Linke Ge

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.

Distinct photolytic mechanisms and products for different dissociation species of ciprofloxacin.

As many antibiotics are ionizable and may have different dissociation forms in the aquatic environment, we hypothesized that the different dissociation species have disparate photolytic pathways, products, and kinetics, and adopted ciprofloxacin (CIP) as a case to test this hypothesis. Simulated sunlight experiments and matrix calculations were performed to differentiate the photolytic reactivity for each dissociation species (H4CIP(3+), H3CIP(2+), H2CIP(+), HCIP(0), and CIP(-)). The results prove that the five dissociation species do have dissimilar photolytic kinetics and products. H4CIP(3+) mainly undergoes stepwise cleavage of the piperazine ring, while H2CIP(+) mainly undergoes defluorination. For H3CIP(2+), HCIP(0), and CIP(-), the major photolytic pathway is oxidation. By density functional theory calculation, we clarified the defluorination mechanisms for the five dissociation species at the excited triplet states: All the five species can defluorinate by reaction with hydroxide ions (OH(-)) to form hydroxylated products, and H2CIP(+) can also undergo C-F bond cleavage to produce F(-) and a carbon-centered radical. This study is a first attempt to differentiate the photolytic products and mechanisms for different dissociation species of ionizable compounds. The results imply that for accurate ecological risk assessment of ionizable emerging pollutants, it is necessary to investigate the environmental photochemical behavior of all dissociation species.

Levels and patterns of polybrominated diphenyl ethers in children's plasma from Dalian, China

Polybrominated diphenyl ethers (PBDEs) are potential persistent organic pollutants which have raised many concerns in recent years. Research focusing on children exposure to PBDEs is important but insufficient. The levels and patterns of PBDEs in childrens plasma from Dalian, China were studied for the first time. Seventeen PBDE congeners (BDE-30, 28, 35, 37, 75, 47, 66, 100, 99, 116, 155, 154, 153, 183, 181, 190 and 209) in 29 plasma samples were measured. Median PBDE concentration was 31.61 ng g(-1) lipid. BDE-153 was the dominant congener, followed by BDE-99, 47, and 183. High abundance of BDE-183 suggested a higher Octa-BDE use in China. No significant differences were observed between males and females or among different age groups. The levels of PBDEs in childrens plasma in the present study were 9-30 times higher than those in non-occupational exposure people from Guangzhou, South China and those in human milk of general adults from other cities of China, but were at the moderate levels of those in children around the world. These results indicate that children in Dalian are at a high risk of exposure to PBDEs.

New insights into the aquatic photochemistry of fluoroquinolone antibiotics: Direct photodegradation, hydroxyl-radical oxidation, and antibacterial activity changes

The ubiquity and photoreactivity of fluoroquinolone antibiotics (FQs) in surface waters urge new insights into their aqueous photochemical behavior. This study concerns the photochemistry of 6 FQs: ciprofloxacin, danofloxacin, levofloxacin, sarafloxacin, difloxacin and enrofloxacin. Methods were developed to calculate their solar direct photodegradation half-lives (td,E) and hydroxyl-radical oxidation half-lives (tOH,E) in sunlit surface waters. The td,E values range from 0.56 min to 28.8 min at 45° N latitude, whereas tOH,E ranges from 3.24h to 33.6h, suggesting that most FQs tend to undergo fast direct photolysis rather than hydroxyl-radical oxidation in surface waters. However, a case study for levofloxacin and sarafloxacin indicated that the hydroxyl-radical oxidation induced risky photochlorination and resulted in multi-degradation pathways, such as piperazinyl hydroxylation and clearage. Changes in the antibacterial activity of FQs caused by photodegradation in various waters were further examined using Escherichia coli, and it was found that the activity evolution depended on primary photodegradation pathways and products. Primary intermediates with intact FQ nuclei retained significant antibacterial activity. These results are important for assessing the fate and risk of FQs in surface waters.

Distribution and characteristic of PAHs in snow of Fildes Peninsula.

Polycyclic aromatic hydrocarbons (PAHs) investigation in different matrices has been reported largely, whereas reports on snow samples were limited. Snow, as the main matrix in the polar region, has an important study meaning. PAHs in snow samples were analyzed to investigate the distribution and contamination status of them in the Antarctic, as well as to provide some references for global migration of PAHs. Snow samples collected in Fildes Peninsula were enriched and separated by solid-phase membrane disks and eluted by methylene dichloride, then quantified by gas chromatography/mass spectrometry. All types of PAHs were detected except for Benzo(a)pyrene. Principal component analysis method was applied to characterize them. Three factors (Naphthalene, Fluorene and Phenanthrene) accounted for 60.57%, 21.61% and 9.80%, respectively. The results showed that the major PAHs sources maybe the atmospheric transportation, and the combustion of fuel in Fildes Peninsula. The comparison of concentration and types of PAHs between accumulated snow and fresh snow showed that the main compound concentrations in accumulated snow samples were higher than those in fresh ones. The risk assessment indicated that the amount of PAHs in the snow samples would not lead to ecological risk.

