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Environmental Science & Technology Nov 2023The activation of peroxydisulfate (PDS) by organic compounds has attracted increasing attention. However, some inherent drawbacks including quick activator decomposition...
The activation of peroxydisulfate (PDS) by organic compounds has attracted increasing attention. However, some inherent drawbacks including quick activator decomposition and poor anti-interference capacity limited the application of organic compound-activated PDS. It was interestingly found that 2,2'-azino-bis (3-ethylbenzothiazoline-6-sulfonate) (ABTS) could act as both activator and electron shuttle for PDS activation to enhance diclofenac (DCF) degradation over a pH range of 2.0-11.0. Multiple reactive species of ABTS, OH, and SO were generated in the PDS/ABTS system, while only ABTS and OH directly contributed to DCF degradation. ABTS, generated via the reactions of ABTS with PDS, SO, and OH, was the dominant reactive species of DCF degradation. No significant decomposition of ABTS was observed in the PDS/ABTS system, and ABTS acted as both activator and electron shuttle. Four possible degradation pathways of DCF were proposed, and the toxicity of DCF decreased after treatment with the PDS/ABTS system. The PDS/ABTS system had good anti-interference capacity to common natural water constituents. Additionally, ABTS was encapsulated into cellulose to obtain ABTS@Ce beads, and the PDS/ABTS@Ce system possessed excellent performance on DCF degradation. This study proposes a new perspective to reconsider the mechanism of activating PDS with organic compounds and highlights the considerable contribution of organic radicals on contaminant removal.
Topics: Oxidation-Reduction; Diclofenac; Electrons; Water Pollutants, Chemical; Organic Chemicals
PubMed: 36260114
DOI: 10.1021/acs.est.2c04318 -
The Science of the Total Environment Jun 2024There has been increasing concern regarding the adverse environmental and health effects of organic pollutants. A list of priority control organic pollutants (PCOPs) can...
There has been increasing concern regarding the adverse environmental and health effects of organic pollutants. A list of priority control organic pollutants (PCOPs) can provide regulatory frameworks for the use and monitoring of organic compounds in the environment. In this study, 20,010 groundwater samples were collected from 15 "first level" groundwater resource zones in China. Fifty (50) organic compounds were analyzed based on their prevalence, occurrence, and physicochemical properties (persistence, bioaccumulation, and toxicity). Results showed that 16 PCOPs, including 12 pesticides, 3 aromatic hydrocarbons (AHs), and 1 phthalate ester, were recognized. Pesticides and AHs accounted for 75 % and 18.75 % of the high-priority pollutants, respectively. There were significant differences in PCOPs between confined and phreatic groundwater. Higher concentrations of pesticides were mainly detected in phreatic groundwater. PCOPs detected in samples from the 15 groundwater resource zones were mainly pesticides and AHs. The groundwater data indicate that the organic compounds detected in the Yellow River Basin (YRB), Yangtze River Basin (YZB), Liaohe River Basin (LRB), and Songhua River Basin (SRB) are mainly categorized as Q1 (high priority) and Q2 (medium priority) pollutants based on the contaminants ranking system in China. The findings from this study offer a snapshot of the wide distribution of PCOPs in the surveyed regions, and are expected to establishing treatment and prevention measures at both the regional and national levels in China.
Topics: China; Water Pollutants, Chemical; Groundwater; Environmental Monitoring; Bioaccumulation; Pesticides; Organic Chemicals
PubMed: 38653420
DOI: 10.1016/j.scitotenv.2024.172656 -
Chemosphere Feb 2024Empirical information about the transport properties of neonicotinoid pesticides through the soil as affected by the ubiquitous low molecular weight organic acids...
Low-molecular-weight organic acids-mediated transport of neonicotinoid pesticides through saturated soil porous media: Combined effects of the molecular structures of organic acids and the chemical properties of contaminants.
