Impacts of LNAPL types on mechanisms and rate of natural source zone depletion.

Understanding the mechanisms of natural source zone depletion (NSZD) will support an improved understanding of the long-term sustainability of NSZD as a site remedy and how NSZD rates may change over time. This is the first study that has quantified and compared the rate of three NSZD mechanisms (methanogenesis, vaporization, and aqueous biodegradation) between two chemically distinct light non-aqueous phase liquid (LNAPL) source zones (aliphatic-rich naphtha for Zone #1 vs aromatic-rich pyrolysis gasoline for Zone #2) within the same geologic and climate conditions. The rates of NSZD attributable to vaporization (400 mg C/m2/d vs. 300 mg C/m2/d) and aqueous biodegradation (92 mg C/m2/d vs. 67 mg C/m2/d) were similar for Zone #1 and #2; however, the rate of methanogenesis NSZD was 6x higher in Zone #1 (1000 mg C/m2/d vs. 170 mg C/m2/d). These results suggest that the aliphatic hydrocarbons content in an LNAPL source may be a factor in the rate of methanogenesis NSZD. For both Zone #1 and #2, total NSZD rate determined using this "three mechanism" measurement method was in reasonable agreement with two other methods used to measure total NSZD rates (CO2 Gradient Method and Dynamic Closed Chamber Method), validating the "three mechanism" method as a tool to measure the total NSZD rate at a site and to provide an improved understanding of the predominant NSZD mechanism. Overall, this study highlights the importance of LNAPL type and chemical characteristics in determining source zone natural attenuation mechanism and its total rates.

Understanding petroleum vapor fate and transport through high resolution analysis of two distinct vapor plumes.

No field study has provided a detailed characterization of the molecular composition and spatial distribution of a vadose zone plume of petroleum volatile organic compounds (VOCs), which is critical to improve the current understanding of petroleum VOC transport and fate. This is study reports a high-resolution analysis of two distinct vapor plumes emanating from two different light non-aqueous phase liquid (LNAPL) sources (an aliphatic-rich LNAPL for Zone #1vs an aromatic-rich LNAPL for Zone #2) at a large petrochemical site. Although deep soil vapor signatures were similar to the source zone LNAPL signatures, the composition of the shallow soil vapors reflected preferential attenuation of certain hydrocarbons over others during upward transport in the vadose zone. Between deeper and shallower soil gas samples, attenuation of aromatics was observed under all conditions, but important differences were observed in attenuation to aliphatic compound classes. Attenuation of all aliphatic compounds was observed under aerobic conditions but little attenuation of any aliphatics was observed under anoxic conditions without methane. In contrast, under methanogenic conditions, paraffins attenuated more than isoparaffins and naphthenes. These results suggest that isoparafins and naphthenes may present more of a vapor intrusion risk than benzene or other aromatic hydrocarbons commonly considered to be petroleum vapor intrusion risk drivers. While the overall vapor composition changed significantly within the vadose zone, diagnostic ratios of relatively recalcitrant alkylcyclopentanes were preserved in shallow soil vapor samples. These alkylcyclopentanes may be useful for distinguishing between petroleum vapor intrusion and other sources of petroleum VOCs detected in indoor air.

Highly efficient extraction of uranium from seawater by polyamide and amidoxime co-functionalized MXene.

