: Kinetics, Pathways, and Multivariate Effects of Main Water Constituents

The ubiquity of fluoroquinolone antibiotics (FQs) in surface waters urges insights into their fate in the aqueous euphotic zone. In this study, eight FQs (ciprofloxacin, danofloxacin, levofloxacin, sarafloxacin, difloxacin, enrofloxacin, gatifloxacin, and balofloxacin) were exposed to simulated sunlight, and their photodegradation was observed to follow apparent first-order kinetics. Based on the determined photolytic quantum yields, solar photodegradation half-lives for the FQs in pure water and at 45 degrees N latitude were calculated to range from 1.25 min for enrofloxacin to 58.0 min for balofloxacin, suggesting that FQs would intrinsically photodegrade fast in sunlit surface waters. However, we found freshwater and seawater constituents inhibited their photodegradation. The inhibition was further explored by a central composite design using sarafloxacin and gatifloxacin as representatives. Humic acids (HA), Fe(III), NO(3)(-), and HA-Cl(-) interaction inhibited the photodegradation, as they mainly acted as radiation filters and/or scavengers for reactive oxygen species. The photodegradation product identification and ROS scavenging experiments indicated that the FQs underwent both direct photolysis and self-sensitized photo-oxidation via *OH and (1)O(2). Piperazinyl N(4)-dealkylation was primary for N(4)-alkylated FQs, whereas decarboxylation and defluorination were comparatively important for the other FQs. These results are of importance toward the goal of assessing the persistence of FQs in surface waters.

Quantum chemical investigation and experimental verification on the aquatic photochemistry of the sunscreen 2-phenylbenzimidazole-5-sulfonic acid.

For ecological risk assessment of the large and ever-increasing number of chemical pollutants, it is of importance to develop computational methods to screen or predict their environmental photodegradation behavior. This study developed a computational method based on the density functional theory (DFT) to predict and evaluate the photodegradation behavior and effects of water constituents, taking a sunscreen and personal care product 2-phenylbenzimidazole-5-sulfonic acid (PBSA) as a model compound. Energy and electron transfer reactions of excited state PBSA (PBSA*) with (3)O(2) and water constituents were evaluated. The computational results indicated that PBSA* could photogenerate (1)O(2) and O(2)(-)·, triplet excited state humic/fulvic acid analogs could not photosensitize the degradation, and the anions (Cl(-), Br(-), and HCO(3)(-)) could not quench PBSA* or its radical cation chemically. Experiments employing simulated sunlight confirmed that PBSA photodegraded via the direct and self-sensitization mechanism involving O(2)(-)·. The photodegradation was pH-dependent. The direct and self-sensitized photodegradation was inhibited by fulvic acid. The main photodegradation products were identified, and the pathways were clarified. These results indicate that the DFT-based computational method can be employed to assess the environmental photochemical fate of organic pollutants.

Different photolysis kinetics and photooxidation reactivities of neutral and anionic hydroxylated polybrominated diphenyl ethers.

Hydroxylated polybrominated diphenyl ethers (HO-PBDEs) pose potential ecological risks due to their endocrine disrupting effects and extensive sources. It is of great importance to know their environmental transformation for the purpose of ecological risk assessment. Photodegradation is an important transformation pathway of HO-PBDEs. As HO-PBDEs ionize in natural waters, the photochemical reactivities of both neutral and anionic HO-PBDEs need to be unveiled. In this study, six HO-PBDEs were selected as model compounds. Their direct photolysis rate constants (k(d)), quantum yields (Φ), light absorptions (A), second-order reaction rate constants with (1)O(2) (k(1O2)) and (·)OH (k(OH)) at different pH were determined, as well as these parameters for the neutral and anionic HO-PBDEs. The k(d), Φ, A, k(1O2) and k(OH) for the anions are much higher than those for the neutral molecules and vary with the bromination degree. Molecular parameters computed with the density functional theory (DFT) were employed to construct structure-reactivity equations. The ether bond strength, the frontier molecular orbital energy and the charge distribution were found to be the intrinsic structural characters governing the photochemical reactivities. The half-lives range from 0.7 to 60.1h for the photodegradation including the direct photolysis and the reactions with (1)O(2) and ()OH in surface waters at 45°N latitude under the continuous solar irradiation of sunny noon on 15 July. Direct photolysis is the dominant pathway. The photochemical reactivities of other HO-PBDEs at a given pH can also be estimated based on the structure-reactivity equations, which is important for the ecological risk assessment of HO-PBDEs.

