[Simultaneous detection of lower aliphatic amines and conventional cations in atmospheric PM2.5 particulates by ion chromatography].

Many amine pollutants exist in the atmosphere. Lower aliphatic amines promote the formation and growth of particles into PM2.5, which damages the heart, lungs, and kidneys of the human body. PM2.5, a common atmospheric particulate pollutant with complex compositions, is the main cause of haze weather. Therefore, measuring the contents of lower aliphatic amines and cations in PM2.5 is of great significance for monitoring environmental air quality and protecting human health. This study established a suppressed ion-chromatographic method with conductivity for the simultaneous detection of four lower aliphatic amines (methylamine, dimethylamine, trimethylamine, and ethylamine) and five cations (Na+, N[Formula: see text], and Ca2+ showed high concentrations. The contents of the four lower aliphatic amines were low; however, the ethylamine content in some samples was high. The results indicate that the proposed method meets the quantification requirements for cations and lower aliphatic amines in PM2.5, with simple processing, high sensitivity, and good accuracy. It can quickly and accurately detect a large number of samples and be used to assess the pollution of small particles in the air as well as trace pollution sources to protect human health.

Performance and mechanism of simultaneous Sb(III) and Cd(II) removal from water by Fe-Mn binary oxide/bone char.

A novel Fe-Mn binary oxide (FMBO)/bone char composite (FMBC) was synthesized and utilized to simultaneously adsorb Sb(III) and Cd(II) from aqueous phase in this study. The successful loading of Fe-Mn binary oxide on the bone char surface was revealed by the results of scanning electron microscope, X-ray diffraction patterns, and energy dispersive spectroscopy of FMBC. The FMBC exhibited remarkable ability of simultaneous removing Sb(III) and Cd(II) from aqueous, and the presence of Cd(II) enhanced Langmuir theoretical maximum adsorption capacity for Sb(III) significantly from 67.8 to 209.0 mg/g. Besides, FMBC could efficiently remove Sb(III) and Cd(II) in the wide initial pH range of 2-7. The influences of ionic strength, co-existing anions, humic acid, and temperature on the adsorption of Sb(III) and Cd(II), and the application potential of FMBC in actual groundwater were investigated. The main mechanisms of Sb(III) and Cd(II) adsorption onto FMBC involved redox, electrostatic interaction, surface complexation, ion exchange, and precipitation. The result of X-ray photoelectron spectroscopy and mapping spectrum analysis revealed that Mn(III) on FMBC played the key role in the Sb(III) oxidation, while FeOOH worked as the adsorption sites of FMBC. Meanwhile, the hydroxyapatite on FMBC also contributed to the removal of Cd(II). The presence of Cd(II) not only increased the positive charge on the surface of FMBC but also formed the Fe-Sb-Cd ternary complex, promoting the removal of Sb. This work provides valuable information for the application of FMBO/bone char as a cost-effective adsorbent to remediate co-pollution of Sb(III) and Cd(II) in aqueous environment.

Exposure and health risk assessment of PM2.5-bound polycyclic aromatic hydrocarbons during winter at residential homes: A case study in four Chinese cities.

Residential indoor PM2.5 were concurrently collected in Hong Kong, Guangzhou, Shanghai, and Xi'an during the winter and early spring seasons of 2016-2017, for updating the current knowledge of the spatial variation of indoor air pollution and the potential health risks in China. PM2.5-bound polycyclic aromatic hydrocarbons (PAHs) were characterized, and the associated inhalation cancer risks were assessed by a probabilistic approach. Higher levels of indoor PAHs were identified in Xi'an residences (averaged at 176.27 ng m-3) with those of other cities ranging from 3.07 to 15.85 ng m-3. Traffic-related fuel combustion was identified as a common contributor to indoor PAHs through outdoor infiltration for all investigated cities. Indoor PAHs profiles showed city-specific differences, while distinctions between profiles based on indoor activities or ambient air quality were limited. Similar with the total PAHs concentrations, the estimated toxic equivalencies (TEQ) with reference to benzo[a]pyrene in Xi'an residences (median at 18.05 ng m-3) were above the recommended value of 1 ng m-3 and were magnitudes higher than the other investigated cities with estimated median TEQ ranging from 0.27 to 1.55 ng m-3. Incremental lifetime cancer risk (ILCR) due to PAHs inhalation exposure was identified with a descending order of adult (median at 8.42 × 10-8) > adolescent (2.77 × 10-8) > children (2.20 × 10-8) > senior (1.72 × 10-8) for different age groups. Considering the lifetime exposure-associated cancer risk (LCR), potential risks were identified for residents in Xi'an as an LCR level over 1 × 10-6 was identified for half of the adolescent group (median at 8.96 × 10-7), and exceedances were identified for about 90 % of the groups of adults (10th percentile at 8.29 × 10-7) and seniors (10th percentile at 1.02 × 10-6). The associated LCR estimated for other cities were relatively insignificant.