Uranium mainly exists in the form of uranyl carbonate in seawater. [UO2(CO3)3]4- has strong stability, which increases the difficulty of uranium extraction from seawater. Meanwhile, the complex marine environment, a large number of coexisting competing ions and biological pollution are all non-negligible disturbing factors. Herein, we introduced amidoxime (AO) groups into the surface of Ti3C2 and grafted polyamides (PA) by a simple one-step hydrothermal method to produce an efficient seawater uranium extraction adsorbent Ti3C2-AO-PA. Owing to the amidoxime groups, the material was highly selective for uranium. And the large number of amino groups in the polyamides gave it ideal resistance to biofouling. The possibility of Ti3C2-AO-PA as an adsorbent for uranium extraction from seawater was confirmed by various characterization techniques, numerous adsorption batch experiments, simulated seawater experiments and antibacterial performance tests. It was demonstrated that the uptake of [UO2(CO3)3]4- by Ti3C2-AO-PA showed fast reaction kinetics (about 120 min), brilliant absorption capacity (81.1 mg·g-1 at pH 8.3), significant high selectivity (32.8 mg-U/g-Ads) and outstanding anti-biological contamination performance (92.9% antibacterial rate). XPS and DFT further indicated that the high extraction ability of Ti3C2-AO-PA for uranium was mainly attributed to the strong complexation of AO and -NH2 with [UO2(CO3)3]4-. These conclusions showed that Ti3C2-AO-PA not only had an ideal application prospect for uranium extraction from seawater, but also provided an available strategy for rapid and selective uranium adsorption from real seawater.

Heterogeneous chemistry of ozone with floor cleaning agent: Implications of secondary VOCs in the indoor environment.

Human daily activities such as cooking, and cleaning can affect the indoor air quality by releasing primary emitted volatile organic compounds (VOCs), as well as by the secondary product compounds formed through reactions with ozone (O3) and hydroxyl radicals (OH). However, our knowledge about the formation processes of the secondary VOCs is still incomplete. We performed real-time measurements of primary VOCs released by commercial floor-cleaning detergent and the secondary product compounds formed by heterogeneous reaction of O3 with the constituents of the cleaning agent by use of high-resolution mass spectrometry. We measured the uptake coefficients of O3 on the cleaning detergent at different relative humidities in dark and under different light intensities (320 nm < λ < 400 nm) relevant for the indoor environment. On the basis of the detected compounds we developed tentative reaction mechanisms describing the formation of the secondary VOCs. Intriguingly, under light irradiation the formation of valeraldehyde was observed based on the photosensitized chemistry of acetophenone which is a constituent of the cleaning agent. Finally, we modeled the observed mixing ratios of three aldehydes, glyoxal, methylglyoxal, and 4-oxopentanal with respect to real-life indoor environment. The results suggest that secondary VOCs initiated by ozone chemistry can additionally impact the indoor air pollution.

Real-time measurements of product compounds formed through the reaction of ozone with breath exhaled VOCs.

Human presence can affect indoor air quality because of secondary organic compounds formed upon reactions between gaseous oxidant species, e.g., ozone (O3), hydroxyl radicals (OH), and chemical compounds from skin, exhaled breath, hair and clothes. We assess the gas-phase product compounds generated by reactions of gaseous O3 with volatile organic compounds (VOCs) from exhaled human breath by real time analysis using a high-resolution quadrupole-orbitrap mass spectrometer (HRMS) coupled to a secondary electrospray ionization (SESI) source. Based on the product compounds identified we propose a reaction mechanism initiated by O3 oxidation of the most common breath constituents, isoprene, α-terpinene and ammonia (NH3). The reaction of O3 with isoprene and α-terpinene generates ketones and aldehydes such as 3,4-dihydroxy-2-butanone, methyl vinyl ketone, 3-carbonyl butyraldehyde, formaldehyde and toxic compounds such as 3-methyl furan. Formation of compounds with reduced nitrogen containing functional groups such as amines, imines and imides is highly plausible through NH3 initiated cleavage of the C-O bond. The detected gas-phase product compounds suggest that human breath can additionally affect indoor air quality through the formation of harmful secondary products and future epidemiological studies should evaluate the potential health effects of these compounds.

The Effect of Human Occupancy on Indoor Air Quality through Real-Time Measurements of Key Pollutants.

