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1.
Molecules ; 29(14)2024 Jul 21.
Artículo en Inglés | MEDLINE | ID: mdl-39064992

RESUMEN

Utilizing Density Functional Theory (DFT) calculations at the B3LYP/QZVP level and incorporating the Conductor-like Polarizable Continuum Model (C-PCM) for solvation, the thermodynamic and chemical activity properties of 21-(hydroxymethoxy)henicosadecaenal, identified in cultured freshwater pearls from the mollusk Hyriopsis cumingii, have been elucidated. The study demonstrates that this compound releases formaldehyde, a potent antimicrobial agent, through dehydrogenation and deprotonation processes in both hydrophilic and lipophilic environments. Moreover, this polyenal exhibits strong anti-reductant properties, effectively scavenging free radicals. These critical properties classify the pearl-derived ingredient as a natural multi-functional compound, serving as a coloring, antiradical, and antimicrobial agent. The 2-(hydroxymethoxy)vinyl (HMV) moiety responsible for the formaldehyde release can be transferred to other compounds, thereby enhancing their biological activity. For instance, tyrosol (4-(2-hydroxyethyl)phenol) can be modified by substituting the less active 2-hydroxyethyl group with the active HMV one, and hinokitiol (4-isopropylotropolone) can be functionalized by attaching this moiety to the tropolone ring. A new type of meso-carrier, structurally modeled on pearls, with active substances loaded both in the layers and the mineral part, has been proposed.


Asunto(s)
Alcohol Feniletílico , Tropolona , Tropolona/análogos & derivados , Tropolona/química , Tropolona/farmacología , Alcohol Feniletílico/análogos & derivados , Alcohol Feniletílico/química , Alcohol Feniletílico/farmacología , Monoterpenos/química , Monoterpenos/farmacología , Formaldehído/química , Animales , Antioxidantes/química , Antioxidantes/farmacología , Antiinfecciosos/química , Antiinfecciosos/farmacología , Estructura Molecular , Termodinámica
2.
Environ Pollut ; 359: 124481, 2024 Oct 15.
Artículo en Inglés | MEDLINE | ID: mdl-38971489

RESUMEN

There are large masses of coal tar asphalt present in old roads, containing high concentrations of polycyclic aromatic hydrocarbons (PAHs). Uncertainty surrounding the risk they pose causes problems during road reconstruction and for the reuse of the asphalt present. To help elucidate potential risks, a parsimonious linear equilibrium partitioning model for the bioavailability of PAHs in soils contaminated by tar asphalt particles was developed. Furthermore, a set of partitioning coefficients for PAHs between sampled coal tar binders and water were determined experimentally, as well as measurements of freely dissolved concentrations using polyoxymethylene samplers in batch tests and column recirculation experiments with various mixtures of different soils (peat and sandy loam) and tar asphalts. The model predictions of freely dissolved concentrations were conservative and within an order of magnitude of measurements in both batch and column tests. The model presented here only relies on soil organic carbon content and the fraction coal tar binder in the soil to model PAH partitioning. This model could be used for more realistic. Low tier risk assessments towards rational prioritization of sensitive areas for risk reduction efforts.


Asunto(s)
Alquitrán , Hidrocarburos , Hidrocarburos Policíclicos Aromáticos , Contaminantes del Suelo , Suelo , Hidrocarburos Policíclicos Aromáticos/análisis , Contaminantes del Suelo/análisis , Alquitrán/química , Suelo/química , Monitoreo del Ambiente/métodos , Modelos Químicos
3.
Molecules ; 29(12)2024 Jun 10.
Artículo en Inglés | MEDLINE | ID: mdl-38930826

RESUMEN

Psittacofulvins are polyenal dyes responsible for coloring parrot feathers and protecting them against photo-oxidation, harmful radicals, and bacterial degradation. To explain the unusual properties of these compounds, the thermodynamic and global chemical activity descriptors characterizing four natural and three synthetic psittacofulvins, as well as their hydroxyl, carboxyl and dialdehyde derivatives, were determined. To this aim, the DFT method at the B3LYP/QZVP theory level and the C-PCM solvation model were used. The calculations enabled the selection of the projected compounds for the greatest bioactivity and potential applicability as multifunctional ingredients in medicines, cosmetics, supplements, and food, in which they may play a triple role as preservative, radical scavenger, and coloring agent. The results obtained provide arguments for the identification of a fifth psittacofulvin within the parrot feather pigment, characterized by ten conjugated double bonds (docosadecaenal).


