Technology review and evaluation of different chemical oxidation conditions on treatability of PFAS

Per‐ and polyfluoroalkyl substances (PFAS) are a class of stable compounds widely used in diverse applications. These emerging contaminants have unique properties due to carbon–fluorine (C–F) bonds, which are some of the strongest bonds in chemistry. High energy is required to break C–F bonds, which results in this class of compounds being recalcitrant to many degradation processes. Many technologies studied that have shown treatment effectiveness for PFAS cannot be implemented in situ. Chemical oxidation is a demonstrated remediation technology for in situ treatment of a wide range of organic environmental contaminants. An overview of relevant literature is presented, summarizing the use of single or combined reagent chemical oxidation processes that offer insight into oxidation–reduction chemistries potentially capable of PFAS degradation. Based on the observations and results of these studies, bench‐scale treatability tests were designed and performed to establish optimal conditions for the formation of specific free radical species, including superoxide and sulfate radicals, via various combinations of oxidants, catalysts, pH buffers, and heat to assess PFAS treatment by chemical oxidants. The study also suggests the possible abiotic transformations of some PFAS when chemical oxidation is or was used for treatment of primary organic contaminants (e.g., petroleum or chlorinated organic compounds) at a site. The bench‐scale tests utilized field‐collected samples from a firefighter training area. Much of the available data related to chemical oxidation of PFAS has only been reported for one or both of the two more commonly discussed PFAS (perfluorooctane sulfonic acid and/or perfluorooctanoic acid). In contrast, this treatability study evaluates oxidation of a diverse list of PFAS analytes. The results of this study and published literature conclude that heat‐activated persulfate is the oxidation method with the best degradation of PFAS. Limited reduction of reported PFAS concentrations in this study was observed in many oxidation reactors; however, unknown mass of PFAS (such as precursors of perfluoroalkyl acids) that cannot be identified in a field collected sample complicated quantification of how much oxidative destruction of PFAS actually occurred.     

Accumulation of perfluorinated compounds in captive Bengal tigers (Panthera tigris tigris) and African lions (Panthera leo Linnaeus) in China

The accumulation of perfluorinated compounds (PFCs) in the sera of captive wildlife species Bengal tigers (Panthera tigris tigris) and African lions (Panthera leo Linnaeus) from Harbin Wildlife Park, Heilongjiang Province, in China were analyzed by high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). Perfluorooctanesulfonate (PFOS) was the predominant contaminant with a mean serum concentration of 1.18 ng mL(-1) in tigers and 2.69 ng mL(-1) in lions. Perfluorononanoic acid (PFNA) was the second most prevalent contaminant in both species. The composition profiles of the tested PFCs differed between tigers and lions, and the percentages of perfluorooctanoic acid (PFOA) were greater in lions than in tigers, indicating different exposures and/or metabolic capabilities between the two species. Assessments of the risk of PFC contamination to the two species were obtained by comparing measured concentrations to points of departure or toxicity reference values (TRVs). Results suggest no risk of PFOS exposure or toxicity for the two species.     

Observational and modeling study of dry deposition on surrogate surfaces in a South China city: implication of removal of atmospheric crustal particles

Dry deposition samples collected during 1999–2001 at a South China site using surrogate surfaces were analyzed by capillary electrophoresis. Collector surface properties played important roles to the dry deposition. The deposition velocities for various species ranged from 0.02 to 1.69 cm s^???1, in general agreement with literature values. More than 90% of Ca^2?+? was deposited by sedimentation and its comparable values of dry or wet removal residence times imply that dry deposition is an important atmospheric removal process for the ubiquitous crustal species in South China, compared with precipitation scavenging. Relatively good agreement was found when the species deposition velocities were modeled based on up-to-date knowledge of particle dry deposition. The total depositions for anthropogenic and crustal species in northern China are likely to be much higher than those in the south, including our site where the fluxes of the acidic species SO₄ ^2??? and NO₃ ^??? were 4.4 and 2.2 g m^???2 year^???1, respectively. The sum of dry deposition for cations Na^?+?, Ca^2?+?, Mg^2?+?, and K^?+? contributes 44% of the total flux, which is equivalent to the value estimated in Europe.     

Temperature and nutrients are significant drivers of seasonal shift in phytoplankton community from a drinking water reservoir,subtropical China

Reservoirs are an important source of water supply in many densely populated areas in southeast China. Phytoplankton plays an important role in maintaining the structure and function of these reservoir ecosystems. Understanding of seasonal succession in phytoplankton communities and its driving factors is essential for effective water quality management in drinking-water reservoirs. In this study, water samples were collected monthly at the surface layers of riverine, transitional, and lacustrine zones from May 2010 to April 2011 in Tingxi Reservoir, southeast China. The phytoplankton showed distinct seasonal shifts in community structure at both taxonomic and functional levels. Cyanophyta was the dominant group in summer, especially species of Raphidiopsis in May and Aphanizomenon in June, and cyanobacterial dominance was promoted by both warmer conditions and excessive nutrients loading. Cyanophyta was gradually replaced by Cryptophyta (e.g., Chroomonas caudata) in abundance and by Bacillariophyta (Fragilaria sp. or Synedra sp. and Melosira sp.) in biomass with decreasing temperature. It appeared that seasonal shifts in phytoplankton composition were closely related to climate, nutrient status, and hydrology in this reservoir. Our partial RDA results clearly showed that water temperature and nutrients (TN and TP) were the most critical factors driving phytoplankton community shift in the abundance and biomass data, respectively. Further, with the global warming, cyanobacterial blooms may increase in distribution, duration, and intensity. In our study, the abundance and biomass of cyanobacteria had significant and positive correlations with temperature and phosphorus. Therefore, a stricter limit on nutrient input should be a priority in watershed management to protect drinking water from the effects of cyanobacterial blooms, especially in high-temperature period.     