Selective formation of acetate intermediate prolongs robust ethylene removal at 0 °C for 15 days.

Efficient ethylene (C2H4) removal below room temperatures, especially near 0 °C, is of great importance to suppress that the vegetables and fruits spoil during cold-chain transportation and storage. However, no catalysts have been developed to fulfill the longer-than-2-h C2H4 removal at this low temperature effectively. Here we prepare gold-platinum (Au-Pt) nanoalloy catalysts that show robust C2H4 (of 50 ppm) removal capacity at 0 °C for 15 days (360 h). We find, by virtue of operando Fourier transformed infrared spectroscopy and online temperature-programmed desorption equipped mass spectrometry, that the Au-Pt nanoalloys favor the formation of acetate from selective C2H4 oxidation. And this on-site-formed acetate intermediate would partially cover the catalyst surface at 0 °C, thus exposing active sites to prolong the continuous and effective C2H4 removal. We also demonstrate, by heat treatment, that the performance of the used catalysts will be fully recovered for at least two times.

Mn-MOF derived manganese sulfide as peroxymonosulfate activator for levofloxacin degradation: An electron-transfer dominated and radical/nonradical coupling process.

Recently, transition metal sulfides have attracted much attention due to their better catalytic capacities as peroxymonosulfate (PMS) activator than their metal oxide counterparts. However, the systematic studies on PMS activation using transition metal sulfides are still lacking. In this work, manganese sulfide (MnS) materials were synthesized via a MOFs-derived method and utilized for PMS activation to degrade levofloxacin (LVF) in water for the first time. As expected, MnS exhibited remarkable LVF degradation efficiency by PMS activation, which was distinctly higher than Mn2O3. The results of quenching experiments, electro spin resonance identification and electrochemical tests indicated that electron-transfer progress was the dominant mechanism in α-MnS/PMS system. Meanwhile, the presence of 1O2 and radicals further became the removal of LVF by α-MnS/PMS system into a radical/nonradical coupling process. The superior electrical conductivity of α-MnS than α-Mn2O3 was revealed by DFT calculations, which resulted in the higher catalytic capacity of α-MnS. The result of XPS also indicated the S species in MnS accelerated the recycle of Mn(IV)/Mn(II) and then promoted the generation of radicals. Furthermore, the influence of various environmental conditions on LVF removal and the reusability of α-MnS were also investigated, which demonstrated the high application potential of α-MnS/PMS system. Finally, six possible pathways of LVF oxidation in the system were proposed based on the identified byproducts and their ecotoxicity was evaluated with ECOSAR method. This work promotes the fundamental understanding of PMS activation by α-MnS and provides useful information for practical application of manganese sulfide in water treatment.

Quantification of Plasma 8-Isoprostane by High-Performance Liquid Chromatography with Tandem Mass Spectrometry in a Case-Control Study of Lung Cancer.

AIM: 8-iso-prostaglandin F2α is a biomarker of lipid peroxidation, and one of the most commonly used measures of oxidative stress. It is an established biomarker of lung cancer risk. It is commonly measured by enzyme-linked immunosorbent assay. Given its importance, we developed a stable isotope dilution UPLC-tandem mass spectrometric method for the rapid determination of 8-isoprostane in blood. METHODS: We tested the discriminatory capability of the method in 49 lung cancer patients, 55 benign lung nodule patients detected by chest X-ray, and 41 patients with chronic obstructive pulmonary disease (COPD) or asthma. RESULTS: Significant differences were found in mean 8-isoprostane levels between the three groups (p = 0.027), and post-hoc tests found higher levels in the lung cancer patients than in patients with benign nodules (p = 0.032) and COPD/asthma (p = 0.014). The receiving operating characteristic area under the curve (AUC) was 0.69 for differentiating the lung cancer group from the benign nodule group, and 0.7 for differentiating from the COPD/asthma group. CONCLUSIONS: The UPLC-MS/MS-based method is an efficient analytical tool for measuring 8-isoprostane plasma concentrations. The results suggest exploring its utility as a marker for early lung cancer screening.