Asunto(s)
Colorantes , Animales , Colorantes/química , Plumas/química , Termodinámica , Loros , Estructura Molecular , Modelos Moleculares
4.
Molecules ; 29(3)2024 Jan 31.
Artículo en Inglés | MEDLINE | ID: mdl-38338412

RESUMEN

On the basis of density functional theory (DFT) at the B3LYP/cc-pVQZ level with the C-PCM solvation model, a comparative analysis of the reactivity of the garlic metabolites 2-propenesulfenic acid (PSA) and allyl mercaptan (AM, 2-propene-1-thiol) was performed. In particular, the thermodynamic descriptors (BDE, PA, ETE, AIP, PDE, and Gacidity) and global descriptors of chemical activity (ionization potential (IP), electron affinity (EA), chemical potential (µ), absolute electronegativity (χ), molecular hardness (η) and softness (S), electrophilicity index (ω), electro-donating (ω-) and electro-accepting (ω+) powers, and Ra and Rd indexes) were determined. The calculations revealed that PSA is more reactive than AM, but the latter may play a crucial role in the deactivation of free radicals due to its greater chemical stability and longer lifetime. The presence of a double bond in AM enables its polymerization, preserving the antiradical activity of the S-H group. This activity can be amplified by aryl-substituent-containing hydroxyl groups. The results of the calculations for the simplest phenol-AM derivative indicate that both the O-H and S-H moieties show greater antiradical activity in a vacuum and aqueous medium than the parent molecules. The results obtained prove that AM and its derivatives can be used not only as flavoring food additives but also as potent radical scavengers, protecting food, supplements, cosmetics, and drug ingredients from physicochemical decomposition caused by exogenous radicals.

5.
Aquat Toxicol ; 265: 106742, 2023 Dec.
Artículo en Inglés | MEDLINE | ID: mdl-37977012

RESUMEN

The production and release of chemicals from human activities are on the rise. Understanding how the aquatic environment is affected by the presence of an unknown number of chemicals is lacking. We employed the chemical activity concept to assess the combined effects of hydrophobic organic contaminants on the phytoplankton species Rodomonas salina. Chemical activity is additive, and refers to the relative saturation of a chemical in the studied matrix. The growth of R. salina was affected by chemical activity, following a chemical activity-response curve, resulting in an Ea50 value of 0.078, which falls within the baseline toxicity range observed in earlier studies. The chlorophyll a content exhibited both increases and decreases with rising chemical activity, with the increase possibly linked to an antioxidant mechanism. Yet, growth inhibition provided more sensitive and robust responses compared to photosynthesis-related endpoints; all measured endpoints correlated with increased chemical activity. Growth inhibition is an ecologically relevant endpoint and integrates thermodynamic principles such as membrane disruption. Our study utilized passive dosing, enabling us to control exposure and determine activities in both the medium and the algae. The concept of chemical activity and our results can be extended to other neutral chemical groups as effects of chemical activity remain independent of the mixture composition.


Asunto(s)
Artrópodos , Contaminantes Químicos del Agua , Animales , Humanos , Clorofila A , Contaminantes Químicos del Agua/toxicidad , Interacciones Hidrofóbicas e Hidrofílicas , Fitoplancton
6.
Environ Sci Technol ; 57(34): 12806-12818, 2023 08 29.
Artículo en Inglés | MEDLINE | ID: mdl-37590934

