Multivariate analysis of carcinogenic equivalence (CEQ) to characterize carcinogenic VOC emissions in a typical petrochemical industrial park in Taiwan.

Large industrial emissions of volatile organic compounds (VOCs) from the petrochemical industry are a critical concern due to their potential carcinogenicity. VOC emissions vary in composition depending on the source and occur in mixtures containing compounds with varying degrees of toxicity. We proposed the use of carcinogenic equivalence (CEQ) and multivariate analysis to identify the major contributors to the carcinogenicity of VOC emissions. This method weights the carcinogenicity of each VOC by using a ratio of its cancer slope factor to that of benzene, providing a carcinogenic equivalence factor (CEF) for each VOC. We strategically selected a petrochemical industrial park in southern Taiwan that embodies the industry's comprehensive nature and serves as a representative example. The CEQs of different emission sources in three years were analyzed and assessed using principal component analysis (PCA) to characterize the major contributing sectors, vendors, sources, and species for the carcinogenicity of VOC emissions. Results showed that while the study site exhibited a 20.7 % (259.8 t) decrease in total VOC emissions in three years, the total CEQ emission only decreased by 4.5 % (15.9 t), highlighting a potential shift in the emitted VOC composition towards more carcinogenic compounds. By calculating CEQ followed by PCA, the important carcinogenic VOC emission sources and key compounds were identified. More importantly, the study compared three approaches: CEQ followed by PCA, PCA followed by CEQ, and PCA only. While the latter two methods prioritized sources based on emission quantities, potentially overlooking less abundant but highly carcinogenic compounds, the CEQ-first approach effectively identified vendors and sources with the most concerning cancer risks. This distinction underscores the importance of selecting the appropriate analysis method based on the desired focus. Our study highlighted how prioritizing CEQ within the analysis framework empowered the development of precise control measures that address the most carcinogenic VOC sources.

Hepatotoxicity evaluations of different surface charged carbon quantum dots in vivo and in vitro.

Recently, carbon quantum dots (CQDs) have become popular because of their simple synthesis and potential applications. Although CQDs have high biocompatibility, their biotoxicity must be verified to reduce the possible risks associated with large-scale application. In this study, the hepatotoxicity of three CQD types, namely diammonium citrate (AC)-based (CQDs-AC), spermidine trihydrochloride (Spd)-based (CQDs-Spd), and AC- and Spd-based CQDs (CQDs-AC/Spd), were evaluated in vivo and in vitro. It was observed in vivo that CQDs-Spd and CQDs-AC/Spd, but not CQDs-AC, caused histopathological damage, including liver steatosis and mild mixed inflammatory cell infiltration; however, reduced liver function was only observed in CQD-Spd-treated mice. The in vitro results revealed that only CQDs-Spd significantly decreased the number of viable HepG2 cells (NADH depletion) and induced oxidative stress (heme oxygenase-1 activation) after 24 h of exposure, which promoted inflammatory factor secretion (NF-κB activation). Additionally, decreasing zonula occludens-2 and α1-antitrypsin protein expression in HepG2 cells suggested that CQD-Spd exposure increases the risk of liver diseases. Our results revealed that CQDs-Spd had greater hepatotoxic potential than CQDs-AC and CQDs-AC/Spd, which might be attributable to their high positive surface charge. Overall, the risk of CQD-induced hepatotoxic risk must be considered when applying positively charged CQDs.

Seasonal Disparities of Human Health Risk and Particle-Bound Metal Characteristics Associated with Atmospheric Particles in a Fishery Harbor.

The effects of atmospheric pollution from ship emissions have been considered for several harbors worldwide. The health risk assessment and source apportionment of particle-bound metals in a fishery harbor were investigated in this study. The most abundant metal elements in particulate matter (PM) on all sampling days in three seasons were Fe (280.94 ± 136.93 ng/m3), Al (116.40 ± 71.25 ng/m3), and Zn (110.55 ± 26.70 ng/m3). The ratios of V/Ni were 1.44 ± 0.31, 1.48 ± 0.09 and 1.87 ± 0.06 in PM10, PM2.5, and PM1, respectively. Meanwhile, the ratios higher than 1 indicated that fuel oil combustion from ship emission in fishery harbor. The highest deposits of total particle-bound metals in the human respiratory tract were in the head airway (HA), accounting for 76.77 ± 2.29% of the total particle-bound metal concentration, followed by 5.32 ± 0.13% and 2.53 ± 0.15% in the alveolar region (AR) and tracheobronchial (TB) region, respectively. The total cancer risk (CR) of inhalation exposure to local residents exceeded 10-6. Mean total CR values followed the sequence: autumn (1.24 × 10-4) > winter (8.53 × 10-5) > spring (2.77 × 10-6). Source apportionment of related metal emissions was mobile pollution emissions (vehicle/boat) (37.10-48.92%), metal fumes of arc welding exhaust (19.68-34.42%), spray-painting process (12.34-16.24%), combustion emissions (6.32-13.12%), and metal machining processes (9.04-16.31%) in Singda fishing harbor. These results suggest that proper control of heavy metals from each potential source in fishing harbor areas should be carried out to reduce the carcinogenic risk of adverse health effects.