Atmospheric deposition of microplastics in the megalopolis (Shanghai) during rainy season: Characteristics, influence factors, and source.

Urban areas are the hardest hit by microplastic pollution, and deposition is an important part of microplastic migration and transport in the atmosphere, therefore, the study of microplastics in an urban atmospheric deposition is of great significance. This study aims to investigate the deposition characteristics of atmospheric microplastics in megapolis, to clarify the influence of meteorological and anthropogenic factors, and to analyze the sources of atmospheric microplastics. Six sampling sites in Shanghai were selected to collect atmospheric deposition samples during the rainy season. The mean deposition flux of microplastics was 3261.22 ± 2847.99 P·m-2·d-1 (median: 2559.70 P·m-2·d-1), and the types were mainly polyamide (PA, 27.79 %), polyethylene terephthalate (PET, 27.29 %), polypropylene (PP, 16.95 %), and polyvinyl fluoride (PVF, 12.88 %). The microplastic with the particle size of <1000 µm accounted for 88.23 %, and the shape was mainly fiber (73.55 %). The results of correlation analysis and variance analysis of microplastic characteristics with meteorological and anthropogenic factors (land-use, atmospheric pollutants, and urban indicators) showed that wind and precipitation had effects on deposition flux, size and shape, and were more significant at small scales (individual cities), while at large scales, the population was the main influence of microplastics. Atmospheric microplastics in Shanghai may be dominated by exogenous sources, through a combination of microplastic characteristics, wind and backward trajectories. This study further reveals the fate of urban atmospheric microplastics, which has implications for the study of global microplastic pollution.

Validation of the Application of Solid Contact Ion-Selective Electrode for Off-Body Sweat Ion Monitoring.

The solid contact ion-selective electrode (ISE) is a promising skin-interfaced monitoring system for sweat ions. Despite a growing number of on-body usages of ISE with fancy new materials and device fabrications, there are very few reports attempting to validate ISE results with a gold standard technique. For this purpose, this work uses inductively coupled plasma-optical emission spectrometry (ICP-OES) as a reference technique to conduct a direct evaluation of the sweat sodium and potassium ion levels obtained by ISE in an off-body approach. Eight healthy male subjects were recruited to collect exercise-induced sweat. It was found that sweat sodium and potassium ions present a rather wide concentration range. The sweat sodium concentration did not vary greatly in an exercise period of half an hour, while the sweat potassium concentration typically decreased with exercise. Mineral drink intake had no clear impact on the sweat sodium level, but increased the sweat potassium level. A paired t-test and mean absolute relative difference (MARD) analysis, a method typically used for evaluating the performance of glucometers, was employed to compare the results of ISE and ICP-OES. The statistical analysis validated the feasibility of ISE for measuring sweat ions, although better accuracy is required. Our data suggests that overweight subjects are likely to possess a higher sweat sodium level.

Study on the cross-flow ultrafiltration of mixtures of macromolecular organic and inorganic salts.

Ultrafiltration (UF) has been widely applied to water treatment in the past few decades, but severe membrane fouling is one of the most significant obstacles for its further development. In reality, the constituents of feed water are complex, and the fouling behavior could be different from that induced by a single foulant. In this study, the membrane fouling induced by mixed organic foulant (sodium alginate, SA) and inorganic ions under various conditions were investigated. The effects of ion concentration and valence on the combined fouling as well as the rejection performance were examined. The results showed that compared to SA alone, the presence of inorganic ions could aggravate the organic fouling of UF membranes significantly. The fouling became more severe as the ion concentration increased. Also, ions with higher valence tended to exacerbate the fouling compared with monovalent ions. It was also found that the existence of inorganic ions had negligible effects on the rejection of organic molecules, however, the rejection of salts can be improved because of the organic matter. In addition, the analysis of the classic fouling models showed that the complete blocking model is the main fouling mechanism of the mixed SA and inorganic salts.

B,N-decorated carbocatalyst based on Fe-MOF/BN as an efficient peroxymonosulfate activator for bisphenol A degradation.

