Distribution in ice is regarded as one of important transport modes for pollutants in seasonal freeze-up waters in cold regions. However, the distribution characteristics and mechanisms of fluorinated antibiotics as emerging contaminants during the water freezing process remain unclear. Here, florfenicol and norfloxacin were selected as model fluorinated antibiotics to investigate their ice-water distribution. Effects of antibiotic molecular structure on the distribution were explored through comparative studies with their non-fluorinated structural analogs. Results showed that phase changes during the ice growth process redistributed the antibiotics, with antibiotic concentrations in water 3.0–6.4 times higher than those in ice. The solute-rich boundary layer with a concentration gradient was presented at the ice-water interface and controlled by constitutional supercooling during the freezing process. The ice-water distribution coefficient (KIW) values of antibiotics increased by 34.8%–38.0% with a doubling of the cooling area. The solute distribution coefficient (Kbₛ) values of antibiotics at −20 °C were 65.6%–70.3% higher than at −10 °C. The KIW and Kbₛ values of all antibiotics were negatively correlated with their water solubilities. The fluorine substituents influenced the binding energies between antibiotics and ice, resulting in a 1.1-fold increase in the binding energy of norfloxacin on the ice surface relative to its structural analog pipemidic acid. The results provide a new insight into the transport behaviors of fluorinated pharmaceuticals in ice-water systems.

Fabric and foam samples from popular children car seats marketed in the United States during 2018 were tested for fluorine content by particle-included gamma ray emission spectroscopy (PIGE, n = 93) and X-ray photoelectron spectroscopy (XPS, n = 36), as well as for per- and polyfluoroalkyl substances (PFAS) by liquid and gas chromatography mass spectrometry (LC/MS and GC/MS, n = 36). PFAS were detected in 97% of the car seat samples analyzed with MS, with total concentrations of 43 PFAS (∑PFAS) up to 268 ng/g. Fabric samples generally had greater ∑PFAS levels than foam and laminated composites of foam and fabric. The three fabric samples with the highest total fluorine content as represented by the highest PIGE signal were also subjected to ultraviolet (UV) irradiation and the total oxidizable precursor (TOP) assay. Results from these treatments, as well as the much higher organofluorine levels measured by PIGE compared to LC/MS and GC/MS, suggested the presence of side-chain fluorotelomer-based polymers (FTPs), which have the potential to readily degrade into perfluoroalkyl acids (PFAAs) under UV light. Furthermore, fluorotelomer (meth)acrylates were found to be indicators for the presence of (meth)acrylate-linked FTPs in consumer products, and thus confirmed that at least half of the tested car seats had FTP-treated fabrics. Finally, extraction of selected samples with synthetic sweat showed that ionic PFAS, particularly those with fluorinated carbons ≤8, can migrate from fabric to sweat, suggesting a potential dermal route of exposure.

In this study, the detoxification mechanisms of water-soluble fluorine in the bottom ash and the distribution of fluorine during the spent potlining (SPL) incineration were characterized in response to four calcium compounds using an experimental tube furnace. CaSiO₃, CaO, Ca(OH)₂, and CaCO₃-assisted SPL incineration converted NaF to low toxicity compounds in the bottom ash yielding a conversion range of 54.24–99.45% relative to the individual SPL incineration. The two main mechanisms of the fluorine transformation were the formations of CaF₂ and Ca₄Si₂O₇F₂. The fluorine transformation efficiency was greater with CaSiO₃ than CaO, Ca(OH)₂, and CaCO₃. Our simulations demonstrated that SiO₂ enhanced the conversion of NaF. The fluorine leaching content of the bottom ash was estimated at 13.71 mg⋅L⁻¹ after the SPL co-incineration with CaSiO₃ (Ca:F = 1.2:1). The acid-alkali solutions had no significant effect on the fluorine leaching content of the bottom ash when 3 ≤ pH ≤ 12. Fluorine during the SPL co-incineration with CaSiO₃ (Ca:F = 1.2:1) at 850 °C for 60 min was partitioned into 83.37, 13.90, and 2.72% in the bottom ash, fly ash, and flue gas, respectively. The transformation and detoxification mechanisms of water-soluble fluorine provide new insights into controls on fluorine emission from the SPL incineration.

