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The efficient and selective removal of refractory antibiotics from high-strength antibiotic production wastewater is crucial but remains a substantial challenge. In this study, a novel ozone micronano-bubble (MNB)-enhanced treatment system was constructed for antibiotic production wastewater treatment. Compared with conventional ozone, ozone MNBs exhibit excellent treatment efficiency for oxytetracycline (OTC) degradation and toxicity decrease. Notably, this study identifies the overlooked singlet oxygen (

We report a novel composite material, referred to as activated charcoal supported titanate nanotubes (TNTs@AC), for highly efficient adsorption and photodegradation of a representative polycyclic aromatic hydrocarbon (PAH), phenanthrene. TNTs@AC was prepared through a one-step hydrothermal method, and is composed of an activated charcoal core and a shell of carbon-coated titanate nanotubes. TNTs@AC offered a maximum Langmuir adsorption capacity of 12.1 mg/g for phenanthrene (a model PAH), which is ∼11 times higher than the parent activated charcoal. Phenanthrene was rapidly concentrated onto TNTs@AC, and subsequently completely photodegraded under UV light within 2 h. The photoregenerated TNTs@AC can then be reused for another adsorption-photodegradation cycle without significant capacity or activity loss. TNTs@AC performed well over a wide range of pH, ionic strength, and dissolved organic matter. Mechanistically, the enhanced adsorption capacity is attributed to the formation of carbon-coated ink-bottle pores of the titanate nanotubes, which are conducive to capillary condensation; in addition, the modified microcarbon facilitates transfer of excited electrons, thereby inhibiting recombination of the electron-hole pairs, resulting in high photocatalytic activity. The combined high adsorption capacity, photocatalytic activity, and regenerability/reusability merit TNTs@AC a very attractive material for concentrating and degrading a host of micropollutants in the environment.

Indoor window film samples were collected in buildings during 2014-2015 for the determination of six phthalate diesters (PAEs). Linear regression analysis suggested that the film mass was positively and significantly correlated with the duration of film growth (from 7 to 77 days). PAEs were detected in all window film samples (n = 64). For all the samples with growth days ranged from 7 to 77 days, the median concentrations of total six PAEs (∑6PAEs) in winter and summer window film samples were 9900 ng/m(2) film (2000 μg/g film) and 4700 ng/m(2) film (650 μg/g film), respectively. Among PAEs analyzed, di-2-ethyl-hexyl phthalate (DEHP) was the major compound (71 ± 9.7%), followed by di-n-butyl phthalate (DBP; 20 ± 7.4%) and diisobutyl phthalate (DiBP; 5.1 ± 2.2%). Positive correlations among PAEs suggested their common sources in the window film samples. Room temperature and relative humidity were negatively and significantly correlated with PAEs concentations (in ng/m(2)). Poor ventilation in cold winter in Noreastern China significantly influenced the concentrations of PAEs in window film which suggested higher inhalation exposure dose in winter. The median hazard quotient (HQ) values from PAEs exposure were below 1, suggesting that the intake of PAEs via three exposure pathways was considered as acceptable.

Methyl siloxanes, which belong to organic silicon compounds and have linear and cyclic structures, are of particular concern because of their potential characteristic of persistent, bioaccumulated, toxic, and ecological harm. This study investigated the trophic transfer of four cyclic methyl siloxanes (octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), and tetradecamethylcycloheptasiloxane (D7)) in a marine food web from coastal area of Northern China. Trophic magnification of D4, D5, D6, and D7 were assessed as the slope of lipid equivalent concentrations regressed against trophic levels of marine food web configurations. A significant positive correlation (R = 0.44, p0.0001) was found between lipid normalized D5 concentrations and trophic levels in organisms, showing the trophic magnification potential of this chemical in the marine food web. The trophic magnification factor (TMF) of D5 was estimated to be 1.77 (95% confidence interval (CI): 1.41-2.24, 99.8% probability of the observing TMF1). Such a significant link, however, was not found for D4 (R = 0.14 and p = 0.16), D6 (R = 0.01 and p = 0.92), and D7 (R = -0.15 and p = 0.12); and the estimated values of TMFs (95% CI, probability of the observing TMF1) were 1.16 (0.94-1.44, 94.7%), 1.01 (0.84-1.22, 66.9%) and 0.85 (0.69-1.04, 48.6%) for D4, D6, and D7, respectively. The TMF value for the legacy contaminant BDE-99 was also estimated as a benchmark, and a significant positive correlation (R = 0.65, p0.0001) was found between lipid normalized concentrations and trophic levels in organisms. The TMF value of BDE-99 was 3.27 (95% CI: 2.49-4.30, 99.7% probability of the observing TMF1), showing the strong magnification in marine food webs. To the best of our knowledge, this is the first report on the trophic magnification of methyl siloxanes in China, which provided important information for trophic transformation of these compounds in marine food webs.