The primarily emitted compounds by human presence, e.g., skin and volatile organic compounds (VOCs) in breath, can react with typical indoor air oxidants, ozone (O3), and hydroxyl radicals (OH), leading to secondary organic compounds. Nevertheless, our understanding about the formation processes of the compounds through reactions of indoor air oxidants with primary emitted pollutants is still incomplete. In this study we performed real-time measurements of nitrous acid (HONO), nitrogen oxides (NOx = NO + NO2), O3, and VOCs to investigate the contribution of human presence and human activity, e.g., mopping the floor, to secondary organic compounds. During human occupancy a significant increase was observed of 1-butene, isoprene, and d-limonene exhaled by the four adults in the room and an increase of methyl vinyl ketone/methacrolein, methylglyoxal, and 3-methylfuran, formed as secondary compounds through reactions of OH radicals with isoprene. Intriguingly, the level of some compounds (e.g., m/z 126, 6-methyl-5-hepten-2-one, m/z 152, dihydrocarvone, and m/z 194, geranyl acetone) formed through reactions of O3 with the primary compounds was higher in the presence of four adults than during the period of mopping the floor with commercial detergent. These results indicate that human presence can additionally degrade the indoor air quality.

Daytime SO2 chemistry on ubiquitous urban surfaces as a source of organic sulfur compounds in ambient air.

The reactions of sulfur dioxide (SO2) with surface-bound compounds on atmospheric aerosols lead to the formation of organic sulfur (OS) compounds, thereby affecting the air quality and climate. Here, we show that the heterogeneous reaction of SO2 with authentic urban grime under near-ultraviolet sunlight irradiation leads to a large suite of various organic compounds including OS released in the gas phase. Calculations indicate that at the core area of Guangzhou, building surface uptake of SO2 is 15 times larger than uptake of SO2 on aerosol surfaces, yielding ~20 ng m-3 of OS that represents an important fraction of the observed OS compounds (60 to 200 ng m-3) in ambient aerosols of Chinese megacities. This chemical pathway occurring during daytime can contribute to the observed fraction of OS compounds in aerosols and improve the understanding of haze formation and urban air pollution.

Unveiling the pH-Dependent Yields of H2O2 and OH by Aqueous-Phase Ozonolysis of m-Cresol in the Atmosphere.

Hydrogen peroxide (H2O2) and hydroxyl radical (OH) are important oxidants in the atmospheric aqueous phase such as cloud droplets and deliquescent aerosol particles, playing a significant role in the chemical transformation of organic and inorganic pollutants in the atmosphere. Atmospheric aqueous-phase chemistry has been considered to be a source of H2O2 and OH. However, our understanding of the mechanisms of their formation in atmospheric waters is still incomplete. Here, we show that the aqueous-phase reaction of dissolved ozone (O3) with substituted phenols such as m-cresol represents an important source of H2O2 and OH exhibiting pH-dependent yields. Intriguingly, the formation of H2O2 through the ring-opening mechanism is strongly promoted under lower pH conditions (pH 2.5-3.5), while higher pH favors the ring-retaining pathways yielding OH. The rate constant of the reaction of O3 with m-cresol increases with increasing pH. The reaction products formed during the ozonolysis of m-cresol are analyzed by an Orbitrap mass spectrometer, and reaction pathways are suggested based on the identified product compounds. This study indicates that aqueous-phase ozonolysis of phenolic compounds might be an alternative source of H2O2 and OH in the cloud, rain, and liquid water of aerosol particles; thus, it should be considered in future model studies.

Inorganic Ions Enhance the Number of Product Compounds through Heterogeneous Processing of Gaseous NO2 on an Aqueous Layer of Acetosyringone.

Methoxyphenols represent important pollutants that can participate in the formation of secondary organic aerosols (SOAs) through chemical reactions with atmospheric oxidants. In this study, we determine the influence of ionic strength, pH, and temperature on the heterogeneous reaction of NO2 with an aqueous film consisting of acetosyringone (ACS), as a proxy for methoxyphenols. The uptake coefficient of NO2 (50 ppb) on ACS (1 × 10-5 mol L-1) is γ = (9.3 ± 0.09) × 10-8 at pH 5, and increases by one order of magnitude to γ = (8.6 ± 0.5) × 10-7 at pH 11. The lifetime of ACS due to its reaction with NO2 is largely affected by the presence of nitrate ions and sulfate ions encountered in aqueous aerosols. The analysis performed by membrane inlet single-photon ionization-time-of-flight mass spectrometry (MI-SPI-TOFMS) reveals an increase in the number of product compounds and a change of their chemical composition upon addition of nitrate ions and sulfate ions to the aqueous thin layer consisting of ACS. These outcomes indicate that inorganic ions can play an important role during the heterogeneous oxidation processes in aqueous aerosol particles.