A novel B,N-decorated carbocatalyst (Fe@BPC-XBN) for peroxymonosulfate (PMS) activation was prepared by a simple pyrolysis method using the iron-based metal organic frameworks (Fe-MOF), boric acid and boron nitride (BN) as precursors. Fe@BPC-20BN removed 93.3% of bisphenol A (BPA) in 90 min compared to 64.9%, 82.1% and 83.5% with Fe@PC, Fe@BPC and Fe@PC-20BN, respectively, with 0.15 g/L catalyst and 1 mM PMS at initial pH of 7. The solo B-doping with boron acid on the Fe-MOF derived porous carbon enhanced its catalytic capacity; moreover, B, N co-doping with BN and boron acid as precursors further promoted the catalytic performance. The addition of BN not only provided more B, N catalytic centers but also improved the stability of the carbocatalyst. In addition, hydroxyl radicals, sulfate radicals, superoxide radicals, and singlet oxygen species were involved in the degradation of BPA. Fe species, -BCO2/-BC2O, pyridinic N, and pyrrolic N groups on the carbon matrix played the important roles in the BPA degradation. The outstanding catalytic performance of Fe@BPC-20BN could be attributed to the synergistic effects between iron nanoparticles and the B/N codoped carbon matrix. This study gives new insights into the design and preparation of high-efficient B,N-decorated carbocatalysts for environmental remediation.

Mobile monitoring of VOCs and source identification using two direct-inlet MSs in a large fine and petroleum chemical industrial park.

Mobile monitoring with direct-inlet MS (DI-MS), one of the most direct and effective ways to track emission sources, can effectively serve air quality management in chemical industrial parks (CIPs). Mobile monitoring using a high mass-resolution proton-transfer-reaction time-of-flight MS (HMR-PTR-TOFMS) and single-photon ionization time-of-flight MS (SPI-TOFMS) was conducted in a large fine and petroleum CIP in eastern China for three days. The high mixing ratios of aliphatic hydrocarbons (AHs), aromatics, oxygenated VOCs (OVOCs), and nitrogenous VOCs (NVOCs) were found in the northeast, middle, north, and northeast of the fine chemical industrial zone (FCIZ), respectively. OVOCs were the most abundant VOC group in this area. Abnormal emissions of aromatics were universal throughout the CIP. We discovered 38 characteristic VOCs by the HMR-PTR-TOFMS, mainly including C6-C10 aromatics, C2-C6 carbonyls, C2-C3 organic acids, and some NVOCs. The time series and spatial distribution of the TVOCs obtained by the two DI-MSs are generally consistent. A comparison of the speciated VOCs at the TVOC peak points illustrates that the characteristic VOCs obtained by different instruments differed significantly: PTR-TOFMS showed an advantage in measuring aromatics and OVOCs; SPI-TOFMS showed an advantage in measuring aromatics and some Ahs; offline GC-MS showed an advantage in measuring AHs, aromatics, some OVOCs, and halohydrocarbons. Similarities were compared between five positive matrix factorization (PMF) model-based fingerprints of VOCs in a previous study and observed profiles of VOCs from mobile monitoring. The emission sources of the five fingerprints were identified and validated: two were widely distributed, one was a chemical reagent production factory, one was an acrylic fiber production plant, and one was a pesticide factory. This study demonstrated methods for analyzing mobile monitoring data, characterizing the VOCs in the fine and petroleum CIP, correlating the results of stationary observation and mobile monitoring, and integrating the source tracing system with DI-MSs.

Study on emission factors of FCC flue gas pollutants in petroleum refineries.

Fluid catalytic cracking (FCC) unit is one of the means to lighten heavy oil in refineries, and its regenerated flue gas is also the main source of air pollutants from refinery. However, it is not clear about the type and amount of pollutants discharged from FCC units in China. The emissions of regenerated pollutants in the stack flue gases of three typical FCC units in China were investigated in this study, including a partial regeneration unit without a CO boiler (U1), a partial regeneration unit with a CO boiler (U2), and a full regeneration unit (U3). Different monitoring methods were used to analyze the concentration of sulfur dioxide (SO2) and nitrogen oxides (NOx), and the results showed that Fourier transform infrared spectroscopy (FTIR) monitoring results of SO2 and NOx are approximately 10 times and 5 times larger than those of the continuous emission monitoring system (CEMS) data, respectively. Also, the contents of characteristic pollutants such as NH3, C6H6, HCN, C8H8, C2H4, CH4, and CO were also monitored by FTIR, and the emission factors based on coke burn-off rate and throughput were investigated. The pollutants in U1 exhibited relatively higher contents with the NH3, HCN, and C6H6 of 116.99, 71.94, and 56.41 mg/Nm3 in flue gas, respectively. The emission of regenerated pollutants in U2 and U3 are significantly different from U1. Regeneration processes (including coke properties, operating modes, and presence or absence of CO boilers) affected pollutants' emission factors in varying degrees. At last, reasonable emission factors based on the different FCC regeneration processes contribute to the prediction, assessment, and control for the pollutant emission.