Air samples were concurrently collected using high volume air samplers for 24 h every week from September 2008 to August 2009 at 15 sites (11 urban, 1 suburban, and 3 background/rural) across China. Twelve polybrominated diphenyl ether (PBDE) congeners (BDE-17, -28, -47, -66, -85, -99, -100, -138, -153, -154, -183, and -209) were measured. Total PBDE concentrations (∑12PBDEs) in air (gas + particle phases) were in the range of 11.0-838 pg m(-3) with a mean of 232 ± 72 (mean ± SE) pg m(-3). The site with the highest concentration was Guangzhou (838 ± 126 pg m(-3)), followed by Beijing (781 ± 107 pg m(-3)). Significant positive correlations were found between PBDEs levels and urban population (R = 0.69, P0.05) and gross industrial output values (R = 0.87, P0.001) as well. BDE-209 was the dominating congener with the contribution of 64 ± 23% to ∑12PBDEs, followed by BDE-47(8 ± 8%) and -99(6 ± 5%) at all urban and suburban sites. At background/rural sites, however, BDE-47 was the dominating congener, followed by BDE-99, together accounting for 52 ± 21% of ∑12PBDEs, while BDE-209 was only 11 ± 2%. It was found that PBDEs at the 15 sites showed a primary distribution and fractionation pattern. This study produced more than 700 pairs of air samples in gaseous and particulate phases with a wide temperature range of ∼60 °C, providing a good opportunity to investigate gas-particle partitioning for individual PBDE congeners. The results of gas-particle partitioning analysis for PBDEs using both subcooled-liquid-vapor pressure (PL)-based and octanol-air partition coefficient (KOA)-based models indicated that PBDEs in air at all sampling sites had not reached equilibrium because the slope values (mO) in the KOA-based equation and the opposite slope values (mP) in the PL-based equation at all 15 sampling sites were less than 1. It also found that both mO and -mP were significantly and positively correlated with the annual average temperatures of sampling sites and also significantly and negatively correlated with the mole masses of PBDE congeners, indicating a general trend that the higher the temperature at the sampling site and the lower the mole mass of the PBDE congeners are, the closer to the equilibrium the congeners approach and vice versa. To our knowledge, this is the first study to report the correlations of the slope values for both the KOA-based and PL-based equations with temperatures at sampling sites and mole masses for individual PBDE congeners.

Large quantities of hexachlorocyclohexanes (HCHs) were historically applied to soils in Zhejiang, a hilly province of eastern China, yet very limited information is publicly available for the present levels and residue characteristics of HCHs in the region. In this work, concentrations of HCHs and enantiomeric fractions (EFs) of α-isomer were analyzed in 58 agricultural soil samples (0-20 cm) collected in Zhejiang province. On the basis of the ratio of α-HCH/β-HCH and the fact that HCHs were banned in 1983 for agricultural use in China, fresh application of technical HCHs in a large quantity was unlikely in this province. Significant correlation was found between soil concentrations and elevation (R = 0.52, P < 0.001) and temperature (R = -0.55, P < 0.0001), but not between soil concentrations and total technical usage (R = -0.24, P = 0.1), suggesting a typical secondary distribution pattern. The soil residue inventories of HCHs derived from the relationship between concentration and elevation indicated 14.2 tons of HCHs left in agricultural soils in plain areas with the average elevation less than 100 m, and 61.6 tons of HCHs left in mountain soils with the average elevation higher than 100 m. It was also found that EFs of α-HCH were significantly negatively correlated with carbon biomass (C(bio)) in soils. This implies that C(bio) might have important impact on orientation and extent of enantioselective degradation of α-HCH in the region, which is, according to our knowledge, the first report of this kind.