RESUMEN

We investigated the trophic magnification potential of perfluoroalkyl substances (PFAS) in a terrestrial food web by using a chemical activity-based approach, which involved normalizing concentrations of PFAS in biota to their relative biochemical composition in order to provide a thermodynamically accurate basis for comparing concentrations of PFAS in biota. Samples of hawk eggs, songbird tissues, and invertebrates were collected and analyzed for concentrations of 18 perfluoroalkyl acids (PFAAs) and for polar lipid, neutral lipid, total protein, albumin, and water content. Estimated mass fractions of PFCA C8-C11 and PFSA C4-C8 predominantly occurred in albumin within biota samples from the food web with smaller estimated fractions in polar lipids > structural proteins > neutral lipids and insignificant amounts in water. Estimated mass fractions of longer-chained PFAS (i.e., C12-C16) mainly occurred in polar lipids with smaller estimated fractions in albumin > structural proteins > neutral lipids > and water. Chemical activity-based TMFs indicated that PFNA, PFDA, PFUdA, PFDoA, PFTrDA, PFTeDA, PFOS, and PFDS biomagnified in the food web; PFOA, PFHxDA, and PFHxS did not appear to biomagnify; and PFBS biodiluted. Chemical activity-based TMFs for PFCA C8-C11 and PFSA C4-C8 were in good agreement with corresponding TMFs derived with concentrations normalized to only total protein in biota, suggesting that concentrations normalized to total protein may be appropriate proxies of chemical activity-based TMFs for PFAS, which predominantly partition to albumin. Similarly, TMFs derived with concentrations normalized to albumin may be suitable proxies of chemical activity-based TMFs for longer-chained PFAS, which predominantly partition to polar lipids.


Asunto(s)
Fluorocarburos , Cadena Alimentaria , Animales , Aves , Albúminas , Agua , Lípidos
7.
Int J Biol Macromol ; 251: 126200, 2023 Aug 09.
Artículo en Inglés | MEDLINE | ID: mdl-37567534

RESUMEN

Non-thermal physical treatments has obvious advantages in regulating the structure and properties of starch compared with chemical treatment. Hance, this article summarized and compared the effects of three kinds of non-thermal physical treatments including grinding and ball milling, high hydrostatic pressure and ultrasonic on the structure, properties and chemical activity of starches from different plants. The potential applications of non-thermal physical modified starch were introduced. And strategies to solve the problems in the current research were put forward. It is found that although starch has a dense structure, the starch granules could be deformed under three kinds of non-thermal physical treatments, which could damage the granule morphology, microstructure, and crystal structure of starch, reduce particle size, increase solubility and swelling power, and promote starch gelatinization. Three kinds of non-thermal physical treated starch could be used as flocculant thickener, starch based edible films and fat substitutes. Non-thermal physical treatments caused the structure of starch to undergo three stages, which were similar to mechanochemical effects. When starch was in the stress stage and the transition stage from aggregation to agglomeration, its active sites significantly increase and move inward, ultimately leading to a significant increase in the chemical activity of starch.

8.
Environ Sci Technol ; 57(29): 10532-10541, 2023 07 25.
Artículo en Inglés | MEDLINE | ID: mdl-37449839

RESUMEN

Interspecies sensitivity to the same chemical can be several orders of magnitude different. Quantifying toxicologically internal levels and toxicokinetic (TK) parameters is critical in elucidating the interspecies sensitivity. Herein, a two-compartmental TK model was constructed to characterize the uptake, distribution, and elimination kinetics toward interspecies sensitivity to an insecticide, imidacloprid. Imidacloprid exhibited the highest lethality to the insect Chironomus dilutus, followed by Lumbriculus variegatus, Hyalella azteca, and Daphnia magna. Interspecies sensitivity of imidacloprid to these invertebrates varied by ∼1000 folds based on water concentrations (LC50). Remarkably, the sensitivity variation decreased to ∼50 folds based on the internal residues (LR50), highlighting the critical role of TK in interspecies sensitivity. A one-compartmental TK model failed to simulate the bioaccumulation of imidacloprid in these invertebrates except for D. magna. Instead, a two-compartmental model successfully simulated the slow elimination of imidacloprid in the remaining three species by internally distinguishing the highly dynamic (C1) and toxicologically available (C2) fractions. We further showed that the species sensitivity of the invertebrates to imidacloprid was significantly related to C2, demonstrating that C2 was toxicologically available and responsible for the toxicity of imidacloprid. This mechanistic-based model bridged the internal distribution of organic contaminants in small invertebrates and the associated toxic potency.