A review of atmospheric microplastics pollution: In-depth sighting of sources, analytical methods, physiognomies, transport and risks.

Micro-sized plastics were first examined for atmospheric environment in 2016. From then on, they have been detected in both indoor and outdoor atmospheric samples, with indoor environments demonstrated as containing a big proportion of these particles. The sparse distribution of these particles, is attributed to their swift and long distance transportation that is mainly eased by their tiny size (1 µm to 5 mm) and low density. Due to ongoing limitation on detectable size, analysis methods together with a lack of standardized sampling and analytical procedures, few studies were conducted on airborne microplastics (MPs). Thus, the facts regarding the occurrence, global spatial distribution, fate, and threats to ecosystem and human health of airborne MPs, are still far from being fully clarified. This literature review is a broad depiction of a state of knowledge on atmospheric MPs. Within it, robust and concise information on the sources, inspection, transport, and threats pertaining to airborne MPs are presented. Particularly, the paper entails some information concerning traffic-generated MPs pollution, which has not been frequently discussed within previously published reports. In addition, this paper has widely unveiled sectors and aspects in need of further attention, with the gaps to be filled pinpointed.

Comparative proteomic analysis of exhaled breath condensate between lung adenocarcinoma and CT-detected benign pulmonary nodule patients.

BACKGROUND: Lung cancer is the leading cause of cancer mortality worldwide. The collection of exhaled breath condensate (EBC) is a non-invasive method that may have enormous potential as a biomarker for the early detection of lung cancer. OBJECTIVE: To investigate the proteomic differences of EBC between lung cancer and CT-detected benign nodule patients, and determine whether these proteins could be potential biomarkers. METHODS: Proteomic analysis was performed on individual samples from 10 lung cancer patients and 10 CT-detected benign nodule patients using data-independent acquisition (DIA) mass spectrometry. RESULTS: A total of 1,254 proteins were identified, and 21 proteins were differentially expressed in the lung adenocarcinoma group compared to the benign nodule group (p< 0.05). The GO analysis showed that most of these proteins were involved in neutrophil-related biological processes, and the KEGG analysis showed these proteins were mostly annotated to pyruvate and propanoate metabolism. Through protein-protein interactions (PPIs) analysis, ME1 and LDHB contributed most to the interaction-network of these proteins. CONCLUSION: Significantly differentially expressed proteins were detected between lung cancer and the CT-detected benign nodule group from EBC samples, and these proteins might serve as potential novel biomarkers of EBC for early lung cancer detection.

Vertically-resolved sources and secondary formation of fine particles: A high resolution tethered mega-balloon study over Shanghai.

Numerous studies have focused on air pollution near the surface in China, yet we still have little knowledge on the characteristics, formation mechanisms, and sources of air pollutants aloft. Based on a tethered mega-balloon platform, the vertical profiles of PM2.5, black carbon (BC), SO2, O3, and meteorological parameters were measured within the lower troposphere of 1000 m over Shanghai. One clean and slightly polluted period (CP) and one heavily polluted period (HP) with continuously measured profiles were compared. The potential source areas of PM2.5 at different altitudes during HP were determined based on the time-lag spatial correlation analysis, indicating the surrounding regions were the main sources of low-altitude particles in Shanghai and farther regions of northern China significantly affected the upper atmosphere. By apportioning the sources of vertical BC profiles, fossil fuel combustion contributed >80% to BC below 600 m during HP, exhibiting a higher contribution than CP. An indicator (i.e. SA/SO2, SA represents secondary aerosols) was established to investigate the vertical evolution of secondary aerosol formation. During CP, relatively low SA/SO2 ratios were observed within the boundary layer due to the weak atmospheric processing. SA/SO2 profiles showed the opposite vertical trend of higher ratios below about 600 m while lower values at high altitudes during HP. Regional and long-range transport regulated the extents of secondary aerosol formation. Northeasterlies transported abundant aged aerosols from northern China while sea breezes suppressed the columnar secondary aerosol formation. This study provided insights into the vertical structures of typical air pollutants in a Chinese megacity and implied that high-resolution measurements of atmospheric vertical profiles were valuable for diagnosing sources and potential secondary formation of fine particles.