Empirical information about the transport properties of neonicotinoid pesticides through the soil as affected by the ubiquitous low molecular weight organic acids (LMWOAs) is lacking. Herein, the impacts of three LMWOAs with different molecular structures, including citric acid, acetic acid, and malic acid, on the mobility characteristics of two typical neonicotinoid pesticides (Dinotefuran (DTF) and Nitenpyram (NTP)) were explored. Interestingly, under acidic conditions, different mechanisms were involved in transporting DTF and NTP by adding exogenous LMWOAs. Concretely, acetic acid and malic acid inhibited DTF transport, ascribed to the enhanced electrostatic attraction between DTF and porous media and the additional binding sites provided by the deposited LMWOAs. However, citric acid slightly enhanced DTF mobility due to the fact that the inhibitory effect was weakened by the steric hindrance effect induced by the deposited citric acid with a large molecular size. In comparison, all three LMWOAs promoted NTP transport at pH 5.0. Because the interaction between NTP with soil organic matter (e.g., via π-π stacking interaction) was masked by the LMWOAs coating on soil surfaces. Nevertheless, LMWOAs could promote the mobility of both neonicotinoid pesticides at pH 7.0 due to the steric hindrance effect caused by the deposited organic acids and the competitive retention between LMWOAs and pesticides for effective surface deposition sites of soil particles. Furthermore, the extent of the promotion effects of LMWOAs generally followed the order of citric acid > malic acid > acetic acid. This pattern was highly related to their molecular structures (e.g., number and type of functional groups and molecular size). Additionally, when the background solutions contained Ca, the bridging effect of cations also contributed to the transport-enhancement effects of LMWOAs. The findings provide valuable information about the mobility behaviors of neonicotinoid pesticides co-existing with LMWOAs in soil-water systems.
Topics: Molecular Structure; Soil; Porosity; Organic Chemicals; Citric Acid; Molecular Weight; Acetic Acid; Neonicotinoids; Soil Pollutants
PubMed: 38056716
DOI: 10.1016/j.chemosphere.2023.140870 -
Environmental Science & Technology Oct 2023Halogenated organic compounds in wastewater are persistent and bioaccumulative contaminants of great concern, but few are known at the molecular level. Herein, we focus...
Halogenated organic compounds in wastewater are persistent and bioaccumulative contaminants of great concern, but few are known at the molecular level. Herein, we focus on nontarget screening of halogenated dissolved organic matter (DOM) in highly concentrated organic matrices of waste leachates and their concentrates. Solid-phase extraction (SPE) was optimized before capturing halogenated signatures via HaloSeeker 2.0 software on mining full-scan high-resolution mass spectrometry (HRMS) fingerprints. This study identified 438 Cl-/Br-containing DOM formulas in 21 leachates and membrane concentrates. Among them, 334 formulas were achieved via SPE with mixed-sorbent cartridges (mixed-SPE), surpassing the 164 formulas achieved through Bond Elut PPL cartridges (PPL-SPE). Herein, only four samples identified via PPL-SPE exhibited a resolution of >50% for extracted Cl-/Br-containing DOM by either SPE. The halogenated DOM constituted 6.87% of the total DOM mass features. Nevertheless, more abundant adsorbable organic halogens deciphered waste leachates and highly concentrated waste streams as reservoirs for halogenated contaminants. Remarkably, 75.7-98.1% of Cl-/Br-containing DOM in primary membrane concentrates remained stable through the secondary membrane treatment, indicating the persistence of these unknown contaminants even post-treatment.
Topics: Dissolved Organic Matter; Mass Spectrometry; Organic Chemicals; Wastewater; Solid Phase Extraction
PubMed: 37822265
DOI: 10.1021/acs.est.3c04422 -
The Science of the Total Environment Nov 2023Small-scale water sources serving villages and towns are the main source of drinking water in rural areas. Compared to centralized water sources, rural water sources are...
Small-scale water sources serving villages and towns are the main source of drinking water in rural areas. Compared to centralized water sources, rural water sources are less frequently monitored for water quality and have poor post-treatment facilities, making them vulnerable to drinking health risks. To reveal the hydrochemical characteristics, contaminant sources, and health risks in rural water sources, 189 water samples were collected from lakes and reservoirs, rivers, and groundwater in North and East China for major ions, nutrient salts, microelements, and stable isotope analysis. Statistical analysis and isotopic tracing were performed, as well as human health risk assessment. The exceeding threshold rates for fluoride (F) and nitrate (NO) in surface water were 1.8 % and 9.1 %, respectively. For groundwater, the exceeding threshold rates were 20.9 % for F, 15.7 % for total iodine (TI), and 4.5 % for NO. F and TI were mainly derived from the leaching of fluoride- and iodine-containing minerals by cationic exchange, and NO is mainly derived from nitrogen in the soil (31.7-43.9 %), the use of ammonia fertilizers (24.3-36.1 %), and the discharge of manure and sewage (19.4-31.9 %). Nitrogen in the soil can be an important source of nitrate in the aquatic environment, and soils with higher clay content have a greater retention effect on the migration of nitrogen pollutants from the surface to the groundwater. F in water sources contributes most to human health risks for drinking, followed by NO and TI, and a higher proportion of groundwater (37 %) present health risks for drinking than surface water (14 %) for children. Authorities should give high priority to optimizing the choice of water sources and technology for water treatment, and rational measures should be taken to protect water sources from the threats of anthropogenic pollution.