Effect of Shewanella oneidensis MR-1 on U(VI) sequestration by montmorillonite.

Bacteria may change the physicochemical properties of montmorillonite and further effect the disposal of high-level radioactive waste. Therefore, we explored the influence of Shewanella oneidensis MR-1 on the elimination of representative radionuclide U(VI) by montmorillonite (MMT). The batch experiments showed that MR-1 significantly enhanced the removal efficiency of U(VI), the adsorption capacity of MMT improved from 8.4 to 16.1 mg/g after addition of MR-1, and the adsorption type changed from Langmuir to Freundlich. FTIR and XPS analysis revealed that hydroxyl, phosphate, carbonyl and amine in MMT + MR-1 were primary actors in the elimination of U(VI). The U 4f high-resolution XPS spectrum of MMT + MR-1 showed U(VI) and U(IV) peaks at the same time, indicating that the adsorption process was accompanied by the reduction reaction, which may be due to the extracellular respiration of MR-1. These investigations are significant to insight the potential significance of microbial processes for the transport and elimination of U(VI) in repositories, which in return will contribute to their safe disposal.

Full and partial posttraumatic stress disorders in adults exposed to super typhoon Lekima: a cross-sectional investigation.

BACKGROUND: Super typhoon Lekima had a maximum wind force of 16 (52 m/s) and hit Wenling city, Zhejiang province in China on August 10, 2019. The typhoon left many victims showing symptoms of posttraumatic stress disorder (PTSD). OBJECTIVE: This study aimed to assess the prevalence of full and partial PTSD to inform targeted interventions for adult victims. METHOD: In total, four thousand seven hundred and forty-six adults who are parents of students in local primary and middle schools were recruited to participate in this study. Participants completed a trauma exposure scale and the Diagnostic and Statistical Manual of Mental Disorders, Fifth Edition PTSD Checklist. Logistic regression analysis was used to examine the factors of full and partial PTSD. RESULTS: Nine hundred and ten (19.2%) adults had full PTSD and 1775 (37.4%) had partial PTSD. Adults with a monthly income > 10,000 RMB (about 1530 dollars) and a high education level (bachelor's degree or above) were less likely to have full or partial PTSD than those with lower income and lower education levels. In addition, married adults were less likely to have full PTSD than divorced or widowed ones. Higher rates of PTSD were observed among those aged ≥40 years, who were injured/trapped, whose family members/friends were injured/trapped, and who lost property. CONCLUSIONS: Partial and full PTSD were common among adults following super typhoon Lekima, and high income, high education level, and married status were protective factors, whereas trauma exposure was a risk factor of PTSD. Target psychological intervention should be provided to these victims who are in low income and education level, divorced and widowed, and experienced more serious trauma.

Orderly Porous Covalent Organic Frameworks-based Materials: Superior Adsorbents for Pollutants Removal from Aqueous Solutions.

Covalent organic frameworks (COFs) are a new type of crystalline porous polymers known for chemical stability, excellent structural regularity, robust framework, and inherent porosity, making them promising materials for capturing various types of pollutants from aqueous solutions. This review thoroughly presents the recent progress and advances of COFs and COF-based materials as superior adsorbents for the efficient removal of toxic heavy metal ions, radionuclides, and organic pollutants. Information about the interaction mechanisms between various pollutants and COF-based materials are summarized from the macroscopic and microscopic standpoints, including batch experiments, theoretical calculations, and advanced spectroscopy analysis. The adsorption properties of various COF-based materials are assessed and compared with other widely used adsorbents. Several commonly used strategies to enhance COF-based materials' adsorption performance and the relationship between structural property and sorption ability are also discussed. Finally, a summary and perspective on the opportunities and challenges of COFs and COF-based materials are proposed to provide some inspiring information on designing and fabricating COFs and COF-based materials for environmental pollution management.