Aqueous photodegradation of the benzophenone fungicide metrafenone: Carbon-bromine bond cleavage mechanism.

Metrafenone (MF), as a new type of benzophenone fungicide, has been widely used in agriculture and is persistent in the environment. Understanding its photochemical fate is essential for the comprehensive evaluation of its ecological risk. In the present work, we reported a detailed study on the photochemical transformation of MF in aqueous solution under irradiation (at λ > 290 nm using a high pressure mercury lamp). MF was relatively photo-reactive showing a low polychromatic quantum yield of photolysis (1.06 × 10-4, 20 µM) counterbalanced by a significant light absorption above 290 nm. A series of photoproducts were identified by high resolution mass spectrometry (HR-MS) analysis, and three different pathways, including oxidation of the methyl group, debromination and replacement of bromine by hydroxyl group were proposed. Among them, debromination was identified as the dominating process that could be achieved via homolytic C-Br bond cleavage from singlet and triplet MF, as confirmed by laser flash photolysis (LFP) experiments and density functional theory (DFT) calculations. Toxicity assessment revealed that photochemical degradation reduced the ecotoxicity of MF efficiently. Nitrate ions and humic acid promoted the MF photolysis, while bicarbonate exhibited no effect. Results obtained in this work would increase our understanding on the environmental fate of MF in sunlit surface waters.

[O3 Source Characteristics of an Industrial Area in the Yangtze River Delta Based on Boundary Observations].

To study the characteristics of ozone sources in a petrochemical industrial park in Shanghai, O3 and its precursors were synchronously and continuously measured for 3 months(June-August 2020) alongside meteorological parameters using an online monitoring system. The Texas Commission on Environmental Quality(TCEQ) method and principal component analysis(PCA) were used to study the contribution of regional background and local O3 concentrations in the industrial zone, the results of which were compared. The results indicated that:① During the observation period, the dominant wind directions in the park were southeast and east, and the average temperature was 27.12℃. The daily average ρ(VOCs-36), ρ(NOx), and ρ(O3) was 32.05-240.51, 10.15-47.51, and 31.81-144.43µg·m-3, respectively. Alkanes are the most abundant of 36 VOCs; ② The regional background concentrations based on the TCEQ method ranged from 32.63 to 191.13µg·m-3, and the local concentrations ranged from 16.08 to 134.25 µg·m-3. The percentage contribution of the regional background ranged from 32.6% to 87.7%. The PCA analysis showed that the regional background concentrations ranged from 66.3 to 219.83µg·m-3; ③ The variations in local O3 concentrations based on the TCEQ analysis broadly correspond to the variations in ozone formation potential in the park. The two analysis methods were consistent, verifying that the results are reliable; and ④ After eliminating the calculation error caused by the abnormal concentrations recorded at some stations, the proportion of background O3 in the region was generally within the range 75%-95% during the observation period. Overall, regional transport was the main source of O3 in the industrial park, and O3 pollution in the surrounding cities should be the focus of pollution control alongside joint prevention and control measures in the Yangtze River Delta region.

Stationary monitoring and source apportionment of VOCs in a chemical industrial park by combining rapid direct-inlet MSs with a GC-FID/MS.

