首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 15 毫秒
1.
2.
An experimental study was conducted to clarify the suppression effect of nitrogen-containing compounds, that is, ammonia and urea, on the formation of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) through the de novo synthesis reaction. In the experiment, graphite and copper chloride contained in a mixture were used as sources of carbon and chlorine, respectively. The granulated sample mixture was charged as a packed-bed in the glass tube and heated at 300 degrees C in the flow of Ar-O2 gas mixture. In some cases, urea was added as aqueous solution to the sample, while ammonia was added to the gas flowed through the sample bed. The amount of PCDD/Fs formed decreases significantly by the addition of both ammonia and urea. Particularly, the addition of urea reduces the amount of PCDD/Fs discharged in the outlet gas by approximately 90%. The oxidation rate of carbon in the early stage of the experiment, that is, the heating period, is promoted bythe addition of nitrogen-containing compounds. However, soon afterthe temperature reaches 300 degrees C, the formation rate becomes lower than that of the case without the addition of nitrogen-containing compounds. On the other hand, organic compounds containing amino (-NH2) or cyanide (-CN) groups and those containing nitrogen within the carbon ring frame were detected in the outlet gas in the case of urea addition. Typically observed aromatic compounds are chlorobenzonitriles, chlorobenzeneamines, and chloropyridines. This suggests a possibility that hydrogen and/or chlorine combined with PCDD/Fs are also substituted by such nitrogen-containing groups, and this decreases the formation rate of their frame of carbon rings. This phenomenon was also consistent with the fact that a significant reduction was observed in the amount of PCDD/Fs released to the outlet gas when urea was added.  相似文献   

3.
Waste printed circuit boards containing brominated flame retardants were pyrolyzed in a high-temperature melting system to observe the formation behaviors of polybrominated dibenzo-p-dioxins (PBDDs) and dibenzofurans (PBDFs). In this study, the results showed that the formation of PBDD/ Fs during pyrolysis can be destroyed under controlled primary combustion conditions. There were two significant factors that influenced the extent of PBDD/F formation. The first factor was temperature. The results showed that, both the total PBDD/F content in the bottom ash and the total PBDD/F emission factor from the flue gas decrease by approximately 50% with an increase of the pyrolysis temperature from 850 to 1200 degrees C. The second factor was the addition of CaO. The possible mechanism involves the reaction between CaO and HBr to form the solid-phase product CaBr2. Thus, the addition of CaO is effective in adsorbing HBr and results in the inhibition of PBDD/F synthesis by more than 90% and further prevents the acid gases (HCl and HBr) that corrode the equipment. In conclusion, due to the persistence and toxicity of PBDD/Fs, a combined regulation for controlling both PCDD/Fs and PBDD/Fs is of great importance for environmental protection issues.  相似文献   

4.
Concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in sediments and flood-plain soils collected along the Tittabawassee River in Michigan ranged from 102 to 53,600 pg/g, dry wt. Mean PCDD/PCDF concentrations in downstream sediment and soil were from 10- to 20-fold greater than those found at locations upstream of Midland, Michigan. Concentrations of PCDD/PCDF in sediments and flood-plain soils from the Tittabawassee watershed were comparable to those found in industrialized areas such as the Housatonic and lower Passaic Rivers in the U.S. Concentrations of PCDDs/PCDFs in soil and sediment were not correlated with total organic carbon (TOC) in sediments or soils. OCDD and 2,3,7,8-TeCDF were the predominant congeners in sediment/soil collected from locations downstream of Midland, Michigan. Principal component analysis of the PCDD/PCDF congener profile suggested the presence of sources originating from a mixture of chlorophenol and other chlorinated compound production. Mass balance analysis of TCDD equivalents (TCDD-EQs) derived from H4IIE-luc bioassay of sediment extracts and 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TEQs) estimated from instrumental analysis suggested that PCDDs/PCDFs were the major dioxin-like compounds present in sediments. A significant correlation existed between bioassay-derived TCDD-EQs and instrumentally measured TEQs (r2 = 0.94).  相似文献   

