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1.
Chemistry of hazardous air pollutants has been studied for many years, yet little is known about how these chemicals, once reacted within urban atmospheres, affect healthy and susceptible individuals. Once released into the atmosphere, 1,3-butadiene (BD) reacts with hydroxyl radicals and ozone (created by photochemical processes), to produce many identified and unidentified products. Once this transformation has occurred, the toxic potential of atmospheric pollutants such as BD in the ambient environment is currently unclear. During this study, environmental irradiation chambers (also called smog chambers), utilizing natural sunlight, were used to create photochemical transformations of BD. The smog chamber/in vitro exposure system was designed to investigate the toxicity of chemicals before and after photochemical reactions and to investigate interactions with the urban atmosphere using representative in vitro samples. In this study, we determined the relative toxicity and inflammatory gene expression induced by coupling smog chamber atmospheres with an in vitro system to expose human respiratory epithelial cells to BD, BDs photochemical degradation products, or the equivalent ozone generated within the photochemical mixture. Exposure to the photochemically generated products of BD (primarily acrolein, acetaldehyde, formaldehyde, furan and ozone) induced significant increases in cytotoxicity, IL-8, and IL-6 gene expression compared to a synthetic mixture of primary products that was created by injecting the correct concentrations of the detected products from the irradiation experiments. Interestingly, exposure to the equivalent levels of ozone generated during the photochemical transformation of BD did not induce the same level of inflammatory cytokine release for either exposure protocol, suggesting that the effects from ozone alone do not account for the entire response in the irradiation experiments. These results indicate that BDs full photochemical product generation and interactions, rather than ozone alone, must be carefully evaluated when investigating the possible adverse health effects to BD exposures. The research presented here takes into account that photochemical transformations of hazardous air pollutants (HAPs) does generate a dynamic exposure system and therefore provides a more realistic approach to estimate the toxicity of ambient air pollutants once they are released into the atmosphere. 相似文献
2.
1,3-Butadiene (BD) is metabolized in humans and rodents to mutagenic and carcinogenic species. Our previous work has focused on developing a physiologically based toxicokinetic (PBTK) model for BD to estimate its metabolic rate to 1,2-epoxy-3-butene (EB), using exhaled breath BD concentrations in human volunteers exposed by inhalation. In this paper, we extend our BD model to describe the kinetics of its four major metabolites EB, 1,2:3,4-diepoxybutane (DEB), 3-butene-1,2-diol (BDD), and 3,4-epoxy-1,2-butanediol (EBD), and to test whether the extended model and experimental data (to be collected for BD and metabolites in humans) are together adequate to estimate the metabolic rate constants of each of the above chemicals. Global sensitivity analyses (GSA) were conducted to evaluate the relative importance of the model parameters on model outputs during the 20min of exposure and the 40min after exposure ended. All model parameters were studied together with various potentially measurable model outputs: concentrations of BD and EB in exhaled air, concentrations of BD and all metabolites in venous blood, and cumulated amounts of urinary metabolites excreted within 24h. Our results show that pulmonary absorption of BD and subsequent distribution and metabolism in the well-perfused tissues compartment are the critical processes in the toxicokinetics of BD and metabolites. In particular, three parameters influence numerous outputs: the blood:air partition coefficient for BD, the metabolic rate of BD to EB, and the volume of the well-perfused tissues. Other influential parameters include other metabolic rates, some partition coefficients, and parameters driving the gas exchanges (in particular, for BD outputs). GSA shows that the impact of the metabolic rate of BD to EB on the BD concentrations in exhaled air is greatly increased if a few of the model's important parameters (such as the blood:air partition coefficient for BD) are measured experimentally. GSA also shows that all the transformation pathways described in the PBTK model may not be estimable if only data on the studied outputs are collected, and that data on a specific output for a chemical may not inform all the transformations involving that chemical. 相似文献
3.