Application of a level IV fugacity model to simulate the long-term fate of hexachlorocyclohexane isomers in the lower reach of Yellow River basin, China

A level IV multimedia fugacity model was established to simulate the fate and transfer of hexachlorocyclohexane (HCH) isomers in the lower reach of the Yellow River basin, China, during 1952-2010. The predicted concentrations of HCHs are in good agreement with the observed ones, as indicated by the residual errors being generally lower than 0.5 logarithmic units. The effects of extensive agricultural application and subsequent prohibition of HCHs are reflected by the temporal variation of HCHs predicted by the model. It is predicted that only 1.8 tons of HCHs will be left in 2010, less than 0.06% of the highest contents (in 1983) in the study area, and about 99% of HCHs remain in soil. The proportions of HCH isomers in the environment also changed with time due to their different physicochemical properties. Although beta-HCH is not the main component of the technical HCHs, it has become the most abundant isomer in the environment because of its persistence. The dominant transfer processes between the adjacent compartments were deposition from air to soil, air diffusion through the air-water interface and runoff from soil to water. Sensitivity analysis showed that degradation rate in soil, parameters related to major sources, and thickness of soils had the strongest influence on the model result. Results of Monte Carlo simulation indicated the overall uncertainty of model predictions, and the coefficients of variation of the estimated concentrations of HCHs in all the compartments ranged from 0.5 to 5.8.

Mathematical model for cyclodextrin alteration of bioavailability of organic pollutants.

While many cyclodextrin-based applications have been developed to assess or enhance bioavailability of organic pollutants, the choice of cyclodextrin (CD) is largely empirical, with little consideration of pollutant diversity and environmental matrix effects. This study aimed at developing a mathematical model for quantifying CD alteration of bioavailability of organic pollutants. Cyclodextrin appears to have multiple effects, together contributing to its bioavailability-enhancing property. Cyclodextrin is adsorbed onto the adsorbent matrix to different extents. The adsorbed CD is capable of sequestrating organic pollutants, highlighting the role of a pseudophase similar to solid environmental matrix. Aqueous CD can reduce adsorption of organic pollutants via inclusion complexation. The two effects cancel each other to a certain degree, which determines the levels of organic pollutants dissolved (comprising freely dissolved and CD-included forms). Additionally, the CD-included form is nearly identical in biological activity to the free form. A mathematical model of one variable (i.e., CD concentration) was derived to quantify effects of CD on the bioavailability of organic pollutants. Model analysis indicates that alteration of bioavailability of organic pollutants by CD depends on both CD (type and level) and environmental matrix. The selection of CD type and amendment level for a given application may be predicted by the model.

Integrated fuzzy concentration addition–independent action (IFCA–IA) model outperforms two-stage prediction (TSP) for predicting mixture toxicity

Mixture toxicities were determined for 12 industrial organic chemicals bearing four different modes of toxic action (MOAs) to Vibrio fischeri, to compare the predictability of the integrated fuzzy concentration addition-independent action (IFCA-IA) model and the two-stage prediction (TSP) model. Three mixtures were designed: The first and second mixtures were based on the ratios of each component at the 1% and 50% effect concentrations (EC(1) and EC(50)), respectively; and the third mixture contained an equimolar ratio of individual components. For the EC(1), EC(50) and equimolar ratio, prediction errors from the IFCA-IA model at the 50% experimental mixture effects were 0.3%, 6% and 0.6%, respectively; while for the TSP model, the corresponding errors were 2.8%, 19% and 24%, respectively. Thus, the IFCA-IA model performed better than the TSP model. The IFCA-IA model calculated two weight coefficients from the molecular structural descriptors, which weigh the relation between concentration addition (CA) and independent action (IA) through the fuzzy membership functions. Thus, MOAs are not pre-requisites for mixture toxicity prediction by the IFCA-IA approach, implying the practicability of this method in toxicity assessment of mixtures.

Inclusion complex of butachlor with β-cyclodextrin: characterization, solubility, and speciation-dependent adsorption.

Due to soil adsorption, higher amounts of the herbicide butachlor are necessary to achieve its herbicidal activity, hence increasing its environmental risks. In this study, the effects of beta-cyclodextrin (beta-CD) on solubility and soil adsorption of butachlor were investigated. Formation of a 1:1 stoichiometric inclusion complex between them with an apparent stability constant of 443 L mol(-1) was confirmed in the solution. Fourier transform infrared spectroscopy showed that the (N-CO) amide bond and alkyl ether moiety of butachlor molecule could enter into the cavity of beta-CD, but the double-substituted aromatic ring was excluded because it was larger size than the cavity. Significant enhancing dissolution of butachlor in the inclusion complex occurred in comparison to the free herbicide. The adsorption of butachlor on soil was reduced with an increase of beta-CD concentration because of the formation of the inclusion complex with low adsorption potency. Although the sorption distribution coefficient of complexed butachlor (i.e., butachlor/beta-cyclodextrin inclusion complex) (K(d,c) = 6.14) was about 14% of that of the free herbicide (K(d,f) = 44.54), the proportion of the adsorbed amount of complexed butachlor to the total adsorbed amount rose with the increase of beta-CD concentration. Thus, the adsorption of inclusion complex cannot be neglected in the presence of high concentrations cyclodextrins, although its water solubility was much higher than that of the free herbicide. These results indicate that beta-CD may be used as a formation additive to improve the solubility of butachlor, reduce its adsorption on soil, and increase the availability of butachlor for weeds.