Recent advances in metal-organic framework membranes for water treatment: A review.

Among many separation membranes reported to date, the favorable polymer affinity and unique physio-chemical performances of metal-organic frameworks (MOFs) including ultra-high surface area, regular and highly controlled porosity have drawn widespread attention in industrial and academic communities. In this comprehensive review, the developmental timeline of MOF containing membranes for water treatment were clarified. The removal efficiencies, elimination mechanisms, as well as possible influencing factors of various MOF containing membranes that applied to water treatment were systematically summarized. The excellent removal performances of MOF containing membranes for various pollutants were determined by the size-exclusion, π-π stacking interaction, electrostatic interaction, hydrogen bonding and so on. Since the progress of engineered MOF containing membranes for practical wastewater treatment applications lags, we further analyzed the potential environmental application of MOF containing membranes from four aspects (stability of MOFs, antifouling performance of membranes, compatibility between MOF fillers and polymer matrix, dispersity of MOF nanoparticles in matrix), hoping to provide some meaningful insights.

Nitrite-Mediated Photooxidation of Vanillin in the Atmospheric Aqueous Phase.

Nitrite (NO2-) and its conjugate acid, nitrous acid (HNO2), have long been recognized as a ubiquitous atmospheric pollutant as well as an important photochemical source of hydroxyl radicals (·OH) and reactive nitrogen species (·NO, ·NO2, ·N2O3, etc.) in both the gas phase and aqueous phase. Although NO2-/HNO2 plays an important role in atmospheric chemistry, our understanding on its role in the chemical evolution of organic components in atmospheric waters is rather incomplete and is still in dispute. In this study, the nitrite-mediated photooxidation of vanillin (VL), a phenolic compound abundant in biomass burning emissions, was investigated under pH conditions relevant for atmospheric waters. The influence of solution pH, dissolved oxygen, and ·OH scavengers on the nitrite-mediated photooxidation of VL was discussed in detail. Our study reveals that the molecular composition of the products is dependent on the molar ratio of NO2-/VL in the solution and that nitrophenols are the major reaction products. We also found that the light absorbance of the oxidative products increases with increasing pH in the visible region, which can be attributed to the deprotonation of the nitrophenols formed. These results contribute to a better understanding of methoxyphenol photooxidation mediated by nitrite as a source of toxic nitrophenols and climatically important brown carbon in atmospheric waters.

Recent Advances in Composites of Graphene and Layered Double Hydroxides for Water Remediation: A Review.

Composites of layered double hydroxides (LDHs) and graphene (G) are exciting nanomaterials because of their unique surface structures and excellent physicochemical properties. Such materials offer the advantages of both components, that is, the large surface area and ample functional groups of graphene and the outstanding layered structure and ion-exchangeability of layered double hydroxides, whilst effectively avoiding the coagulation of graphene and the instability of pristine layered double hydroxides, and they have been widely investigated for applications in water remediation. This Minireview begins by summarizing the most common methods for the synthesis of G@LDH composites, including hydrothermal treatment, coprecipitation, and in situ growth. Then, we review the adsorption and catalytic ability of G@LDH materials in the removal of contaminants from water, such as heavy metal ions, radionuclides, dyes, and other organic pollutants. Finally, we discuss the challenges and offer a perspective on the directions of future research of G@LDH composites.

Environmental remediation of heavy metal ions by novel-nanomaterials: A review.