Masao Kuwahara Natsuki Kato Katsura Munakata 《Bioscience, biotechnology, and biochemistry》2013,77(3):232-244
A herbicide, sodium pentachlorophenoxide (Na-PCP), used in Japan, is easily decomposed with sunlight after its application in the rice field. The photochemical reaction of Na-PCP in an aqueous solution on exposure to sunlight afforded numerous products which were mainly accompanied with chloranilic acid and a yellow compound (I). The chemical structure of the yellow compound I was established as being 3, 4, 5-trichloro-6-(2′-hydroxy-3′, 4′, 5′, 6′-tetrachlorophenoxy)-o-benzoquinone by chemical and spectroscopic evidences.Minor decomposition products of sodium pentachlorophenoxide (Na-PCP) in an aqueous solution by sunlight have been isolated. Chemical structures of them are described, and infrared and ultraviolet spectra are presented in support of these stractures. These illustrate a new type of oxidative reaction of phenols. 相似文献
4.
城市街道空气污染物扩散模型综述 总被引:2,自引:0,他引:2
城市街道是城市居民的活动场所,其空气质量与居民健康密切相关.空气污染扩散模型是模拟和评估街道空气质量的重要方法,近年来广受关注,但模型应用存在问题,亟待解决.本文介绍了4种常用的空气污染物扩散模型:ENVI-met、FLUENT、MISKAM和OSPM.通过工作原理、运算流程、时空分辨率等的对比分析,明确了各模型的适用范围及其对街道峡谷内空气质量模拟能力的差异,阐述了各模型在时间尺度、物理建模、天气模拟、湍流模拟及光化学污染方面处理能力的局限性,提出了模型优化途径.通过综合分析4种模型的研究案例,总结了模型应用中存在的问题,提出未来研究可以通过激光雷达等新技术提高模型参数的获得精度,并强调综合模拟污染效应与热效应等对评估城市街道空气质量的重要性. 相似文献
5.
Artiukhov VG Basharina OV Vashanov GA Gusinskaia VV Nakvasina MA 《Radiatsionnaia biologiia, radioecologiia / Rossi?skaia akademiia nauk》2001,41(1):78-103
The results of our research devoted to the study of photophysical and photochemical transformations of some compound proteins of oxidative, antioxidant, transport and immune systems of an organism under conditions of different microenvironment (presence of chemical modificators, the change of pH, temperature, doses and spectral composition of ultraviolet irradiation) have been analyzed. Methods and the degree of modulation of UV-sensitivity of proteins of the mentioned systems have been discussed. Conditions, on which the used chemical agents show photoprotective and photosensitizing effect on protein molecules, have been found. 相似文献
6.
A study was made on the induction of sister-chromatid exchanges (SCE) in cultured Chinese hamster V79 cells exposed to the photochemical reaction products of toluene plus NO2 in the gas phase. The photochemical reaction products of toluene plus NO2 were obtained by photochemical reaction of a toluene--NO2/dry air system in a photochemical smog chamber and then exposed to cultured cells for 2 h using a system for in vitro gas exposure. SCEs were induced at all concentrations of the photochemical reaction products employed in the present study, and the highest SCE frequency observed for the highest concentration tested for each component was 3.6 times higher than that of the control. Cytogenotoxicity which was evaluated with induced-SCEs of the photochemical reaction products of toluene plus NO2 was much the same as that of the previously reported photochemical reaction products of propylene plus NO2 (Shiraishi and Bandow, 1985), but was considerably stronger than that of typical gaseous air pollutants such as NO2 alone and O3 alone. 相似文献
7.
Selig Hecht 《The Journal of general physiology》1926,8(3):291-301
1. Experiments are presented which show that the latent period in the photosensory response of Ciona is inversely proportional to the duration of the exposure period to light. From this it is found that the velocity of the chemical reaction which determines the latent period is directly proportional to the concentration of photochemical products formed during the exposure period. This is interpreted as showing that the two processes form a coupled photochemical reaction, of which the secondary reaction proceeds only in the presence of products from the primary reaction. This coupling may be a catalysis or a direct chemical relation. 2. Further experiments show that the relation between temperature and the latent period is accurately described by the Arrhenius equation in which µ = 16,200. The precise numerical value of µ tentatively identifies the latent period process as an oxidation reaction which is catalyzed by iron. 3. The photocatalytic properties of certain iron compounds are used as a model for the coupled photochemical reaction suggested for the photosensory mechanism of Ciona and Mya. 相似文献
8.