Asunto(s)
Insecticidas , Contaminantes Químicos del Agua , Animales , Modelos Epidemiológicos , Toxicocinética , Invertebrados , Neonicotinoides/toxicidad , Insecticidas/toxicidad , Nitrocompuestos/toxicidad , Contaminantes Químicos del Agua/toxicidad
9.
Small Methods ; : e2300236, 2023 Jul 07.
Artículo en Inglés | MEDLINE | ID: mdl-37415544

RESUMEN

Organic matter accumulation in water can cause serious problems such as oxygen depletion and quality deterioration of waters. While calcium carbonate has been used as green and low-cost adsorbent for water treatment, its efficiency in reducing the chemical oxygen demand (COD) of water, which is a measure of organic pollution, is restrained by the limited specific surface area and chemical activity. Herein, inspired by the high-magnesium calcite (HMC) found in biological materials, a feasible method to synthesize fluffy dumbbell-like HMC with large specific surface area is reported. The magnesium inserting increases the chemical activity of the HMC moderately but without lowering its stability too much. Therefore, the crystalline HMC can retain its phase and morphology in aqueous environment for hours, which allows the establishment of adsorption equilibrium between the solution and the adsorbent that retains its initial large specific surface area and improved chemical activity. Consequently, the HMC exhibits notably enhanced capability in reducing the COD of lake water polluted by organics. This work provides a synergistic strategy to rationally design high-performance adsorbents by simultaneously optimizing the surface area and steering the chemical activity.

10.
Food Res Int ; 165: 112532, 2023 03.
Artículo en Inglés | MEDLINE | ID: mdl-36869532

RESUMEN

It is difficult to improve the quality of chemical-modified starch by traditional technology. Hence, in this study, mung bean starch with poor chemical activity was used as raw material, the native starch was treated and the cationic starch was prepared under high hydrostatic pressure (HHP) at 500 MPa and 40 °C. By studying the changes in the structure and properties of native starch after HHP treatment, the influence mechanism of HHP on improving the quality of cationic starch was analyzed. Results showed high pressure could make water and etherifying agent enter the starch granules through pores, and HHP made the structure of starch undergone three stages similar to mechanochemical effect. After HHP treated for 5 and 20 min, the degree of substitution, reaction efficiency and other qualities of cationic starch increased remarkably. Hence, proper HHP treatment could help to improve the chemical activity of starch and quality of cationic starch.


Asunto(s)
Vigna , Presión Hidrostática , Cationes , Almidón , Agua
11.
Huan Jing Ke Xue ; 44(2): 691-698, 2023 Feb 08.
Artículo en Chino | MEDLINE | ID: mdl-36775593

RESUMEN

In order to understand the effect of volatile organic compounds (VOCs) on ozone pollution, the concentrations, chemical composition variations, and ozone formation potential (OFP) were studied under different O3 concentrations, using high-resolution online monitoring data obtained in the urban site of Beijing in autumn of 2019. The results showed that the average concentration of VOCs was (22.22±10.10)×10-9, with the largest contribution of VOCs from alkanes (55.65%), followed by that of oxygenated volatile organic compounds (OVOCs) (16.23%) and alkenes (8.13%). Three ozone pollution episodes were captured during the observation period. The average concentration of VOCs on pollution days was (26.22±12.52)×10-9, which was 60.17%higher than that on clear days (16.37±7.19)×10-9. The value of ozone formation potential (OFP) on pollution days was 113.63 µg·m-3, which was 56.55%higher than that on clear days. The contributions of OVOCs and aromatics to OFP on pollution days increased by 6.51%and 1.55%, respectively, whereas that of alkenes declined (8.72%). The ratios of toluene to benzene (T/B) and benzene, toluene, and ethylbenzene (B:T:E) were 1.55 and 0.36:0.55:0.09, respectively, indicating that vehicle exhaust had significant effects on VOCs in autumn in urban Beijing. The back-trajectory results indicated a high contribution of southern air masses to atmospheric VOCs variations in autumn in urban Beijing.