Fast and comprehensive monitoring of VOCs, required for air quality management in large-scale chemical industrial parks in China, cannot be accomplished by stationary measurements using conventional GC-FID or GC-MS alone due to their low temporal resolutions and limited detectable ranges. Novel direct-inlet mass spectrometry (DI-MS) has been widely applied for real-time monitoring of VOCs. To verify its applicability in industrial settings, high mass-resolution proton-transfer-reaction time-of-flight MS (HMR-PTR-TOFMS), single-photon ionization time-of-flight MS (SPI-TOFMS), together with online GC-FID/MS were simultaneously deployed at the boundary of one of the largest chemical industrial parks in eastern China. Aromatics, acetonitrile, acetic acid, ethyl acetate, aliphatic hydrocarbons, 1,2-dichloroethane, and acetone were detected as the main pollutants. These three instruments detected 12 common species, among which ethyl acetate, toluene, C8-aromatics, and methyl ethyl ketone showed similar time series and levels. Acetone, benzene, chlorobenzene, styrene, and C9-aromatics showed only similar time series. The HMR-PTR-TOFMS uniquely detected 14 species, mainly oxidized VOCs, nitriles, and amines, which greatly helps acknowledge the pollutants in the chemical industrial area. Positive matrix factorization, using the HMR-PTR-TOFMS and GC-FID/MS datasets, was used to identify eight sources. Four of the identified sources were mainly detected by the HMR-PTR-TOFMS, with pollutants mainly comprised of nitriles, amines, carbonyls, and organic acids, most of which were hazardous and/or odorous. These four sources accounted for 41.5% and 33.2% of the total VOCs and ozone formation potential, respectively. The complementary nature of GC-FID/MS and HMR-PTR-TOFMS in VOC source apportionment in industrial settings is of great practical use for advanced VOCs abatement. Thus, the high mass resolution DI-MSs are suggested to be a supplementary measurement for fence-line monitoring. Although with a relatively short period attempt, this study has wide implications for the fence-line stationary observational modes and source apportion methods combining with traditional observations.

Cu(II) assisted peroxymonosulfate oxidation of sulfonamide antibiotics: The involvement of Cu(III).

Cu(II) is generally considered to be a poor activator for PMS decomposition, thus the potential impact of trace Cu(II) on PMS induced oxidation of typical pollutants is always overlooked. In this study, we reported that trace Cu(II) could significantly promote PMS induced degradation of four selected sulfonamide antibiotics (SAs), namely, sulfamehoxazole (SMX), sulfathiazole (STZ), sulfamerazine (SMZ), and sulfamonomethoxine (SMM). Different from conventional PMS-induced oxidation process, high-valent Cu(III) was ascertained as the primary reactive intermediate for SAs degradation, which was confirmed by raman tests and electron paramagnetic resonance (EPR). High concentrations of Cu(II) or PMS were beneficial to degradation of the selected contaminants. In PMS/Cu(II) oxidation system, all the selected SAs could undergo several different degradation pathways including continuous oxidation of aniline group, hydroxylation and S-N bond cleavage. In particular, for six-membered SAs, such as SMZ and SMM, a SO2 extrusion pathway was also detected. The potential mechanism for Cu(III) formation was also proposed, which was believed to be highly related to the nature of the SAs. Hydroxylamine-SAs (N4-OH-SAs), generated from direct PMS oxidation of SAs, was deduced as the "promoter" for the whole oxidation process. And the generation of Cu(III) was likely to proceed through the interaction between PMS and Cu(I), which possibly derived from the reduction of Cu(II) by N4-OH-SAs. The results obtained in this study validated the contribution of Cu(III) to the elimination of pollutants and expanded our understanding of the oxidation process of PMS in the presence of trace amounts of Cu(II).

Influence of wet flue gas desulfurization on the pollutants monitoring in FCC flue gas.

Fluid catalytic cracking (FCC) unit emits a large amount of flue gas, which is a major concern of environmental protection supervision. Wet flue gas desulfurization (WFGD) technologies have been widely used to control the emissions of SO2 in refineries. In this study, stack tests for pollutants emission of a typical FCC unit were conducted. The emission characteristics of the FCC unit indicated that WFGD would cause a large amount of water vapor in the flue gas, which indirectly leads to large quantities of salt pollutants entrained in the flue gas including ammonium sulfite ((NH4)2SO3) and ammonium sulfate ((NH4)2SO4). A strong correlation among the concentrations of SO2, NH3, and H2O was observed, and factor analysis shows that these concentrations are dominated by a common factor. It was also found that a mass quantity of NH4+ and SO32- existed in the condensate water of the flue gas. The TG-MS analysis shows that (NH4)2SO3 could be decomposed at 94.1 °C, and NH3, SO2, and H2O are released as reaction products in the form of gas. Therefore, a part of the NH3 and SO2 obtained by Fourier transform infrared spectroscopy (FTIR) monitoring may be derived from the decomposition of (NH4)2SO3 in the flue gas due to the high temperature during the sampling process, which was also confirmed in a lab experiment. The hot and wet sampling process will lead to overestimation of NH3 and SO2 emissions rather than FTIR method itself when monitoring the high-humidity FCC flue gas. Thus, the concentration of H2O in the flue gas and the type of sampling process need to be taken into consideration during the monitoring process.