Nitrous oxide (N2O) is primarily produced by the microbially-mediated nitrification and denitrification processes in soils. It is influenced by a suite of climate (i.e. temperature and rainfall) and soil (physical and chemical) variables, interacting soil and plant nitrogen (N) transformations (either competing or supplying substrates) as well as land management practices. It is not surprising that N2O emissions are highly variable both spatially and temporally. Computer simulation models, which can integrate all of these variables, are required for the complex task of providing quantitative determinations of N2O emissions. Numerous simulation models have been developed to predict N2O production. Each model has its own philosophy in constructing simulation components as well as performance strengths. The models range from those that attempt to comprehensively simulate all soil processes to more empirical approaches requiring minimal input data. These N2O simulation models can be classified into three categories: laboratory, field and regional/global levels. Process-based field-scale N2O simulation models, which simulate whole agroecosystems and can be used to develop N2O mitigation measures, are the most widely used. The current challenge is how to scale up the relatively more robust field-scale model to catchment, regional and national scales. This paper reviews the development history, main construction components, strengths, limitations and applications of N2O emissions models, which have been published in the literature. The three scale levels are considered and the current knowledge gaps and challenges in modelling N2O emissions from soils are discussed. 相似文献
9.
Background, aim, and scope Traditional life cycle impact assessment methodologies have used aggregated characterization factors, neglecting spatial and
temporal variations in regional impacts like photochemical oxidant formation. This increases the uncertainty of the LCA results
and diminishes the ease of decision-making. This study compares four common impact assessment methods, CML2001, Eco-indicator
99, TRACI, and EDIP2003, on their underlying models, spatial and temporal resolution, and the level at which photochemical
oxidant impacts are calculated. A new characterization model is proposed that incorporates spatial and temporal differentiation.
Materials and methods A photochemical air quality modeling system (CAMx-MM5-SMOKE) is used to simulate the process of formation, transformation,
transport, and removal of photochemical pollutants. Monthly characterization factors for individual US states are calculated
at three levels along the cause–effect chain, namely, fate level, human and ecosystem exposure level, and human effect level.
Results and discussion The results indicate that a spatial variability of one order of magnitude and a temporal variability of two orders of magnitude
exist in both the fate level and human exposure and effect level characterization factors for NOx. The summer time characterization factors for NOx are higher than the winter time factors. However, for anthropogenic VOC, the summer time factors are lower than the winter
time in almost half of the states. This is due to the higher emission rates of biogenic VOCs in the summer. The ecosystem
exposure factors for NOx and VOC do not follow a regular pattern and show a spatial variation of about three orders of magnitude. They do not show
strong correlation with the human exposure factors. Sensitivity analysis has shown that the effect of meteorology and emission
inputs is limited to a factor of three, which is several times smaller than the variation seen in the factors.
Conclusions Uncertainties are introduced in the characterization of photochemical precursors due to a failure to consider the spatial
and temporal variations. Seasonal variations in photochemical activity influence the characterization factors more than the
location of emissions. The human and ecosystem exposures occur through different mechanisms, and impacts calculated at the
fate level based only on ozone concentration are not a good indicator for ecosystem impacts.
Recommendations and perspectives Spatial and temporal differentiation account for fate and transport of the pollutant, and the exposure of and effect on the
sensitive human population or ecosystem. Adequate resolution for seasonal and regional processes, like photochemical oxidant
formation, is important to reduce the uncertainty in impact assessment and improve decision-making power. An emphasis on incorporating
some form of spatial and temporal information within standard LCI databases and using adequately resolved characterization
factors will greatly increase the fidelity of a standard LCA.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
10.
Furocoumarins (psoralens) are photosensitizers of plant origin, which increase the sensitivity of biological objects to near ultraviolet (UV-A, 320-400 nm). In combination with UV-A, they are successfully used for treating many dermal and autoimmune diseases (PUVA therapy and photophoresis). Along with therapeutic effects, the furocoumarin photochemotherapy induces a number of side-effects (erythema, edema, hyperpigmentation, and premature aging of skin). All photobiological effects of furocoumarins result from their photochemical reactions. Therefore, in order to advance the therapy, it is necessary to know the photochemical mechanisms of induction of both side- and therapeutic effects. The types of photoreactions of furocoumarins classified with respect to reactive photoproducts interacting with substrate were considered. Primary emphasis was placed on reactions proceeding with the participation of photooxidation products of furocoumarins. Among these photoproducts, at least two types can be distinguished. Some of them possess membranotoxic properties, others produce the immunosuppressory action in vivo. The photochemical mechanisms of the formation of the photoproducts of furocoumarins are different. It was found that, by varying the illumination conditions (intensity of UV-A radiation or the concentration of the photosensitizer), it is possible to obtain the photoproducts of furocoumarins that have either membranotoxic or immunosuppressory properties. It was found that the mechanisms of the immunosuppressive action of the photooxidation products of furocoumarins have some features in common with those underlying the PUVA therapy and photophoresis. It is assumed that the photochemical basis of the therapeutic action of furocoumarins is the reactions with the involvement of the products of their photooxidation. 相似文献
11.