12.
J Expo Sci Environ Epidemiol ; 33(2): 283-291, 2023 03.
Artículo en Inglés | MEDLINE | ID: mdl-34531536

RESUMEN

BACKGROUND: Fugacity, the driving force for transdermal uptake of chemicals, can be difficult to predict based only on the composition of complex, non-ideal mixtures such as personal care products. OBJECTIVE: Compare the predicted transdermal uptake of benzophenone-3 (BP-3) from sunscreen lotions, based on direct measurements of BP-3 fugacity in those products, to results of human subject experiments. METHODS: We measured fugacity relative to pure BP-3, for commercial sunscreens and laboratory mixtures, using a previously developed/solid-phase microextraction (SPME) method. The measured fugacity was combined with a transdermal uptake model to simulate urinary excretion rates of BP-3 resulting from sunscreen use. The model simulations were based on the reported conditions of four previously published human subject studies, accounting for area applied, time applied, showering and other factors. RESULTS: The fugacities of commercial lotions containing 3-6% w/w BP-3 were ~20% of the supercooled liquid vapor pressure. Simulated dermal uptake, based on these fugacities, are within a factor of 3 of the mean results reported from two human-subject studies. However, the model significantly underpredicts total excreted mass from two other human-subject studies. This discrepancy may be due to limitations in model inputs, such as fugacity of BP-3 in lotions used in those studies. SIGNIFICANCE: The results suggest that combining measured fugacity with such a model may provide order-of-magnitude accurate predictions of transdermal uptake of BP-3 from daily application of sunscreen products.


Asunto(s)
Cosméticos , Protectores Solares , Humanos , Administración Cutánea , Benzofenonas
13.
Angew Chem Int Ed Engl ; 62(6): e202213336, 2023 02 01.
Artículo en Inglés | MEDLINE | ID: mdl-36218046

RESUMEN

The remarkable progress of applied black phosphorus nanomaterials (BPNMs) is attributed to BP's outstanding properties. Due to its potential for applications, environmental release and subsequent human exposure are virtually inevitable. Therefore, how BPNMs impact biological systems and human health needs to be considered. In this comprehensive Minireview, the most recent advancements in understanding the mechanisms and regulation factors of BPNMs' endogenous toxicity to mammalian systems are presented. These achievements lay the groundwork for an understanding of its biological effects, aimed towards establishing regulatory principles to minimize the adverse health impacts.


Asunto(s)
Nanoestructuras , Fósforo , Animales , Humanos , Nanoestructuras/toxicidad , Mamíferos
14.
J Int Soc Prev Community Dent ; 12(4): 463-467, 2022.
Artículo en Inglés | MEDLINE | ID: mdl-36312575

RESUMEN

Aim and Objective: The relevance of the study was explained by the fact that free radicals, known to be a product of lipid peroxidation, damage the integrity of cell membranes and corresponding intracellular structures, disrupting their functioning. The purpose of this cross-sectional study was to investigate the effect of free-radical lipid peroxidation in the blood on the body of dentists without diseases of the bronchi and lungs. Materials and Methods: The chemiluminescent properties of the blood hemolysate of 65 dentists were measured. Blood was collected in a test tube with an anticoagulant, and the plasma was aspirated with a Pasteur pipette. The hemolysate was aspirated two times. Distilled water was added to the sediment of erythrocytes, the mixture was shaken, and centrifuged. Statistical processing of morphometric indicators was carried out using the software package "Statistica 6.0." Results: The direct dependence of the spontaneous chemiluminescence (SCL) growth parameters in the blood hemolysate of dentists on their length of service was determined. Conclusion: The conclusions indicate a direct correlation between the growth parameters of the SCL index in the blood hemolysate of dentists and their length of service. The applied value of this study lies in the possibility of practical application of the results obtained to qualitatively investigate the effect of lipid peroxidation processes on the body of dentists.

15.
Huan Jing Ke Xue ; 43(8): 3944-3952, 2022 Aug 08.
Artículo en Chino | MEDLINE | ID: mdl-35971693

RESUMEN

To investigate the characteristics and source apportionment of atmospheric volatile organic compounds (VOCs) in Dalian, the concentration level, composition characteristics, reaction activity, and source apportionment of atmospheric VOCs in Dalian were analyzed based on high-resolution online observation VOCs data from June to August 2020. The results showed that the average φ(VOCs) was (10.21±5.71)×10-9, in which alkanes accounted for 66.35%, alkenes for 11.89%, alkynes for 7.75%, and aromatics for 14.01%. VOCs and NOx were high at night and low during the day, whereas the change trend of O3 was opposite. Considering the species activity, it was determined that toluene, ethylene, m/p-xylene, 1-hexene, n-butane, isopentane, n-pentane, and isoprene were the key species affecting atmospheric VOCs in Dalian. Priority control of olefin and aromatic hydrocarbon emissions is the key to improve O3 pollution in summer in Dalian. By applying the positive matrix factorization (PMF) model, six major VOCs sources were extracted, namely traffic sources (26.38%), combustion sources (22.75%), industrial emission sources (17.09%), solvent usage sources (14.59%), natural sources (11.72%), and others (7.47%). The emissions of traffic sources and combustion sources are the key pollution sources for O3 prevention and control in Dalian in summer.