Dechlorane Plus (DP) is a high production volume, chlorinated flame retardant. Despite its long production history, it was only recently found in the environment. The first "sightings" of DP were in the North American Great Lakes, but subsequent work has indicated that DP is a global contaminant. For example, DP has recently been detected along a pole-to-pole transect of the Atlantic Ocean. Although it was initially thought that DP was produced only in North America, another DP production plant has recently been identified in China. During the course of characterizing DP in the environment, other "DP-like" compounds were identified. These DP analogs, some created from impurities contained in the starting materials during DP's synthesis, have also been detected globally. Screening-level modeling data are in general agreement with available environmental measurements, suggesting that DP and it analogs may be persistent, bioaccumulative, and subject to long-range transport and that these chemicals may be candidates for Annex D evaluation under the United Nations Stockholm Convention on Persistent Organic Pollutants. However, more research is required to better quantify the emissions, exposures, and toxicological effects of DP and its analogs in the environment. In particular, there is a need to obtain more monitoring, bioaccumulation, degradation rate, and toxicity information.

Benzophenones and benzotriazoles are widely used as ultraviolet (UV) light filters and stabilizers in cosmetics, skin creams, and body lotions and as corrosion inhibitors in building materials, automobile components, and automotive antifreeze cooling systems. Benzophenones and benzotriazoles have been reported to occur in the environment. Some of these UV filters have been reported to possess significant estrogenic activity. Despite this, very few studies have examined their occurrence and profiles in the environment. In this work, we determined five benzophenone-type UV filters and two benzotriazole-type corrosion inhibitors, namely, 2-hydroxy-4-methoxybenzophenone (2OH-4MeO-BP), 2,4-dihydroxybenzophenone (2,4OH-BP), 2,2'-dihydroxy-4-methoxybenzophenone (2,2'OH-4MeO-BP), 2,2',4,4'-tetrahydroxybenzophenone (2,2',4,4'OH-BP), 4-hydroxybenzophenone (4OH-BP), 1H-benzotriazole (1H-BT), and 5-methyl-1H-benzotriazole (5Me-1H-BT), in sediment and sewage sludge samples, using liquid-liquid extraction and liquid chromatography-tandem mass spectrometry (LC-MS/MS). In addition, four benzotriazole-type UV stabilizers, namely, 2-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole (UV-326), 2,4-di-t-butyl-6-(5-chloro-2H-benzotriazole-2-yl) phenol (UV-327), 2-(2H-benzotriazole-2yl)-4,6-di-t-pentylphenol (UV-328), and 2-(5-t-butyl-2-hydroxyphenyl) benzotriazole (TBHPBT) were determined by gas chromatography (GC)-mass spectrometry (MS). The limits of quantitation (LOQ) were in the ranges of 0.06-0.33 ng g⁻¹ dry weight (dw) and 0.1-1.65 ng g⁻¹ dw for sediment and sludge samples, respectively. Recoveries of target compounds spiked into sample matrices and passed through the entire analytical procedure ranged from 70% to 116% (RSD: 3.32-13.8%) and from 82% to 106% (RSD: 2.89-8.09%) for the compounds analyzed by LC-MS/MS and GC-MS, respectively. The methods were applied to the analysis of sediment samples from the Songhua, Saginaw, and Detroit Rivers; the sum concentrations of target compounds were 3.29-9.93, 5.81-22.5, and 190-389 ng g⁻¹ dw, respectively. Five sludge samples collected from five wastewater treatment plants in northeastern China contained the sum concentrations of target compounds in the range of 104-6370 ng g⁻¹ dw. The concentration of UV-328 in sludge was the highest (mean: 1300 ng g⁻¹ dw) among the target compounds. To our knowledge, this is the first work to report the occurrence of 2OH-4MeO-BP, 2,4OH-BP, 2,2'OH-4MeO-BP, 2,2',4,4'OH-BP, and 4OH-BP in sediment and sludge samples.

Dechloranes, including Dechlorane Plus (DP), Mirex (Dechlorane), Dechlorane 602 (Dec 602), Dechlorane 603 (Dec 603), and Dechlorane 604 (Dec 604), were determined using GC-MSD for water, sediment and oyster samples collected at 15 sampling sites near the Bohai and Huanghai Sea shore area of northern China in 2008. DP and Mirex were detected in most water, sediment, and oyster samples, which indicated widespread distribution of these two compounds. The mean concentrations in water, sediment and oyster samples, respectively, were 1.8 ng/L, 2.9 ng/g dry weight (dw) and 4.1 ng/g wet weight (ww) for total DP, and 0.29 ng/L, 0.90 ng/g dw, and 2.0 ng/g ww for Mirex. Dec 602 and Dec 603 were not detected in water but in small portions of the sediment and oyster samples, showing a low level of contamination by these two chemicals in the region. Strong and significant correlations were found between total DP and Mirex concentrations in water, sediment and oyster samples, probably suggesting similar local sources of these two chemicals. Dec 604 was not found in any samples. The biota-sediment accumulation factor (BSAF) of DP, Mirex, and Dec 602 declined along with the increase of their logarithm of octanol-water partition coefficients (log Kow), possibly indicating that compounds with lower log Kow (like Mirex and Dec 602) accumulated more readily in biota. The mean fractional abundance of syn-DP (fsyn) was 0.34 in water samples, a value lower than that in Chinese commercial mixture (0.41), while the mean fsyn for surface sediment (0.44) and oyster (0.45) samples were higher than technical values. Enrichment of syn-DP in oyster was in agreement with previously reported findings in Great Lakes fish. Enrichment of syn-DP in marine surface sediments, however, is contrary to data reported for fresh water sediments. To our knowledge this is the first report of Dec 602, Dec 603, and Dec 604 in a marine environment and also the first report of Dechloranes in marine biota.

