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.

Rapid synthesis of Ti-MCM-41 by microwave-assisted hydrothermal method towards photocatalytic degradation of oxytetracycline.

This study employed microwave-assisted hydrothermal method to synthesize Ti-MCM-41, which are mesoporous materials with a high surface area and excellent photocatalytic ability. Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and ultraviolet-visible spectroscopy (UV-Vis) were employed. The XRD findings showed that Ti-MCM-41 exhibited a peak at 2θ of 2.2°, which was attributed to the hexagonal MCM-41 structure. The BET (Brunauer-Emmett-Teller) results agreed with the TEM findings that Ti-MCM-41 has a pore size of about 3-5nm and a high surface area of 883m(2)/g. FTIR results illustrated the existence of Si-O-Si and Si-O-Ti bonds in Ti-MCM-41. The appearance of Ti 2p peaks in the XPS results confirmed the FTIR findings that the Ti was successfully doped into the MCM-41 structure. Zeta (ζ)-potential results indicated that the iso-electric point (IEP) of Ti-MCM-41 was at about pH3.02. In this study, the photocatalytic degradation of oxytetracycline (OTC) at different pH was investigated under Hg lamp irradiation (wavelength 365nm). The rate constant (K'obs) for OTC degradation was 0.012min(-1) at pH3. Furthermore, TOC (total organic carbon) and high resolution LC-MS (liquid chromatography-mass spectrometry) analyses were conducted to elucidate the possible intermediate products and degradation pathway for OTC. The TOC removal efficiency of OTC degradation was 87.0%, 74.4% and 50.9% at pH3, 7 and 10, respectively. LC-MS analysis results showed that the degradation products from OTC resulted from the removal of functional groups from the OTC ring.

Photocatalytic degradation of Rhodamine B by microwave-assisted hydrothermal synthesized N-doped titanate nanotubes.

Microwave-induced nitrogen-doped titanate nanotubes (NTNTs) were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR), Zeta potential analysis, specific surface area (SBET), and UV-Visible spectroscopy. TEM results indicate that NTNTs retain a tubular structure with a crystalline multiwall and have a length of several hundred nanometers after nitrogen doping. XRD findings demonstrate that the crystalline structure of NTNTs was dominated by anatase, which is favored for photocatalytic application. The Ti-O-N linkage observed in the XPS N 1s spectrum is mainly responsible for narrowing the band gap and eventually enhancing the visible light photoactivity. FT-IR results demonstrated the existence of H3O⁺, which could be excited by photo-generated holes to form hydroxyl radicals and degrade environmental pollutants. After sintering at 350°C, the UV-Vis absorbance edges of NTNTs significantly shift to the visible-light region, which indicates N atom doping into the nanotubes. Photocatalytic degradation of Rhodamine B (RhB) via NTNTs show good efficiency, with pseudo first-order kinetic model rate constants of 3.7 × 10⁻³, 2.4 × 10⁻³ and 8.0 × 10⁻4 sec⁻¹ at pH3, 7, and 11, respectively.

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.

The Influences of Pore Blockage by Natural Organic Matter and Pore Dimension Tuning on Pharmaceutical Adsorption onto GO-Fe3O4.

The ubiquitous presence of pharmaceutical pollution in the environment and its adverse impacts on public health and aquatic ecosystems have recently attracted increasing attention. Graphene oxide coated with magnetite (GO-Fe3O4) is effective at removing pharmaceuticals in water by adsorption. However, the myriad compositions in real water are known to adversely impact the adsorption performance. One objective of this study was to investigate the influence of pore blockage by natural organic matter (NOM) with different sizes on pharmaceutical adsorption onto GO-Fe3O4. Meanwhile, the feasibility of pore dimension tuning of GO-Fe3O4 for selective adsorption of pharmaceuticals with different structural characteristics was explored. It was shown in the batch experiments that the adsorbed pharmaceutical concentrations onto GO-Fe3O4 were significantly affected (dropped by 2-86%) by NOM that had size ranges similar to the pore dimensions of GO-Fe3O4, as the impact was enhanced when the adsorption occurred at acidic pHs (e.g., pH 3). Specific surface areas, zeta potentials, pore volumes, and pore-size distributions of GO-Fe3O4 were influenced by the Fe content forming different-sized Fe3O4 between GO layers. Low Fe contents in GO-Fe3O4 increased the formation of nano-sized pores (2.0-12.5 nm) that were efficient in the adsorption of pharmaceuticals with low molecular weights (e.g., 129 kDa) or planar structures via size discrimination or inter-planar π-π interaction, respectively. As excess larger-sized pores (e.g., >50 nm) were formed on the surface of GO-Fe3O4 due to higher Fe contents, pharmaceuticals with larger molecular weights (e.g., 296 kDa) or those removed by electrostatic attraction between the adsorbate and adsorbent dominated on the GO-Fe3O4 surface. Given these observations, the surface characteristics of GO-Fe3O4 were alterable to selectively remove different pharmaceuticals in water by adsorption, and the critical factors determining the adsorption performance were discussed. These findings provide useful views on the feasibility of treating pharmaceutical wastewater, recycling valuable pharmaceuticals, or removing those with risks to public health and ecosystems.