Asunto(s)
Contaminantes Atmosféricos , Ozono , Compuestos Orgánicos Volátiles , Contaminantes Atmosféricos/análisis , China , Monitoreo del Ambiente , Ozono/análisis , Estaciones del Año , Emisiones de Vehículos/análisis , Compuestos Orgánicos Volátiles/análisis
16.
Environ Sci Technol ; 55(16): 11183-11191, 2021 08 17.
Artículo en Inglés | MEDLINE | ID: mdl-34338513

RESUMEN

A calculation estimating the effect concentration (EL/LL50) of a water-accommodated fraction (WAF) for mixture toxicity is proposed. The method is based on chemical activity where the activity of a molecule is its effective concentration taking into account intermolecular interactions. First, the thermodynamic influence of each constituent on the solubility of the others within the mixture (i.e. the concentration of each constituent in the "loading rate") is determined. Then, the non-bioavailable fraction is determined and removed to calculate the true concentration of each constituent exerting toxicity. Finally, the loading rate is adjusted until the sum of activities of the bioavailable fractions is equal to the fraction-weighted average of toxic activity of each constituent. This process is a mechanistic interpretation of experimental WAF tests. The methodology has been validated comparing toxic loading rates of 13 reliable experimental WAF studies on fish, daphnids, and algae. The predictions were all within a factor of 2 of the study outcomes and can be considered as accurate as the laboratory studies. This is in contrast to the standard additivity method which consistently overestimates the toxicity of these mixtures by at least a factor of 2 up to over an order of magnitude or even more.


Asunto(s)
Contaminantes Químicos del Agua , Animales , Disponibilidad Biológica , Solubilidad , Agua , Contaminantes Químicos del Agua/análisis , Contaminantes Químicos del Agua/toxicidad
17.
Huan Jing Ke Xue ; 42(8): 3595-3603, 2021 Aug 08.
Artículo en Chino | MEDLINE | ID: mdl-34309246

RESUMEN

In late August 2020, a period of O3 pollution occurred in the main urban area of Chongqing and lasted for approximately 2 weeks (till early September). Ambient air samples, collected using Summa Canisters and DNPH sampling columns at three observation sites in the main urban area, were used to study the composition, photochemical reaction activity, and source apportionment of volatile organic compounds (VOCs) during the period of O3 pollution. The results showed that the mean volume fraction of TVOCs in the main urban area of Chongqing during the observation period was 45.08×10-9, and the components were ranked by volume fraction in the following order:OVOCs, alkanes, halohydrocarbons, alkenes, aromatics, and alkynes. Formaldehyde, ethylene, and acetone made up the higher volume fraction of VOCs, together accounting for more than 30% of TVOCs. OVOCs and alkenes contributed more to · OH loss rate (Li·OH) and ozone formation potential (OFP) and were the key VOCs components for ozone generation. The main active species in the OVOCs component were formaldehyde, acetaldehyde, and acrolein; the main active species in the alkene component were isoprene, ethylene, and n-butene. The ratio of xylene to ethylbenzene in VOCs was low, and they showed a significant correlation, indicating that the VOCs air mass in the main urban area was highly aging and affected by long-distance transmission from other areas. The source apportionment results of the PMF model showed five main sources of VOCs, namely secondary generation (27.67%), vehicle exhaust (26.56%), industrial emission (17.86%), plant (14.51%), and fossil fuel combustion (13.4%).


Asunto(s)
Contaminantes Atmosféricos , Ozono , Compuestos Orgánicos Volátiles , Contaminantes Atmosféricos/análisis , China , Monitoreo del Ambiente , Ozono/análisis , Emisiones de Vehículos/análisis , Compuestos Orgánicos Volátiles/análisis
18.
Chemosphere ; 265: 129174, 2021 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-33340835