Topics: Child; Humans; Nitrates; Fluorides; Drinking Water; Nitrogen Isotopes; Iodine; Environmental Monitoring; Organic Chemicals; Nitrogen; Water Quality; Groundwater; Soil; China; Water Pollutants, Chemical
PubMed: 37474072
DOI: 10.1016/j.scitotenv.2023.165561 -
Environment International Dec 2023Ultrafine particles and volatile organic compounds (VOCs) have been detected from material extrusion 3D printing, which is widely used in non-industrial environments....
Ultrafine particles and volatile organic compounds (VOCs) have been detected from material extrusion 3D printing, which is widely used in non-industrial environments. This study consolidates data of 447 particle emission and 58 VOC emission evaluations from a chamber study using a standardized testing method with various 3D printing scenarios. The interquartile ranges of the observed emission rates were 10-10 #/h for particles and 0.2-1.0 mg/h for total VOC. Print material contributed largely to the variations of particle and total VOC emissions and determined the most abundantly emitted VOCs. Printing conditions and filament specifications, included printer brand, print temperature and speed, build plate heating setup, filament brand, color and composite, also affected emissions and resulted in large variations observed in emission profiles. Multiple regression showed that particle emissions were more impacted by various print conditions than VOC emissions. According to indoor exposure modeling, personal and residential exposure scenarios were more likely to result in high exposure levels, often exceeding recommended exposure limits. Hazardous VOCs commonly emitted from 3D printing included aromatics, aldehydes, alcohols, ketones, esters and siloxanes, among which were various carcinogens, irritants and developmental and reproductive toxins. Therefore, 3D printing emits a complex mixture of ultrafine particles and various hazardous chemicals, exposure to which may exceed recommended exposure limits and potentially induce acute, chronic, or developmental health effects for users depending on exposure scenarios.
Topics: Volatile Organic Compounds; Particulate Matter; Aldehydes; Ketones; Printing, Three-Dimensional; Air Pollution, Indoor
PubMed: 37952412
DOI: 10.1016/j.envint.2023.108316 -
Environmental Pollution (Barking, Essex... May 2024Silicone wristbands are a noninvasive personal exposure assessment tool. However, despite their utility, questions remain about the rate at which chemicals accumulate on...
Silicone wristbands are a noninvasive personal exposure assessment tool. However, despite their utility, questions remain about the rate at which chemicals accumulate on wristbands when worn, as validation studies utilizing wristbands worn by human participants are limited. This study evaluated the chemical uptake rates of 113 organic pollutants from several chemical classes (i.e., polychlorinated biphenyls (PCB), organophosphate esters (OPEs), alkyl OPEs, polybrominated diphenyl ethers (PBDEs), brominated flame retardants (BFR), phthalates, pesticides, and polycyclic aromatic hydrocarbons (PAHs) over a five-day period. Adult participants (n = 10) were asked to wear five silicone wristbands and then remove one wristband each day. Several compounds were detected in all participants' wristbands after only one day. The number of chemicals detected frequently (i.e. in at least seven participants wristbands) increased from 20% of target compounds to 26% after three days and more substantially increased to 34% of target compounds after four days of wear. Chemicals detected in at least seven participants' day five wristbands (n = 24 chemicals) underwent further statistical analysis, including estimating the chemical uptake rates over time. Some chemicals, including pesticides and phthalates, had postive and significant correlations between concentrations on wristbands worn five days and concentrations of wristbands worn fewer days suggesting chronic exposure. For 23 of the 24 compounds evaluated there was a statistically significant and positive linear association between the length of time wristbands were worn and chemical concentrations in wristbands. Despite the differences that exist between laboratory studies using polydimethylsiloxane (PDMS) environmental samplers and worn wristbands, these results indicate that worn wristbands are primarily acting as first-order kinetic samplers. These results suggest that studies using different deployment lengths should be comparable when results are normalized to the length of the deployment period. In addition, a shorter deployment period could be utilized for compounds that were commonly detected in as little as one day.
Topics: Humans; Adult; Silicones; Flame Retardants; Environmental Pollutants; Environmental Monitoring; Male; Female; Environmental Exposure; Halogenated Diphenyl Ethers; Polychlorinated Biphenyls; Polycyclic Aromatic Hydrocarbons; Pesticides; Young Adult; Wrist; Phthalic Acids
PubMed: 38574945
DOI: 10.1016/j.envpol.2024.123877 -
Environmental Science and Pollution... Oct 2023With an increase in production and application of various engineering nanomaterials (ENMs), they will inevitably be released into the environment. Adsorption of various...