Recently, novel-nanomaterials with excellent sorption capacities, mild stability, and environmental-friendly performance, have enabled massive developments in capturing heavy metal ions. This review firstly introduces the preparation and modification of novel-nanomaterials (e.g., MOFs, nZVI, MXenes, and g-C3N4). Then, the heavy metal ions' sorption properties and the impact of environmental conditions have been discussed. Subsequently, the sorption mechanisms are verified through batch experiments, spectral analysis, surface complexation models, and theoretical calculations. Finally, the applications prospects of novel-nanomaterials in removing heavy metal ion polluted water have also been discussed, which provide perspective for future in-depth research and practical applications.

Photochemical Aging of Guaiacol by Fe(III)-Oxalate Complexes in Atmospheric Aqueous Phase.

Fe(III)-oxalate complexes are likely abundant in clouds, fogs and aerosol water. They are photoreactive and can act as an important source of reactive oxygen species (·OH, H2O2 and HO2·) in tropospheric aqueous phases. Although the mechanisms involved in ferrioxalate photolysis have been investigated extensively, few kinetic and mechanistic information is available on the aging of dissolved organic compounds by this photochemical system. In this work, the Fe(III)-oxalate mediated photooxidation of guaiacol (GUA), a model for phenolic compounds emitted from biomass burning, was investigated under typical pH conditions of the atmospheric water. The effect of Fe(III) concentration, oxalate concentration and pH on the photooxidation of GUA was studied in detail. Our results revealed that oxalate can inhibit the oxidation of GUA by Fe(III) under the dark condition. However, the iron-catalyzed photooxidation of GUA can be strongly promoted in the presence of oxalate due to the formation of photoactive Fe(III)-oxalate complexes. GUA was rapidly oxidized to form a number of polymeric, functionalized and open-ring products with low volatility. Detailed reaction pathways for the photooxidation of GUA by Fe(III)-oxalate complexes were proposed based on the results of high-resolution mass spectrometry. This work suggests that ferrioxalate photochemistry can play an important role in the transformation of dissolved organics in atmospheric aqueous phases.

Synthesis of rod-like metal-organic framework (MOF-5) nanomaterial for efficient removal of U(VI): batch experiments and spectroscopy study.

With the widespread application of radionuclide 235U(VI), it is inevitable that part of U(VI) is released into the natural environment. The potential toxicity and irreversibility impact on the natural environment has become one of the most forefront pollution problems in nuclear energy utilization. In this work, rod-like metal-organic framework (MOF-5) nanomaterial was synthesized by a solvothermal method and applied to efficiently adsorb U(VI) from aqueous solutions. The batch experimental results showed that the sorption of U(VI) on MOF-5 was strongly dependent on pH and independent of ionic strength, indicating that the dominant interaction mechanism was inner-sphere surface complexation and electrostatic interaction. The maximum sorption capacity of U(VI) on MOF-5 was 237.0 mg/g at pH 5.0 and T = 298 K, and the sorption equilibrium reached within 5 min. The thermodynamic parameters indicated that the removal of U(VI) on MOF-5 was a spontaneous and endothermic process. Additionally, the FT-IR and XPS analyses implied that the high sorption capacity of U(VI) on MOF-5 was mainly attributed to the abundant oxygen-containing functional groups (i.e., CO and CO). Such a facile preparation method and efficient removal performance highlighted the application of MOF-5 as a candidate for rapid and efficient radionuclide contamination's elimination in practical applications.

[Monitoring method of extraction process for Schisandrae Chinensis Fructus based on near infrared spectroscopy and multivariate statistical process control].

To establish an on-line monitoring method for extraction process of Schisandrae Chinensis Fructus, the formula medicinal material of Yiqi Fumai lyophilized injection by combining near infrared spectroscopy with multi-variable data analysis technology. The multivariate statistical process control (MSPC) model was established based on 5 normal batches in production and 2 test batches were monitored by PC scores, DModX and Hotelling T2 control charts. The results showed that MSPC model had a good monitoring ability for the extraction process. The application of the MSPC model to actual production process could effectively achieve on-line monitoring for extraction process of Schisandrae Chinensis Fructus, and can reflect the change of material properties in the production process in real time. This established process monitoring method could provide reference for the application of process analysis technology in the process quality control of traditional Chinese medicine injections.