More toxic and photoresistant products from photodegradation of fenoxaprop-p-ethyl.

The photodegradation pathway of the commonly used herbicide fenoxaprop-p-ethyl (FE) was elucidated, and the effects of the photodegradation on its toxicity evolution were investigated. Under solar irradiation, FE could undergo photodegradation, and acetone enhanced the photolysis rates significantly. The same photoproducts formed under the irradiation of lambda > 200 nm and lambda > 290 nm through rearrangement, loss of ethanol after rearrangement, de-esterification, dechlorination, photohydrolysis, and the breakdown of the ether linkages. One of the main transformation products, 4-[(6-chloro-2-benzoxazolyl)oxy] phenol (CBOP), was resistant to photodegradation under the irradiation of lambda > 290 nm, and its photolysis rate was seven times slower than the parent under the irradiation of lambda > 200 nm. Among the metabolites, CBOP (48 h EC50 of 1.49-1.64 mg/L) and hydroquinone (48 h EC50 of 0.25-0.28 mg/L) were more toxic to Daphnia magna than the parent FE (48 h EC50 of 4.2-6.9 mg/L). Thus, more toxic and photoresistant products were generated from photolysis of the herbicide. Ecotoxicological effects of phototransformed products from pesticides should be emphasized for the ecological risk assessment of these anthropogenic pollutants.

Contributions of deposited particles to pine needle polycyclic aromatic hydrocarbons

The contributions of deposited particles (P) to polycyclic aromatic hydrocarbon (PAH) levels in pine (Cedrus deodar) needles sampled from the Dalian region were evaluated by washing off the particles from pine needle surfaces. P values ranged from 4.4 +/- 2.2% for fluorene to 69.9 +/- 4.0% for indeno(1,2,3-cd)pyrene, and positively correlated with the logarithm of octanol-air partition coefficients (log K OA) of each PAH significantly. P and the total levels of 14 PAHs under study ( summation PAHs), that ranged from 490 to 3241 ng g(-1) dw (dry weight) with median value of 1521 ng g(-1) dw, were high for traffic areas, and low for residential or park areas, implying the significant contributions of PAHs in both gas and particle phases emitted by vehicles. However, PAH profiles in pine needles were not significantly altered by the washing, due to the low fractions (2-5%) of the 5- and 6-ring PAHs in summation PAHs. The high wind speed and frequently alternating wind directions in the Dalian spring could quicken the depuration processes of pine needle PAHs. Thus, the local meteorological conditions and source variations should be taken into account when using pine needles to implicate seasonal variations of atmospheric semi-volatile organic compounds.

Dechlorination of chloroacetanilide herbicides by plant growth regulator sodium bisulfite

Chloroacetanilide herbicides are frequently detected in groundwater and surface waters, and pose high risks to aquatic biota. In this study, sodium bisulfite (NaHSO(3)), a plant growth regulator used in China, was used to remove three chloroacetanilide herbicides including alachlor, acetochlor and S-metolachlor. These herbicides were rapidly dechlorinated by NaHSO(3) in neutral conditions. The dechlorination was accelerated with increasing pH, temperature and NaHSO(3) concentrations. Kinetic analysis and mass spectrum identification revealed that the reaction followed S(N)2 nucleophilic substitution, in which the chlorine was replaced by the reactive specie sulfite. Alachlor and its isomer acetochlor had similar reaction rates, whereas they were more readily transformed than S-metolachlor that had larger steric hindrance and weaker electrophilicity. The transformation products were chloroacetanilide ethane sulfonic acids (ESAs), which were also encountered as major metabolites of these herbicides in natural environment via common metabolic pathways and were less toxic to green algae compared to the parent herbicides. These results indicate that NaHSO(3) can accelerate transformation of chloroacetanilide herbicides to the less toxic transformation products by nucleophilic substitution and dechlorination in aquatic environment. NaHSO(3) can be potentially used for the removal of chloroacetanilide herbicides from wastewater effluent, spill sites and accidental discharge.