Volatile hydrocarbon emissions from vehicles and vertical ventilations in the Hsuehshan traffic tunnel, Taiwan.

The concentrations of 56 volatile organic hydrocarbons (VOCs) were measured simultaneously in the southbound bore, the northbound bore and the exhaust air shafts of the Hsuehshan tunnel near Yilan, Taiwan during 2007 and 2008. A total of 60 integrated air samples were collected using stainless steel canisters and analyzed using GC/FID and GC/MS. The highest temperature and lowest relative humidity were observed at the exit of the tunnel owing to the accumulation in the tunnel of waste heat that was exhausted from vehicles. The five most abundant species in all samples were ethylene, acetylene, isopentane, propylene, and toluene. The exit/entrance ratios of total non-methane hydrocarbon (NMHC) concentration were 7.8 and 4.8 for the southbound and northbound bores, respectively. Furthermore, the most abundant species of emission rate (ER) is toluene (21.93-42.89 mg s(-1)), followed by isopentane, ethylene, propylene and 1-butene, with ER ranging from 2.50 to 9.31 mg s(-1) for the three shafts. The ozone formation potential (OFP)/total NMHC ratios in three exhaust air shafts show that the reactivities of these emissions are similar to those of vehicle emissions.

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.

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.

Microwave-assisted deep eutectic solvents/dimethyl sulfoxide system for efficient valorization of sugar bagasse waste into platform chemicals: A biorefinery approach for circular bioeconomy.

The exploitation of lignocellulosic biomass (LB) such as sugar bagasse waste in biorefineries is the most cost-effective and favourable sustainable approach to producing essential platform chemicals, materials, and energy environmentally benignly. Herein, a microwave-mediated deep eutectic solvents (DESs)/dimethyl sulfoxide (DMSO) system for efficiently processing LB waste into platform chemicals was proposed thereof. Under optimized appropriate diverse parameters such as solvent varieties, catalyst dosage, DMSO addition, reaction time and temperature, the proposed catalytic system (i.e., microwave mediated DESs/DMSO system) has demonstrated significant yields of 5-hydroxymethylfurfural (5-HMF), furfural (FF) and levulinic acid (LevA) of 31.29 %, 28.38 % and 35.65 %, respectively. These favourable results were obtained at the reaction temperature of 140 °C for 40 min. The anticipated catalytic system's activation energy (Ea) was found to be 29.11 kJ/mol. Hence, a practical, inexpensive and sustainable process with the potential of high-value platform chemicals, explicitly for a sustainable strategy in a circular bioeconomy was proposed.

Emissions of C2 - C12 hydrocarbons in the Hsuehshan tunnel, Taiwan.

The concentrations of 56 hydrocarbons from C2 to C12 were measured simultaneously in the southbound bore, the northbound bore and the exhaust air shafts of the Hsuehshan tunnel near Yilan, Taiwan for 12 days during 2007 and 2008. A total of 60 integrated air samples were collected using stainless steel canisters and analyzed using GC/FID and GC/MS. The five most abundant species in all samples were ethylene, acetylene, isopentane, propylene and toluene. The exit/entrance ratios of total non-methane hydrocarbons (NMHC) concentration were 7.8 and 4.8 for the southbound and northbound bores, respectively. Furthermore, the exhaust from the vertical shafts affects air quality in the neighborhood. The most abundant species of emission rate (ER) was toluene (21.93-42.89 mg/sec), followed by isopentane, ethylene, propylene and 1-butene, with ER ranging from 2.50 to 9.31 mg/sec. The species in the three exhaust air shafts showed that the reactivities of these emissions are similar to those of vehicle emissions. Notably, the control of emissions in the vertical shafts of the vehicle tunnel will be important in the future.

Applying model simulation and photochemical indicators to evaluate ozone sensitivity in southern Taiwan.