Two global atmospheric transport models for persistent toxic substances were employed to quantify the intercontinental atmospheric transport of lindane in 2005 using a recently constructed global lindane emission inventory. The focus of this numerical investigation was to identify, on an intercontinental scale, the major sources of lindane that contributed to the contamination of North America and the Arctic. Both models simulated several strong episodic trans-Pacific atmospheric transport events of lindane from its sources in Asia to the western seaboard of North America. Modeling results also detected, forthe firsttime, an important atmospheric pathway for persistent toxic substances from Western Africa/Western Europe to the Caribbean, the southern United States, and the eastern seaboard of North America. Several episodic lindane transAtlantic atmospheric transport events were found from May to October. These events were associated primarily with the easterly trade winds and the African easterly wave that extends from the subtropical eastern Atlantic to the Caribbean. This atmospheric pathway for toxic chemicals has a substantial implication for the level of toxic substances in North America. Atmospheric mechanisms contributing to these transport events are briefly discussed. Multiple modeling scenarios were studied to assess the contribution of lindane sources in Europe, Asia, and North America to its fate in the Arctic. Results show that these continental contributions are season-dependent with the highest contribution from Europe in the spring.

Atrazine is one of the most widely used herbicides in North America and has been primarily applied to corn production in the Great Lakes basin for over 30 years. During 1996-2002, atrazine concentrations in the atmospheric gas and particle phases were investigated at three Canadian Integrated Atmospheric Deposition Network (IADN) sites including two lakeside sites (Burnt Island and Point Petre) and a rural inland site (Egbert). Strong seasonality with peak concentrations occurring in late April-early July was observed. An atrazine usage map for Canada (sum: 870 t) and the United States (sum: 34 500 t) in 2002 was created. Local application and regional atmospheric transport both appear to contribute to its atmospheric occurrence, while the latter might episodically result in high concentrations events. No strong temperature dependence was observed for atrazine particle-gas partitioning. Recent measurement results of atrazine in precipitation samples collected at Egbert and another agricultural site, Vineland, through the Canadian Atmospheric Network for Currently Used Pesticides (CANCUP), are also presented, Dry, wet, and gas exchange deposition all contribute to atmospheric inputs of atrazine to the Great Lakes. For Lake Ontario, gas exchange is estimated to be of similar magnitude to dry and wet deposition.

Polychlorinated biphenyl (PCB) concentrations in surface soil samples (0-20 cm) from 52 sites (4 background, 39 rural, and 9 urban) across China in 2005 are presented. The average concentration of total PCBs among all the sites was 515 pg/g dry weight (dw), approximately one-tenth of that in global background soil in 1998. Differences of less than 1 order of magnitude were found between all background and rural sites, indicating a generally uniform distribution of PCBs in Chinese background/rural surface soil. While the major PCB homologue group in global background soil is hexa-PCB followed by penta-PCB, the major PCB homologue group in Chinese background/rural soil is tri-PCB followed by di-PCB, indicating a rather fresh signature in comparison to the much weathered PCBs in global surface soil. The correlation between sigmaPCBs and also each PCB homologue group per soil organic carbon (SOC) content in background/rural soil with longitude from 80 degrees to 122 degrees East was studied. The results indicated the strong influence of PCBs concentrations in Chinese background/rural soil by proximity to source region and SOC content, and also provided evidence for urban fractionation effect of PCBs in soil in the city of Shanghai and the longitudinal fractionation of PCBs in Chinese background/ rural soil from east to west. This work is the first comprehensive and spatial study of its kind for PCBs in Chinese surface soil on a national scale, and the data presented in this study can provide baseline information for establishing a long-term PCBs monitoring program in China.