Photoelectrochemical degradation of trichloroethylene by iron modified TiO2 nanotube arrays.

In this study, iron was deposited to titanium dioxide nanotube arrays (TNAs) by impregnation method to enhance its photocatalytic ability. The as-synthesized iron-modified TNAs (Fe-TNAs) was employed in a photoelectrochemical (PEC) system to degrade trichloroethylene (TCE). Results of AFE-SEM analysis showed that the iron nanoparticles (NPs) were successfully attached evenly to the nozzle of Fe-TNAs. Results of XRD analysis confirmed the findings of EDS and XPS, indicating the success of iron modification. The absorption wavelength of Fe-TNAs-27 mL red-shifts to 543 nm which corresponds to the band gap of 2.54 eV after iron modification. Mott-Schottky analysis yielded a donor density of 7.21 × 1020 and 2.30 × 1020/cm3 for TNAs and Fe-TNAs-27 mL, respectively. The photo-generated electrons had a lifetime (τel) of 21.49 and 39.19 ms for TNAs and Fe-TNAs-27 mL, respectively, illustrating the reduce of recombination of photo-generated electron-hole pairs. process. PEC methods performed the most effective way to degrade TCE with a rate constant of 0.079 min-1 in Fe-TNAs PEC system. Mechanism of Fe-TNAs PEC system was proposed in detail.

LED-driven photocatalysis of toluene, trichloroethylene and formaldehyde by cuprous oxide modified titanate nanotube arrays.

In this study, cuprous oxide modified titanate nanotube arrays photocatalyst (Cu2O/TNAs), a p-n type hetero-structure, was successfully synthesized by square wave voltammetry electrodeposition method (SWVE) with copper (II) acetate monohydrate as precursor. Cu2O/TNAs photocatalysts were characterized by SEM, XRD, XPS, and UV-vis DRS to investigate the physical and chemical properties such as surface structure, light absorption, and element composition. Results of characterization indicated that the Cu2O nanoparticles (Cu2O NPs) were firmly deposited on the surface of TNAs without significant morphological change. The enhanced photocatalytic (PC) performance of as-synthesized materials was exemplified by the test of photocurrent, which revealing that the average photocurrent density of Cu2O/TNAs (0.95 µA cm-2) was 1.38 times higher than TNAs (0.69 µA cm-2) under 24.2 mW cm-2 LED irradiation. Three VOCs (volatile organic compounds), namely, Toluene, Formaldehyde and Trichloroethylene can be completely removed in the Cu2O/TNAs PC process with rate constants (kobs) of 2.08 × 10-2, 3.11 × 10-2, and 6.58 × 10-2 min-1, respectively, with the effort of the synergism of the photo-generated holes and hydroxyl radicals. Detail mechanism of hetero-junction Cu2O/TNAs composite PC system was proposed to clarify the redox reaction.

Iron Modified Titanate Nanotube Arrays for Photoelectrochemical Removal of E. coli.

This study used iron modified titanate nanotube arrays (Fe/TNAs) to remove E. coli in a photoelectrochemical system. The Fe/TNAs was synthesized by the anodization method and followed by the square wave voltammetry electrochemical deposition (SWVE) method with ferric nitrate as the precursor. Fe/TNAs were characterized by SEM, XRD, XPS, and UV-vis DRS to investigate the surface properties and light absorption. As a result, the iron nanoparticles (NPs) were successfully deposited on the tubular structure of the TNAs, which showed the best light utilization. Moreover, the photoelectrochemical (PEC) properties of the Fe/TNAs were measured by current-light response and electrochemical impedance spectroscopy. The photocurrent of the Fe/TNAs-0.5 (3.5 mA/cm2) was higher than TNAs (2.0 mA/cm2) and electron lifetime of Fe/TNAs-0.5 (433.3 ms) were also longer than TNAs (290.3 ms). Compared to the photolytic (P), photocatalytic (PC), and electrochemical (EC) method, Fe/TNAs PEC showed the best removal efficiency for methyl orange degradation. Furthermore, the Fe/TNAs PEC system also performed better removal efficiency than that of photolysis method in E. coli degradation experiments.