Spectrophotometric Determination of Atmospheric Acidity by means of the Displacement of the Equilibrium of Acid-Base Indicators

A method is described for determining acidity by means of the spectrophotometric determination of the displacement of the equilibrium of açid-base indicators. The method is simple, sensitive and free of known interferences. There is no dependence on costly or sophisticated equipment and the results obtained are reliable and reproducible.     

Pyrolysis Kinetics and Residue Characteristics of Petrochemical Industrial Sludge

ABSTRACT

This study investigated the pyrolysis characteristics of sludge from wastewater treatment plants in the petrochemical industry and focused on the pyrolysis kinetics, elemental composition of residue, and volatile organic compounds (VOCs) of exhaust gas. As pyrolysis temperature increased to 773 K, the increasing rate of crude oil production tended to a stable condition. The result indicated that the optimal temperature of crude oil and water mixed production was 773 K. When pyrolysis temperature increased from 673 to 973 K, carbon, oxygen, nitrogen, and hydrogen concentrations of residue decreased and the sulfur concentration of residue increased. The concentrations of benzene, toluene, ethylbenzene, and styrene increased by the increasing pyrolysis temperature. We found that the reaction order of sludge pyrolysis was 2.5 and the activation energy of the reaction was 11.06 kJ/mol. We believe that our pyrolysis system is transitional between devolatilization and combustion.     

Development of regenerative dye impregnated mesoporous silica materials for assessing exposure to ammonia

The mesostructured materials MCM-41 and SBA-15 were studied as possible supports of bromocresol green (BG) dye impregnation for the ammonia gas detection because of their large surface area, high regenerative property, and high thermal stability. X-ray diffraction, transmission electron microscopy, scanning electron microscope, and N₂ adsorption analysis were used to characterize the prepared materials. These materials could sense ammonia via visible color change from yellowish-orange to blue color. The color change process of the nanostructured materials was fully reversible during 10 cyclic tests. The results indicated that the ammonia absorption responses of the two nanostructured materials were both very sensitive, and high linear correlation and high precision were achieved. As the gaseous ammonia concentrations were 50 and 5 ppmv, the response times for the SBA-15/BG were only 1 and 5 min, respectively. Moreover, the BG dye-impregnated SBA-15 was less affected by the variation in the relative humidity. It also had faster response for the detection of NH₃, as well as lower manufacturing price as compared to that of the dye-impregnated MCM-41. Such feature enables SBA-15/BG to be a very promising material for the detection of ammonia gas.

Implications: The detector tube is a convenient ambient ammonia detection device. However, almost all the commercial detector tubes can be used once only, which not only increases the purchase cost but also produces lots of waste. In this study, we developed two sensing materials that are sensitive for repeated usage. The two mesoporous silica-based materials, MCM-41 and SBA-15, are impregnated by an organic dye of bromocresol green to induce color change behavior that can be easily observed by the naked eye, and it is concluded that dye-impregnated SBA-15/BG is a very promising material for the detection of ammonia gas.     

Background levels of Persistent Organic Pollutants in humans from Taiwan: Perfluorooctane sulfonate and perfluorooctanoic acid

Perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) have recently received attention due to their widespread contamination of the environment. PFOS and PFOA are stable in the environment and resistant to metabolism, hydrolysis, photolysis and biodegradation. PFOS and PFOA have been found in human blood and tissue samples from both occupationally exposed workers and the general worldwide population. This study aimed to determine the background levels of PFOS and PFOA in the Taiwanese population, investigate related factors, and compare exposure in Taiwan to that in other countries. The concentration of PFOS in the 59 serum samples collected from the general population in Taiwan ranged from 3.45 to 25.65 ng mL⁻¹ (median: 8.52), and the concentration of PFOA ranged from 1.55 to 7.69 ng mL⁻¹ (median: 3.22). There was a significant positive correlation (r = 0.51; p < 0.0001) between PFOS and PFOA concentrations. Males had higher concentrations of PFOA and PFOS than females. PFOS levels in serum increased with age. This study is the first investigation to reveal the PFOS and PFOA levels of serum samples in the general population of Taiwan. The levels of PFOS and PFOA in Taiwanese serum samples were comparable with those from other countries (PFOS: 5.0–35 ng mL⁻¹, PFOA: 1.5–10 ng mL⁻¹).     

Characteristic Study of Ambient Air Total Gaseous Mercury (TGM) Concentrations During Rainy and Non-Rainy Periods at a Traffic Site in Taiwan

This investigation studied the concentrations of ambient air total gaseous mercury (TGM) during the rainy periods at the Hung-Kuang traffic sampling site in central Taiwan from May 26 to June 16, 2014. The results were compared with those of a previous study for ambient air TGM during non-rainy daytime and nighttime periods at the Hung-Kuang traffic sampling site, which was conducted during March 21 to July 20, 2012. The observed mean concentration of ambient air TGM was 1.16 ng/m³ during the rainy periods at the Hung-Kuang traffic sampling site. The mean ambient air TGM concentrations were higher in the non-rainy sampling period in daytime than in the rainy sampling period from this study. The mean ratio of non-rainy sampling period in daytime to that of rainy sampling period for ambient air TGM were 3.15. Furthermore, the mean ambient air TGM concentrations were higher in the non-rainy sampling period in nighttime in than in the rainy sampling period for this study. The mean rations for non-rainy sampling period in nighttime to that of the rainy sampling period for ambient air TGM were 2.70. The results obtained in this study also revealed that the ambient air TGM concentrations during the rainy period had the lowest concentrations when compared with the other sampling sites in other world regions.