With the phase out of perfluorooctanesulfonate (PFOS) and perfluorooctanoic acid (PFOA), the composition profiles of poly- and perfluoroalkyl substance (PFAS) in our living environment are unclear. In this study, 25 PFASs were analyzed in indoor dust samples collected from urban, industrial, and e-waste dismantling areas in China. PFOS alternatives, including 6:2 chlorinated polyfluorinated ether sulfonate (6:2 Cl-PFESA) (median: 5.52 ng/g) and 8:2 chlorinated polyfluorinated ether sulfonate (8:2 Cl-PFESA) (1.81 ng/g), were frequently detected. By contrast, PFOA alternatives, such as hexafluoropropylene oxide dimer acid (HPFO-DA, Gen-X) and ammonium 4,8-dioxa-3H-perfluorononanoate (ADONA), were not found in any of the dust samples. As expected, all legacy PFASs were widely observed in indoor dust, and 4 PFAS precursors were also detected. Dust concentrations of 6:2 Cl-PFESA were strongly correlated (p < 0.05) with those of 8:2 Cl-PFESA regardless of sampling sites. 6:2 Cl-PFESA was also significantly associated with that of PFOS in industrial and e-waste (p < 0.01) areas. Association analysis suggested that the sources of PFOS and its alternatives are common or related. Although ∑Cl-PFESA concentration was lower than that of PFOS (17.4 ng/g), industrial areas had the highest 6:2 Cl-PFESA/PFOS ratio (0.63). Composition profiles of PFASs in the industrial area showed the forefront of fluorine change. Thus, the present findings suggested that Cl-PFESAs are widely used as PFOS alternatives in China, and high levels of human Cl-PFESA exposure are expected in the future. Short-chain PFASs (C4–C7) were the predominant PFASs found in dust samples, contributing to over 40% of ∑total PFASs. Furthermore, perfluoro-1-butanesulfonate/PFOS and perfluoro-n-butanoic acid (PFBA)/PFOA ratios were 2.8 and 0.72, respectively. These findings suggested shifting to the short-chain PFASs in the environment in China. To the authors knowledge this is the first study to document the levels of 6:2 Cl-PFESA, 8:2 Cl-PFESA in indoor dust.

The concentration distributions, compositional profiles and seasonal variations of 17 perfluoroalkyl acids (PFAAs) in PM₁₀ (particles with aerodynamic diameters < 10 μm) were determined in seven coastal cities of the Bohai and Yellow Seas. The detection rates of perfluorooctanoic acid (PFOA) and short-chain components (perfluoroalkyl carboxylic acids (PFCAs) with ≤7 carbon atoms and perfluoroalkane sulfonic acids (PFSAs) with ≤5 carbon atoms) were much higher than those of other long-chain PFAA species. The annual average concentration of total PFAAs in PM₁₀ ranged from 23.6 pg/m³ to 94.5 pg/m³ for the sampling cities. The monthly mean concentrations of PFAAs in PM₁₀ in some sampling cities reached a peak value in winter, while no significant seasonal differences presented in other cities. High concentrations of PFAAs in the northern cities generally occurred during the local heating period (from November to March). Generally, the dominant components of PFAAs were PFOA and perfluorobutyric acid (PFBA). Some significantly positive correlations (p < 0.01) between the 10 dominant components were revealed in the sampling cities, which implied similar sources and fate behaviors. Based on the simulated 72-hr backward trajectory tracking of air masses, the clustering results demonstrated the sampling cities were affected mainly by the atmospheric transport in sequence from the northwest, the southwest and the open seas, and many transport trajectories of air masses passed by the local fluorine chemical manufacturers in Liaoning, Shandong, Jiangsu, and Hubei Provinces. The estimated average daily intake (ADI) corresponding to the residents in different age groups indicated insignificant contributions to PFOA and perfluorooctane sulfonate (PFOS) exposures by inhalation of PM₁₀ compared to ingestion by daily diet, while the higher ADI of PFOA than the reported levels for adults should be a concern. The calculated hazard ratios (HR) exhibited low noncancer risks by inhalation exposure to PFOA and PFOS in PM₁₀.

A rough estimate of the annual amount of sulfur, arsenic, mercury and fluoride emission from spontaneous combustion of coal gangue in China was determined. The weighted mean concentrations of S, As, Hg, and F in coal gangue are 1.01%, 7.98, 0.18, and 365.54 mg/kg, respectively. Amounts of S, As, Hg, and F emissions from coal gangue spontaneous combustion show approximately 1.13 Mt, and 246, 45, and 63,298 tons in 2013, respectively. The atmospheric release amount of sulfur from coal gangue is more than one tenth of this from coal combustion, and the amounts of As, Hg, and F are close to or even exceed those from coal combustion. China's coal gangue production growth from 1992 to 2013 show an obvious growth since 2002. It may indicate that Chinese coal gangue has become a potential source of air pollution, which should be included in emission inventories.

Concentrations of 13 perfluoroalkyl substances (PFASs) were quantified in 79 surface soil samples from 17 coastal cities in three provinces and one municipality along the Bohai and Yellow Seas. The ∑PFASs concentrations ranged from less than limitation of quantification (LOQ) to 13.97 ng/g dry weight (dw), with a mean of 0.98 ng/g dw. The highest concentration was observed along the Xiaoqing River from Shandong province, followed by that from the Haihe River in Tianjin (10.62 ng/g dw). Among four regions, ∑PFASs concentrations decreased in the order of Tianjin, Shandong, Liaoning and Hebei, which was consistent with levels of urbanization. Fluorine chemical industries allocated in Shandong and Liaoning played important roles in terms of point emission and contamination of PFASs, dominated by perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS). Intensive anthropogenic activities involved in urbanization possibly resulted in increasing releases of PFASs from industrial and domestic sources.