RESUMEN

Reliable delineation of aquatic toxicity cut-offs for poorly soluble hydrocarbons is lacking. In this study, vapor and passive dosing methods were applied in limit tests with algae and daphnids to evaluate the presence or absence of chronic effects at exposures corresponding to the water solubility for representative hydrocarbons from five structural classes: branched alkanes, mono, di, and polynaphthenic (cyclic) alkanes and monoaromatic naphthenic hydrocarbons (MANHs). Algal growth rate and daphnid immobilization, growth and reproduction served as the chronic endpoints investigated. Results indicated that the dosing methods applied were effective for maintaining mean measured exposure concentrations within a factor of two or higher of the measured water solubility of the substances investigated. Chronic effects were not observed for hydrocarbons with an aqueous solubility below approximately 5 µg/L. This solubility cut-off corresponds to structures consisting of 13-14 carbons for branched and cyclic alkanes and 16-18 carbons for MANHs. These data support reliable hazard and risk evaluation of hydrocarbon classes that comprise petroleum substances and the methods described have broad applicability for establishing empirical solubility cut-offs for other classes of hydrophobic substances. Future work is needed to understand the role of biotransformation on the observed presence or absence of toxicity in chronic tests.


Asunto(s)
Petróleo , Contaminantes Químicos del Agua , Hidrocarburos/toxicidad , Interacciones Hidrofóbicas e Hidrofílicas , Petróleo/toxicidad , Solubilidad , Tolueno , Contaminantes Químicos del Agua/análisis , Contaminantes Químicos del Agua/toxicidad
19.
J Hazard Mater ; 410: 124646, 2021 05 15.
Artículo en Inglés | MEDLINE | ID: mdl-33250309

RESUMEN

It is a great challenge to accurately estimate chemical activity of hydrophobic organic contaminants in field soils. Ex-situ and in-situ determinations were developed for this purpose based on low-density polyethylene (LDPE) passive sampling and non-equilibrium correction by release of performance reference compounds (PRCs) previously spiked to the samplers. This work investigated kinetic processes of target contaminants' uptake into and PRCs' release from the sampler in an ex-situ soil suspension incubated for 100 days. A close agreement of kinetic parameters for pyrene's (target) uptake into and deuterated pyrene's (PRC) release from LDPE indicated their similar exchange kinetics. Three kinetic models were developed to correct uptake of target compounds in non-equilibrium conditions via release processes of PRCs. The second-order kinetic model was recommended for ex-situ measurements. The PRC-based non-equilibrium corrections were further applied to in-situ static passive sampling from several weeks to months in a PAH-contaminated field site. Two-weeks' deployments were sufficient for quantifying lighter PAHs (logKOA < 8.0), but not recommended to accurately estimate heavier PAHs (logKOA > 9.0), even if over four months. Concentration estimates from the in-situ and ex-situ passive samplings were comparable in order of magnitude with traditional estimation from equilibrium partitioning models considering both organic and black carbon fractions.

20.
Huan Jing Ke Xue ; 41(6): 2586-2595, 2020 Jun 08.
Artículo en Chino | MEDLINE | ID: mdl-32608772

RESUMEN

As important precursors of near-surface ozone, secondary organic aerosols (SOAs), and volatile organic compounds (VOCs) play an important role in photochemical reactions and fine particle formation. In this study, real-time VOCs were measured continuously by Syntech Spectras GC955 analyzers at the regional background site of the North China Plain from September 1 to 27, 2017. The VOC concentration levels, compositions, spatiotemporal variations, and the ozone formation potential during the observation period were investigated. The potential sources of initial VOCs indicated from the diagnostic ratios were further studied. The averaged total mixing ratio of VOCs was 12.53×10-9. Among all measured VOC species, alkanes were the most abundant species, which accounted for 65.3% of the total concentrations, followed by alkenes (26.7%) and aromatics (6.5%). In addition, the total OH radical loss rate of VOCs (L·OH) was 5.2 s-1. In particular, the contribution of C4-C5 alkenes to L·OH was as high as 61%, followed by C2-C3 alkenes, with a 12.8% contribution of L·OH. The average ozone formation potential of VOCs was 36.5×10-9. Among all the measured VOC species, alkenes were the most abundant species, which accounted for 71.2%. Among alkenes, the contribution of C4-C5 alkenes was the most prominent. Although the concentration of alkanes in Shangdianzi was much higher than other VOC species, the ozone formation potential was lower. Diagnostic ratios and source implications suggested that Shangdianzi was affected mainly by biomass/biofuel/coal burning, with substantially elevated benzene levels during the observation period, whereas a slight influence of traffic-related emissions was observed.

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