With an increase in production and application of various engineering nanomaterials (ENMs), they will inevitably be released into the environment. Adsorption of various organic chemicals onto ENMs will impact on their environmental behavior and toxicology. It is unrealistic to experimentally determine adsorption equilibrium constants (K) for the vast number of organics and ENMs due to high cost in expenditure and time. Herein, appropriate molecular dynamics (MD) methods were evaluated and selected by comparing experimental K values of seven organics adsorbed onto graphene with the MD-calculated ones. Machine learning (ML) models on K of organics adsorption onto graphene and black phosphorus nanomaterials were constructed based on a benchmark data set from the MD simulations. Lasso models based on Mordred descriptors outperformed ML models built by support vector machine, random forest, k-nearest neighbor, and gradient boosting decision tree, in terms of cross-validation coefficients (Q > 0.90). The Lasso models also outperformed conventional poly-parameter linear free energy relationship models for predicting logK. Compared with previous models, the Lasso models considered more compounds with different functional groups and thus have broader applicability domains. This study provides a promising way to fill the data gap in logK for chemicals adsorbed onto the ENMs.
Topics: Graphite; Molecular Dynamics Simulation; Adsorption; Organic Chemicals; Machine Learning
PubMed: 37759049
DOI: 10.1007/s11356-023-29962-z -
Food Chemistry Mar 2024Biocatalysis entails the use of purified enzymes in the manufacturing of flavouring chemicals food industry as well as at the laboratory level. These biocatalysts can... (Review)
Review
Biocatalysis entails the use of purified enzymes in the manufacturing of flavouring chemicals food industry as well as at the laboratory level. These biocatalysts can significantly accelerate organic chemical processes and improve product stereospecificity. The unique characteristics of biocatalyst helpful in synthesizing the environmentally friendly flavour and aroma compounds used as a food additive in foodstuffs. With methods like enzyme engineering on biotechnological interventions the efficient tuning of produce will fulfil the needs of food industry. This review summarizes the biosynthesis of different flavour and aroma component through microbial catalysts and using advanced techniques which are available for enzyme improvement. Also pointing out their benefits and drawbacks for specific technological processes necessary for successful industrial application of biocatalysts. The article covers the market scenario, cost economics, environmental safety and regulatory framework for the production of food flavoured chemicals by the bioprocess engineering.
Topics: Food Additives; Biotechnology; Flavoring Agents; Biocatalysis; Organic Chemicals
PubMed: 37832337
DOI: 10.1016/j.foodchem.2023.137217 -
Environmental Science & Technology Nov 2023The partitioning of semivolatile organic compounds (SVOCs) between the condensed and gas phases can have significant implications for the properties of aerosol...
The partitioning of semivolatile organic compounds (SVOCs) between the condensed and gas phases can have significant implications for the properties of aerosol particles. In addition to affecting size and composition, this partitioning can alter radiative properties and impact cloud activation processes. We present measurements and model predictions on how activity and pH influence the evaporation of SVOCs from particles to the gas phase, specifically investigating aqueous inorganic particles containing dicarboxylic acids (DCAs). The aerosols are studied at the single-particle level by using optical trapping and cavity-enhanced Raman spectroscopy. Optical resonances in the spectra enable precise size tracking, while vibrational bands allow real-time monitoring of pH. Results are compared to a Maxwell-type model that accounts for volatile and nonvolatile solutes in aqueous droplets that are held at a constant relative humidity. The aerosol inorganic-organic mixture functional group activity coefficients thermodynamic model and Debye-Hückel theory are both used to calculate the activities of the species present in the droplet. For DCAs, we find that the evaporation rate is highly sensitive to the particle pH. For acidity changes of approximately 1.5 pH units, we observe a shift from a volatile system to one that is completely nonvolatile. We also observe that the pH itself is not constant during evaporation; it increases as DCAs evaporate, slowing the rate of evaporation until it eventually ceases. Whether a DCA evaporates or remains a stable component of the droplet is determined by the difference between the lowest p of the DCA and the pH of the droplet.
Topics: Organic Chemicals; Dicarboxylic Acids; Thermodynamics; Aerosols; Hydrogen-Ion Concentration
PubMed: 37885068
DOI: 10.1021/acs.est.3c02894