Ozone sensitivity was investigated using CAMx simulations and photochemical indicator ratios at three sites (Pingtung City, Chao-Chou Town, and Kenting Town) in Pingtung County in southern Taiwan during 2003 and 2004. The CAMx simulations compared fairly well with the hourly concentrations of ozone. Simulation results also showed that Pingtung City was mainly a volatile organic compounds (VOC)-sensitive regime, while Chao-Chou Town was either a VOC-sensitive or a NOx-sensitive regime, depending on the seasons. Measurements of three photochemical indicators (H2O2, HNO3, and NOy) were conducted, and simulated three transition ranges of H2O2/HNO3 (0.5-0.8), O3/HNO3 (10.3-16.2) and O3/NOy (5.7-10.8) were adopted to assess the ozone sensitive regime at the three sites. The results indicated that the three transition ranges yield consistent results with CAMx simulations at most times at Pingtung City. However, both VOC-sensitive and NOx-sensitive regimes were important at the rural site Chao-Chou Town. Kenting Town, a touring site at the southern end of Taiwan, was predominated by a NOx-sensitive regime in four seasons.

Simultaneous hydrogen production and ibuprofen degradation by green synthesized Cu2O/TNTAs photoanode.

This study aimed to produce a clean energy, hydrogen, and to remove pollutants simultaneously in water by photoelectrochemical (PEC) method. The photo-anode of cuprous oxide modified titanate nanotube arrays (Cu2O/TNTAs) was synthesized by using lactic acid, green tea, and coffee as reductants individually. The characterizations of Cu2O/TNTAs were performed by ultraviolet-visible diffuse reflectance spectroscopy (UV-vis DRS), field emission scanning electron microscope (FE-SEM), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD) to investigate the physical and chemical properties such as structure, crystallization, element contents, and optical performance. The electrochemical analyses of Cu2O/TNTAs showed the photo-current of Cu2O/TNTAs-t (using green tea as reductant) was 2.4 times higher than pure TNTAs, illustrating the effective separation of electron-hole pairs after Cu2O modification. The photoelectrochemical performances of Cu2O/TNTAs-t and Cu2O/TNTAs-c (using coffee as the reductant) were better than Cu2O/TNTAs-L (using lactic acid as the reductant) in terms of photo-current density, Ibuprofen degradation, and hydrogen generation, implying that depositing Cu2O on TNTAs can significantly improve the electron mobility by reducing the recombination rate of electron-hole pairs, which is beneficial to simultaneously ibuprofen degradation and hydrogen production.

Green synthesis of nano-silver-titanium nanotube array (Ag/TNA) composite for concurrent ibuprofen degradation and hydrogen generation.

Silver deposited titanate nanotube array composite (Ag/TNA-c) was successfully synthesized using tea leaves and ground coffee as reducing agent for the first time. The synthesis method was effective, eco-friendly, and reproducible in producing quality nano-composite. The Ag/TNA composite was characterized via XPS, SEM, UV-vis, XRD, and electrochemical analyses for chemical and physical properties. Additionally, chlorogenic acid, caffeine, and catechin were selected as reducing agents for purpose of comparison. Results indicated that catechin and chlorogenic acid were the main reducing agents responsible for Ag+ reduction in tea leaves and ground coffee, respectively. The synthesized Ag/TNA-c exhibited the best photocatalytic (PC) performance in terms of photo-current response, EIS, Ibuprofen degradation, and hydrogen generation in a PEC system. Pairing with a Pt cathode, the photoelectrochemical (PEC) system using the synthesized Ag/TNA composite photo-anode, was capable of concurrent anodic oxidation of Ibuprofen and cathodic generation of hydrogen. Deposition of nano-Ag particles on TNA enhanced the concurrent oxidation and reduction reaction in the PEC system. Results of ESR analysis confirmed the role of hydroxyl radical on Ibuprofen degradation over Ag/TNA-c in the PEC system. Mechanism of Ag/TNA PEC system was proposed to illustrate the oxidation and reduction 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.

Conversion of rice husk into fermentable sugar and silica using acid-catalyzed ionic liquid pretreatment.

Rice husk is a bulky byproduct with a high silica content from rice milling. In this study, the application of an acid-catalyzed ionic liquid (IL) pretreatment was studied for processing rice husks with a rugged structure. The pretreatment conditions were 130°C for 30 min with 1.2 wt% HCl. The results of enzymatic hydrolysis demonstrated that cellulose conversion of HCl-BMIMCl-treated at 48 h was increased by 660.05%, 538.81%, and 376.55% compared with the untreated, HCl-treated, and BMIMCl-treated rice husks, respectively. Composition analysis demonstrated that most of the hemicellulose was removed in the acid-IL combined treatment. Moreover, scanning electron microscopy, X-ray diffraction (XRD), and Fourier transform infrared analyses indicated that the crystalline structure and outer silica layer of the rice husks were efficiently broken up. The results revealed that the HCl-catalyzed dissolution is highly favorable for the industrial application of rick husks in the production of fermentable sugar and high-purity silica.