Genotoxic, carcinogenic, and teratogenic hazards arising out of pollution in the marine environment are discussed in this article, with special reference to the situation in the Mediterranean area. A number of chemical compounds or complex mixtures relevant to marine pollution, either natural or of anthropogenic origin, are tentatively listed, along with protective factors which may play a counteracting role in the same environment. Harmful substances tend to undergo interactions and transformations in seawater, sediments, and marine biota, due to physical, chemical, microbial, or light-mediated mechanisms. Bioaccumulation phenomena in marine organisms may result from food-chain biomagnification processes or from concentration of pollutants by filter feeders. A variety of sources can account for marine pollution by genotoxic, carcinogenic, and teratogenic compounds, but there is a relative paucity of analytical data concerning the Mediterranean. Metabolic transformations of xenobiotics occur in all marine organisms, the biochemical mechanisms in fish being comparable to those which have been extensively investigated in mammals. Induction of metabolic pathways, and especially of the mixed-function oxygenase system, represents the earliest warning signal of exposure to pollutants. Occurrence of neoplastic diseases is documented by experimental and field studies in marine vertebrates as well as in invertebrates. The association with local pollution phenomena has been recognized in several studies, but other etiopathogenetic factors may be also involved, and in some cases tumors have been reported to be unrelated to chemical pollution. Genotoxic agents have been detected by means of suitable techniques in seawater, sediments, and marine organisms. Several studies have investigated the presence of carcinogen-DNA adducts, DNA damage and repair processes, and cytogenetic alterations, such as chromosomal aberrations, sister-chromatid exchanges, and micronuclei, in tissues of marine organisms. However, monitoring of these end-points under field conditions encounters some limitations and problems. Even more fragmentary is the information on teratogenic effects in marine organisms, although interesting test systems have been set up. On the whole, a quite extensive database on all these toxicological issues is already available in the literature, but further studies are warranted for an adequate assessment of genotoxic, carcinogenic, and teratogenic hazards, and possibly counteracting factors in the marine environment, and specifically in the Mediterranean Sea. 相似文献
12.
贝类毒素严重威胁水产品的质量,而且给人类健康带来潜在危害。由于其结构多样、作用机制复杂,贝类毒素监控计划通常使用动物方法,不仅成本高、定量难,而且不符合"3R"的要求。运用减轻动物痛苦和减少数量的优化方法,开发新的基于毒性作用机制和结构分析的细胞功能检测法、免疫学方法、化学分析法和生物传感器方法,这些动物试验替代方法的研究提高了贝类毒素监测的有效性,经过科学验证和认可后可用于监控目的 。 相似文献
13.
Models of sulfur dynamics in forest and grassland ecosystems with emphasis on soil processes 总被引:1,自引:1,他引:0
The major S constituents in terrestrial ecosystems include inorganic SO
4
2–
, C-bonded S and ester sulfate with the organic fractions constituting the major soil S pools. Conceptual models of S dynamics link inorganic SO
4
2–
flux to organic sulfur transformations and other elements such as N and C. Mass balance models have been useful in ascertaining whether a system is at steady-state with respect to adsorption processes and/or nutritional demands of vegetation for S. Chemical equilibrium/surface complexation models have been used to evaluate the effects of a complex of factors, including effects of pH on SO4
– adsorption and precipitation; these models have not generally been integrated into ecosystem models of S dynamics. Models such as ILWAS, Birkenes, Storgama, Trickle-Down and MAGIC were developed to ascertain surface water acidification processes within watersheds; these models incorporated SO4
2– adsorption in some formulation combined with hydrological considerations. None of these models explicitly treat organic S transformations and fluxes. In contrast, grassland ecosystem models detail organic S transformations, but give little attention to adsorption and hydrologic factors. More detailed simulation models of S transformations in forest and grassland soils have recently been developed, but these results have yet to be incorporated into ecosystem and watershed models. 相似文献
14.