Comparative health risk of inhaled exposure to organic solvents, toxic metals, and hexavalent chromium from the use of spray paints in Taiwan.

The study investigated the exposure of spray painters to organic solvents, toxic metals, and hexavalent chromium over 21 working days in 2017. The results found these concentrations of 12 VOCs to be below the short-term exposure limit (STEL) established by the US Occupational Safety and Health Administration (OSHA). The mass concentration of total particulate matter (PM) exposure to workers was 20.01 ± 10.78 mg/m3, which exceeds OSHA's permissible exposure level of 15 mg/m3. The mean concentration of the total metals for all particle sizes was 109.1 ± 12.0 µg/m3, and those for lead (496,017.0 ng/m3) and iron (252,123.8 ng/m3) were the highest of metal elements. Significantly, the mean concentrations of Pb and As exceeded OSHA's permissible exposure limits (PELs) of 0.05 and 0.01 mg/m3, respectively. The total hexavalent chromium concentration was 1163.01 ng/m3, and the individual particle sizes (PM1-2.5, PM1, and PM0.25) were strongly and positively correlated with the Cr(VI) concentrations for PM2.5. The study determined that approximately 56.14% of the hexavalent chromium inhaled during the spray-painting process was deposited in the upper respiratory system of the head airway region, followed by the alveolar and tracheobronchial regions, with fractions of 11.93 and 0.05%, respectively. Although the mean ratio of hexavalent chromium to total chromium was only 3.6% for all particle sizes, the cancer risk of the total particles in Cr(VI) (1.6 × 10-3) exceeded the acceptable risk value (10-6). The cancer risks of As and Cr(VI) associated with quasi-ultrafine particles, PM0.5-1, PM1-2.5, and PM> 2.5, also exceeded 10-6. Comparison of the carcinogenicity risk of VOCs and metals suggests that the adverse health effect of inhaled particles on spray-painting workers is more serious than that from VOC exposure.

Dispersant-modified iron nanoparticles for mobility enhancement and TCE degradation: a comparison study.

Dispersants including Tween 20, Tween 40, Tween 60, and polyacrylic acid (PAA) were used to modify nanoscale zero-valent iron (nZVI). All dispersants dispersed nZVI effectively. PAA-modified nZVI was more stable than nZVI that was modified with Tween surfactant. Iron nanoparticles that were prepared using 0.5-5.0% (vol%) of PAA remained in suspension for more than 2 h. nZVI that was modified using Tween surfactant remained in suspension for 30-60 min, and there was complete sedimentation of bare iron in 10 min. When 2.0-5.0% (vol%) of Tween surfactant was used, the stability of the nZVI that was modified using Tween 20 was much better than that for nZVI that was modified using Tween 40 or Tween 60. The results for the transportation test show that nZVI that was prepared using 2% (vol%) of Tween 20 exhibited the best mobility in porous media. Approximately 83-90% of TCE was degraded by bare, PAA-modified, and Tween 20-modified nZVI, and about 63-67% of TCE was removed by nZVI that was modified using Tween 40 and Tween 60 during 20 days of reaction. The production of cis-dichloroethene (DCE) and 1,1-DCE demonstrates that TCE is removed via reductive dechlorination. The results of this study show that PAA- and Tween 20-modified nZVI are more practical for in situ remediation because they exhibit good mobility and degrade TCE effectively.

Effects of heavy metals on health risk and characteristic in surrounding atmosphere of tire manufacturing plant, Taiwan.