Studies on the substrate-dependent photocatalytic properties of Cu2O heterojunctions.

Cu2O is a promising material for photocatalysis because of its absorption ability in the ultraviolet (UV)-visible light range. Cu2O deposited on conductive Ti and fluorine-doped tin oxide (FTO) substrates behaves as a photocathode. Cu2O deposited on an n-type semiconductor such as TiO2 nanotube arrays (TNA)/Ti behaves as a photoanode and has demonstrated better photocatalytic activity than that of TNA/Ti. The substrate-dependent photocatalytic properties of Cu2O heterojunctions are not well studied. In this work, the photocatalytic properties of a Cu2O/TNA/Ti junction as a photoanode and of Cu2O/Ti and Cu2O/FTO junctions as photocathodes without bias were systematically studied to understand their performance. The Cu2O/TNA/Ti photoanode exhibited higher photocurrent spectral responses than those of Cu2O/Ti and Cu2O/FTO photocathodes. The photoanodic/photocathodic properties of those junctions were depicted in their energy band diagrams. Time-resolved photoluminescence indicated that Cu2O/TNA/Ti, Cu2O/Ti, and Cu2O/FTO junctions did not enhance the separation of photogenerated charges. The improved photocatalytic properties of Cu2O/TNA/Ti compared with TNA/Ti were mainly attributed to the UV-visible light absorption of Cu2O.

A field pilot-scale study on heavy metal-contaminated soil washing by using an environmentally friendly agent-poly-γ-glutamic acid (γ-PGA).

In this study, a farmland contaminated by heavy metals (Cu, Zn, Ni, and Cr) was selected to evaluate the performance of poly-γ-glutamic acid (γ-PGA) on the removal of heavy metals in soil washing. The highest heavy metal concentrations at the contaminated site were Cu: 1180 mg/kg, Zn: 1450 mg/kg, Ni: 287 mg/kg, and Cr: 316 mg/kg. Batch experiments designed by Taguchi Method were conducted first to assess the effect of different washing conditions on the removal of heavy metals in laboratory. The results of batch experiments show that factors that affected the removal efficiency of heavy metals was of the order γ-PGA concentration > washing time > liquid/soil ratio > rotational speed. The optimal operating parameters for heavy metal removal were γ-PGA 3.5%, liquid/soil ratio 15/1, washing time 60 min, and rotational speed 100 rpm. Under the optimal conditions, up to 50.7% of the major target metal, Cu, was removed. Heavy metals in the soil were mainly Fe-Mn oxide bound and organically bound. On-site treatment using the optimal operating parameters caused 54.3% of Cu removal. When the soil was washed 3 times by γ-PGA, the removal efficiency of Cu was improved to 74.3%. After the treatment, the change in soil bacterial number was insignificant, indicating that γ-PGA is an environmentally friendly washing reagent.

Degradation of trichloroethylene by photoelectrochemically activated persulfate.

Chlorine-containing organic compounds were discharged informally as a result of untreated industrial wastewater, which caused groundwater pollution. In this study, titanium dioxide nanotube arrays (TNAs) were modified with copper oxide to photoelectrochemical (PEC) active persulfate to degrade trichloroethylene (TCE). The SEM results show copper nano-particles with a cubic shape were successfully deposited on the surface of TNAs. The results of UV-vis analysis indicate the absorption wavelengths red-shift to 550-600 nm for better light utilization. CuO/TNAs were dominated by the anatase phase after sintering at 450 °C with significant visible light response. The chemical contents for the surface of CuO/TNAs are 23.7, 53.4, 18.4 and 4.4% for C, O, Ti and Cu, respectively. The photocurrent of CuO/TNAs is 1.89 times higher than that of TNAs-93 cm^2-1hr under 100 W Hg-lamp illuminations. This demonstrates the efficiency of light utilization of TNAs was improved by the modification with copper nanoparticles. The degradation rate of TCE in the anodic chamber is more effective than that in the cathodic chamber because of the synergistic effect of hydroxyl and sulfate radicals. The mechanism of TCE degradation via persulfate in the PEC system was proposed and discussed in detail.

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.