Distribution characteristics and indicator significance of Dechloranes in multi-matrices at Ny-Ålesund in the Arctic

In recent years, Dechloranes have been widely detected in the environment around the world. However, understanding and knowledge of Dechloranes in remote regions, such as the Arctic, remain lacking. Therefore, the concentrations of 5 Dechloranes in surface seawater, sediment, soil, moss, and dung collected from Ny-Ålesund in the Arctic were measured with the concentrations 93 pg/L, 342, 325, 1.4, and 258 pg/g, respectively, which were much lower than those in Asian and European regions. The mean ratios of anti-Dechlorane Plus (DP) to total DP (ƒanti) in seawater, sediment, soil, moss, dung, and atmospheric samples were 0.36, 0.21, 0.18, 0.27, 0.66, and 0.43, respectively. Results suggested that the main source of DP in seawater, sediment, soil, and moss was long-range atmospheric transport. However, the ratio identified in dung was different, for which the migration behavior of the organism is probably the main source of DP.

Concentration-dependent photodegradation kinetics and hydroxyl-radical oxidation of phenicol antibiotics.

Thiamphenicol and florfenicol are two phenicol antibiotics widely used in aquaculture and are ubiquitous as micropollutants in surface waters. The present study investigated their photodegradation kinetics, hydroxyl-radical (OH) oxidation reactivities and products. Firstly, the photolytic kinetics of the phenicols in pure water was studied as a function of initial concentrations (C0) under UV-vis irradiation (λ>200nm). It was found that the kinetics was influenced by C0. A linear plot of the pseudo-first-order rate constant vs C0 was observed with a negative slope. Secondly, the reaction between the phenicol antibiotics and OH was examined with a competition kinetic method under simulated solar irradiation (λ>290nm), which quantified their bimolecular reaction rate constants of (2.13±0.02)×10(9)M(-1)s(-1) and (1.82±0.10)×10(9)M(-1)s(-1) for thiamphenicol and florfenicol, respectively. Then the corresponding OH oxidated half-lives in sunlit surface waters were calculated to be 90.5-106.1h. Some main intermediates were formed from the reaction, which suggested that the two phenicols underwent hydroxylation, oxygenation and dehydrogenation when OH existed. These results are of importance to assess the phenicol persistence in wastewater treatment and sunlit surface waters.

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.

Aqueous photochemical degradation of hydroxylated PAHs: Kinetics, pathways, and multivariate effects of main water constituents.

Hydroxylated polycyclic aromatic hydrocarbons (OH-PAHs) are contaminants of emerging concern in the aquatic environment, so it is of great significance to understand their environmental transformation and toxicity. This study investigated the aqueous photochemical behavior of four OH-PAHs, 9-Hydroxyfluorene (9-OHFL), 2-Hydroxyfluorene, 9-Hydroxyphenanthrene and 1-Hydroxypyrene, under simulated sunlight irradiation (λ>290 nm). It was observed that their photodegradation followed the pseudo-first-order kinetics. Based on the determined quantum yields, their calculated solar apparent photodegradation half-lives in surface waters at 45° N latitude ranged from 0.4min for 9-Hydroxyphenanthrene to 7.5 × 10(3)min for 9-OHFL, indicating that the OH-PAHs would intrinsically photodegrade fast in sunlit surface waters. Furthermore, 9-OHFL as an example was found to undergo direct photolysis, and self-sensitized photooxidation via OH rather than (1)O2 in pure water. The potential photoreactions involved photoinduced hydroxylation, dehydrogenation and isomerization based on product identification by GC-MS/MS. 9-OHFL photodegraded slower in natural waters than in pure water, which was attributed to the integrative effects of the most photoreactive species, such as Fe(III), NO3(-), Cl(-) and humic acid. The photomodified toxicity was further examined using Vibrio fischeri, and it was found that the toxicity of photolyzed 9-OHFL did not decrease significantly (p>0.05) either in pure water or in seawater, implying the comparable or higher toxicity of some intermediates. These results are important for assessing the fate and risks of OH-PAHs in surface waters.