The Svalbard archipelago in arctic Norway receives considerable semivolatile organic contaminant (SOC) inputs from the atmosphere. To measure the history of net SOC accumulation there, we analyzed the upper 40 m of an ice core from Austfonna, the largest ice cap in Eurasia, for several legacy organochlorine (OC) compounds and current-use pesticides (CUPs) including organophosphorus (OP), triazine, dinitroaniline, and chloroacetamide compounds. Five OP compounds (chlorpyrifos, terbufos, diazinon, methyl parathion, and fenitrothion), two OCs (methoxychlor and dieldrin), and metolachlor--an herbicide--had historical profiles in the core. The highest OC concentration observed was aldrin (69.0 ng L(-1)) in the surface sample (1992-1998). The most concentrated OP was dimethoate (87.0 ng L(-1)) between 1986 and 1992. The surface sample also had highest concentrations of pendimethalin (herbicide, 18.6 ng L(-1)) and flutriafol, the lone observed fungicide (9.6 ng L(-1)). The apparent atmospheric persistence of CUPs likely results from little or no oxidation by OH* during the dark polar winter and in spring. Long-range atmospheric pesticide transport to Svalbard from Eurasia is influenced by the positive state of the North Atlantic Oscillation Index since 1980 and also by occasional fast-moving summer air masses from northern Eurasian croplands.

A coupled atmospheric transport model was employed to study six scenarios to assess the contribution of reemission and long-range transport of toxaphene from different sources in the United States to its environmental fate in the Great Lakes ecosystem in the year 2000. Modeled air concentrations at the first model level (1.5 m) range from less than 5 pg m(-3) over the upper Great lakes (Lakes Superior and Huron) to several tens of picograms per cubic meter over the lower Great Lakes (Lakes Erie and Ontario) in the summer but drop off to the range from 0.05 to 2 pg m(-3) in the wintertime. The modeled toxaphene depositions to the lakes suggest a decreasing trend from the mid-1990s to 2000. Modeling results showed that, on an annual basis, for the Great Lakes basin as a whole, the southeast U.S. sources made the largest contribution to the toxaphene air concentrations and dry and wet depositions at 72%, 78%, and 88% respectively. The model results also showed that a significant proportion of these contributions occur during relatively short episodic events due primarily to the interseasonal changes in atmospheric circulation patterns.

As the contamination of beta-hexachlorocyclohexane (beta-HCH) in the Arctic air, seawater, and biota is an environmental concern, there is a need for emission inventories of beta-HCH to be used by the modeling community to predict the fate and transport of beta-HCH. This paper presents such emission inventories for beta-HCH. The total global usage of beta-HCH between 1945 and 2000 is estimated at 850 kt, 230 kt of which was emitted to the atmosphere over the same time period. Usage of beta-HCH was estimated to be around 36 kt in 1980 and 7.4 kt in 1990. Total beta-HCH emissions in 1980 were 9.8 kt with 83% attributed to the application in 1980 and 17% to soil residues due to prior applications. Total beta-HCH emissions in 1990 were 2.4 kt with 78% attributed to the application in 1990 and 22% to soil residues. While it assumed that no usage of technical HCH occurred in 2000, the global beta-HCH emissions in this year due to soil residues were estimated at 66 t. It has shown that the global beta-HCH emissions have undergone a "southward tilt" over the time period studied as more northern countries have banned the use of technical HCH.

The global usage of technical HCH and lindane in 1980 and 1990 are presented. The total global usage for technical HCH was estimated to be 40 000 t in 1980 and 29 000 t in 1990, and for lindane it was 5900 t in 1980 and 4000 t in 1990. Based on these data, the global usage of both α-HCH and γ-HCH were calculated. The total usage of α-HCH was around 28 000 t in 1980 and 20 400 t in 1990, while the total usage of γ-HCH was around 11 900 t in 1980 and 8400 t in 1990. The ratio of γ-HCH to α-HCH was 0.43 in 1980 and 0.41 in 1990. The usage data on countries are then mapped to a grid system with 1° × 1° longitude/latitude resolution to be useful for modeling. It is suggested that banning usage of technical HCH by a number of countries, such as China in the early 1980s and the former Soviet Union in the beginning of 1990s, may contribute to the decline of the atmospheric concentrations of both α-HCH and γ-HCH in 1992−1993. While many countries banned use of technical HCH in 1980s, lindane was still used by many...