The health and environmental effects of metal-containing carbon black (CB) particles emitted from a CB feeding area near a tire manufacturing plant were investigated. The mass ratios of PM1 and PM0.1 (UFPs) relative to TSP were 13.84% ± 4.88% and 50.84% ± 4.29%, respectively. The most abundant elements in all fractions were Fe, Al, and Zn. The mean percentage contributions of Al, Fe, Zn, Cu, and Co to the coarse particles ranged from 49.1% to 69.1%, thus indicating that the Al, Fe, and Zn contents in the CB particles were affected by workplace emissions. The ratios of the total mean deposition fluxes of atmospheric particle-bound heavy metals in the human respiratory tracts of workers/adults, workers/children, and adults/children were approximately 5.5, 11.0, and 2.0, respectively. The integrated risks of five elements via two exposure pathways to adults and children were 1.1 × 10-4 and 1.7 × 10-5, respectively; these numbers reflect the high cumulative carcinogenic risk posed by these toxic metals to local residents (both adults and children; limit, 10-6). These results demonstrate the potential health risk presented by particle-bound heavy metals to humans residing near tire manufacturing plants via inhalation and dermal contact exposure.

Enhanced bioelectricity generation and azo dye treatment in a reversible photo-bioelectrochemical cell by using novel anthraquinone-2,6-disulfonate (AQDS)/MnOx-doped polypyrrole film electrodes.

A novel anthraquinone-2,6-disulfonate/MnOx-doped polypyrrole film (AQDS/Mn/PPy) electrode was prepared by one-step electropolymerization method and was used to improve performance of a reversible photo-bioelectrochemical cell (RPBEC). The RPBEC was operated in polarity reversion depended on dark/light reaction of alga Chlorella vulgaris by which sequential decolorization of azo dye and mineralization of decolorization products coupled with bioelectricity generation can be achieved. The results showed that formation of uniform AQDS/Mn/PPy film significantly enhanced electroactive surface area and electrocatalytic activity of carbon electrode. The RPBEC with AQDS/Mn/PPy electrodes demonstrated 77% increases in maximum power and 73% increases in Congo red decolorization rate before polarity reversion, and 198% increases in maximum power and 138% increases in decolorization products mineralization rate after polarity reversion, respectively, compared to the RPBEC with bare electrode. This was resulted from simultaneous dynamics improvement in half-reaction rate of anode and photo-biocathode due to enhanced electron transfer and algal-bacterial biofilm formation.

Nano zerovalent iron particles induce pulmonary and cardiovascular toxicity in an in vitro human co-culture model.

Despite promising environmental applications for nano zerovalent iron (nZVI), concerns remain about the potential accumulation and toxic effects of nZVI particles. Here, we use an alveolar-capillary co-culture model to investigate a possible link between low-level epithelial exposure to nZVI and pulmonary and cardiovascular toxicity. While nZVI was unable to pass through the epithelial barrier into the endothelium, nZVI exposure did cause oxidative and inflammatory responses in both epithelial and endothelial cells. Therefore, toxic effects induced by nZVI are not restricted to epithelial cells but can be transferred into the endothelium. Communication between A549 and EA.hy926 cells is responsible for amplification of nZVI-induced toxic responses. Decreases in transepithelial electrical resistance and zonula occludens proteins after epithelial exposure to nZVI impaired epithelial barrier integrity. Increases in oxidized α1-antitrypsin and oxidized low-density lipoprotein in the co-culture model suggest that nZVI exposure increases the risk of chronic obstructive pulmonary disease and atherosclerosis. Therefore, inhalation of nZVI has the potential to induce cardiovascular disease through oxidative and inflammatory mediators produced from the damaged lung epithelium in chronic lung diseases.

Characteristics of particle-bound polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in atmosphere used in carbon black feeding process at a tire manufacturing plant.

Concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were estimated for different particle size distributions in a carbon black feeding process at a tire manufacturing plant on 15 days in March and April of 2014. A total of 75 integrated air samples were collected using a micro-orifice uniform deposition impactor (MOUDI). Particle-bound PCDD/Fs were analyzed using a high-resolution gas chromatograph/high-resolution mass spectrometer (HRGC/HRMS). Concentrations of thoracic particles and total particles produced in the carbon black feeding process of a tire manufacturing plant were measured in ranges of 0.19-2.61 and 0.28-4.22 mg/m(3), respectively. On all sampling days, the three most abundant species of PCDD/Fs were OCDD, 1,2,3,4,6,7,8-HpCDF, and OCDF. The mean concentrations of total PCDD/Fs were 0.74-6.83 pg/m(3) within five particle size ranges. Total I-TEQ in particulate matter (PM)<1.0 was 2.2 and 3.2 times higher than those in PM>18 and PM2.5-10, respectively. However, the total I-TEQ of thoracic PM contributed approximately 74 % of the total I-TEQ of total PM. The assessment of health risk indicates that exposure to fractions of thoracic PM by inhalation poses a significant cancer risk (>10(-6)).