Spatially Explicit Characterization of Acidifying and Eutrophying Air Pollution in Life-Cycle Assessment 总被引:1,自引:0,他引:1
Mark A. J. Huijbregts Wolfgang Schöpp Evert Verkuijlen Reinout Heijungs Lucas Reijnders 《Journal of Industrial Ecology》2000,4(3):75-92
Abstract: Simple models are often used to assess the potential impact of acidifying and eutrophying substances released during the life cycle of products. As fate, background depositions, and ecosystem sensitivity are not included in these models, environmental life-cycle assessment of products (LCA) may produce incorrect results for these impact categories. This paper outlines the spatially explicit regional air pollution information and simulation model (RAINSLCA), which was developed for the calculation of acidification and terrestrial eutrophication potentials of ammonia (NH3) and nitrogen oxide (NOx) air emissions and acidification potentials for sulfur dioxide (SO2) air emissions for Europe and a number of European regions, taking fate, 相似文献
15.
Selig Hecht 《The Journal of general physiology》1927,10(5):781-809
1. Data are presented for the dark adaptation of four species of animals. They show that during dark adaptation the reaction time of an animal to light of constant intensity decreases at first rapidly, then slowly, until it reaches a constant minimum. 2. On the assumption that at all stages of adaptation a given response to light involves a constant photochemical effect, it is possible to describe the progress of dark adaptation by the equation of a bimolecular reaction. This supposes, therefore, that dark adaptation represents the accumulation within the sense cells of a photosensitive material formed by the chemical combination of two other substances. 3. The chemical nature of the process is further borne out by the fact that the speed of dark adaptation is affected by the temperature. The velocity constant of the bimolecular process describing dark adaptation bears in Mya a relation to the temperature such that the Arrhenius equation expresses it with considerable exactness when µ = 17,400. 4. A chemical mechanism is suggested which can account not only for the data of dark adaptation here presented, but for many other properties of the photosensory process which have already been investigated in these animals. This assumes the existence of a coupled photochemical reaction of which the secondary, "dark" reaction is catalyzed by the products of the primary photochemical reaction proper. This primary photochemical reaction itself is reversible in that its main products combine to form again the photosensitive material, whose concentration controls the behavior of the system during dark adaptation. 相似文献
16.
Several reinforcement-based models have been proposed to explain transitive-like behavior in nonverbal transitive inference tasks. These models assume that the initial training required for memorizing the premises produces an ordered series of associative values (A>B>C>D>E); these values can then be used to select the "transitively correct" stimulus in a novel pair (e.g., BD). Our study experimentally tested this assumption by using resistance-to-extinction and resistance-to-reinforcement techniques to obtain empirical measures of associative strength for Stimuli B and D. We first measured the associative strengths of these stimuli after completion of initial training with overlapping pairs of colored squares (A+B-, B+C-, C+D-, and D+E-) using resistance-to-extinction and resistance-to-reinforcement procedures. Next, we used massed presentations of Pair D+E- (termed bias reversal) that ought to increase the associative value of Stimulus D, and again measured the associative strengths of the stimuli. None of our experimental measures of associative strength correlated with pigeons' behavior in the BD test or with BD performance predicted by associative models either before or after bias reversal (Wynne, 1995; Siemann and Delius, 1998). These results question validity of reinforcement-based models for explaining animals' behavior in nonverbal TI tasks. 相似文献
17.
Amanda V. Steckert Samira S. Valvassori Morgana Moretti Felipe Dal-Pizzol João Quevedo 《Neurochemical research》2010,35(9):1295-1301
In this work, we review the studies of oxidative stress markers, showing association with the pathophysiology of bipolar disorder
(BD). BD is a prevalent, chronic and highly disabling psychiatric disorder. Several hypotheses have been postulated to explain
the exact neurochemical mechanisms underlying the pathophysiology of BD, including a role for monoamines, gamma-amino butyric
acid (GABA), glutamate, and second messenger singling pathways. More recently, oxidative stress has been implicated in the
pathogenesis of BD. Recent studies have reported increased products of lipid peroxidation and alterations of the major antioxidants
enzymes in patients with BD. It has been widely demonstrated that the generation of reactive oxygen species (ROS) plays a
critical role in the pathophysiology of several neuropsychiatric disorders, such BD. 相似文献
18.
Cancer risk assessment for 1,3-butadiene: dose-response modeling from an epidemiological perspective
Sielken RL Valdez-Flores C Gargas ML Kirman CR Teta MJ Delzell E 《Chemico-biological interactions》2007,166(1-3):140-149
The dose-response assessment of the association between 1,3-butadiene (BD) and leukemia mortality among workers in the North American synthetic rubber industry is explored. Analyses are based on the most recent University of Alabama at Birmingham epidemiological study and exposure estimation. The U.S. EPA Science Advisory Board recommendations of using the most recent data and giving consideration to peak exposures to BD have been followed. If cumulative BD ppm-years is to be used as the predictor of the leukemia rate ratio, then the performance of that predictor is statistically significantly improved if the slope in the predictor is estimated with age and the cumulative number of BD peaks (where a BD peak is any exposure, regardless of duration, to a BD concentration above 100 ppm) added as categorical covariates. After age and the cumulative number of BD peaks are incorporated as categorical covariates in the Poisson regression model, the estimated concentration (EC(001)) corresponding to an excess risk of 0.001 as a result of continuous environmental exposure is 11.2 ppm; however, the estimated slope for BD cumulative ppm-years in the linear rate ratio for leukemia used to derive this EC(001) is not statistically significantly different from zero. Sensitivity analyses using alternative models indicate either essentially no risk or estimated EC(001) values of 9 and 77 ppm. Analyses suggesting the absence of a statistically significant low-dose risk versus cumulative BD ppm-years are presented. Sensitivity analyses of other malignant neoplasms of lymphatic and hematopoietic tissue (specifically, lymphoid and myeloid neoplasms) resulted in conclusions about the dose-response modeling methodology that were supportive of the methodology used for leukemia. 相似文献
19.
Chemical and photochemical probing of DNA complexes 总被引:3,自引:0,他引:3
P E Nielsen 《Journal of molecular recognition : JMR》1990,3(1):1-25
An overview of the chemical and photochemical probes which over the past ten years have been used in studies of DNA/ligand complexes and of non-B-form DNA conformations is presented with emphasis on the chemical reactions of the probes with DNA and on their present 'use-profile'. The chemical probes include: dimethyl sulfate, ethyl nitroso urea, diethyl pyrocarbonate, osmium tetroxide, permanganate, aldehydes, methidiumpropyl-EDTA-Fell (MPE), phenanthroline metal complexes and EDTA/FeII. The photochemical probes that have been used include: psoralens, UVB, acridines and uranyl salts. The biological systems analysed by use of these probes are reviewed by tabulation. 相似文献
20.
Gene expression measurements have successfully been used for building prognostic signatures, i.e for identifying a short list of important genes that can predict patient outcome. Mostly microarray measurements have been considered, and there is little advice available for building multivariable risk prediction models from RNA-Seq data. We specifically consider penalized regression techniques, such as the lasso and componentwise boosting, which can simultaneously consider all measurements and provide both, multivariable regression models for prediction and automated variable selection. However, they might be affected by the typical skewness, mean-variance-dependency or extreme values of RNA-Seq covariates and therefore could benefit from transformations of the latter. In an analytical part, we highlight preferential selection of covariates with large variances, which is problematic due to the mean-variance dependency of RNA-Seq data. In a simulation study, we compare different transformations of RNA-Seq data for potentially improving detection of important genes. Specifically, we consider standardization, the log transformation, a variance-stabilizing transformation, the Box-Cox transformation, and rank-based transformations. In addition, the prediction performance for real data from patients with kidney cancer and acute myeloid leukemia is considered. We show that signature size, identification performance, and prediction performance critically depend on the choice of a suitable transformation. Rank-based transformations perform well in all scenarios and can even outperform complex variance-stabilizing approaches. Generally, the results illustrate that the distribution and potential transformations of RNA-Seq data need to be considered as a critical step when building risk prediction models by penalized regression techniques. 相似文献