5.
A direct density functional theory (DFT) kinetic calculation is carried out for the homogeneous gas-phase formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from the cross-condensation of 2,4-dichlorophenoxy radical (2,4-DCPR) with 2-chlorophenoxy radical (2-CPR) and 2,4,6-trichlorophenoxy radical (2,4,6-TCPR). The possible formation mechanism is investigated and compared with the PCDD/F formation mechanism from the self-condensation of 2,4-DCPR, 2-CPR, and 2,4,6-TCPR. The rate constants and their temperature dependence of the crucial elementary reactions are computed by the canonical variational transition-state theory with the small curvature tunneling contribution over the temperature range of 600-1200 K. This study shows that the multichlorine substitutions suppress the PCDD/F formations. Because of a lack of experimental kinetic data, the present theoretical results are expected to be useful and reasonable to estimate the kinetic properties, such as the pre-exponential factors, the activation energies, and the rate constants, of the elementary reactions involved in the formation of PCDD/Fs.  相似文献   

6.
Few studies have investigated the human exposure to the ensemble of dioxin-related compounds (DRCs) released from uncontrolled e-waste recycling, especially from a toxic effect standpoint. This study evaluated the TCDD toxic equivalents (TEQs) in persistent extracts of settled house dust from two Vietnamese e-waste recycling sites (EWRSs) using the Dioxin-Responsive Chemically Activated LUciferase gene eXpression assay (DR-CALUX), combined with chemical analysis of PCDD/Fs, DL-PCBs, PBDD/Fs, and monobromo PCDD/Fs to determine their TEQ contribution. The CALUX-TEQ levels in house dust ranged from 370 to 1000 pg g(-1) in the EWRSs, approximately 3.5-fold higher than in the urban control site. In EWRS house dust, the concentrations of the unregulated PBDFs were 7.7-63 ng g(-1), an order of magnitude higher than those of regulated DRCs (PCDD/Fs and DL-PCBs), and PBDFs were also principal CALUX-TEQ contributors (4.2-22%), comparable to PCDD/Fs (8.1-29%). The CALUX-TEQ contribution of DRCs varied, possibly depending on thermal processing activities (higher PCDD/F-TEQs) and PBDE content in the waste (higher PBDF-TEQs). However, the percentage of unknown dioxin-like activities was high in all dust samples, indicating large contribution from unidentified DRCs and/or synergy among contaminants. Estimates of TEQ intake from dust ingestion suggest that children in the EWRSs may be adversely affected by DRCs from dust.  相似文献   

7.
Migration of polyisobutylene from polyethylene/polyisobutylene film into foods has been studied in domestic applications such as wrapping of foods and reheating in a microwave oven. The results of these migration studies were obtained by direct measurement using newly developed analytical methods utilizing nuclear magnetic resonance (NMR) and infra-red (IR) spectroscopy as well as predictively from assessment of loss of polyisobutylene from the film. Total levels of polyisobutylene migration into cheese were found to be 8-10 mg/kg, into cake 1-5 mg/kg, and into sandwiches ranged from < 1 to 4 mg/kg. Reheating foods covered with film in the microwave oven, gave migration levels ranging from < 0.01 mg/kg for contact with steam only, up to 0.5 mg/kg for severe splashing of food onto the film and 4 mg/kg for reheated pizza. Migration of polyisobutylene was shown to be skewed towards the low molecular weight fraction of the additive. In typical films, the molecular weight range of polyisobutylene was shown to be 300-6000 daltons (95% limits) centred on 1300 daltons, whereas the additive that had migrated into cheese was found to range from 130-2200 daltons, centred on 520 daltons.  相似文献   

8.
Ethanol is currently receiving increased attention because of its use as a biofuel or fuel additive and because of its influence on air quality. We used stable isotopic ratio measurements of (13)C/(12)C in ethanol emitted from vehicles and a small group of tropical plants to establish ethanol's δ(13)C end-member signatures. Ethanol emitted in exhaust is distinctly different from that emitted by tropical plants and can serve as a unique stable isotopic tracer for transportation-related inputs to the atmosphere. Ethanol's unique isotopic signature in fuel is related to corn, a C4 plant and the primary source of ethanol in the U.S. We estimated a kinetic isotope effect (KIE) for ethanol's oxidative loss in the atmosphere and used previous assumptions with respect to the fractionation that may occur during wet and dry deposition. A small number of interpretive model calculations were used for source apportionment of ethanol and to understand the associated effects resulting from atmospheric removal. The models incorporated our end-member signatures and ambient measurements of ethanol, known or estimated source strengths and removal magnitudes, and estimated KIEs associated with atmospheric removal processes for ethanol. We compared transportation-related ethanol signatures to those from biogenic sources and used a set of ambient measurements to apportion each source contribution in Miami, Florida-a moderately polluted, but well ventilated urban location.  相似文献   

9.
Polychlorinated biphenyls (PCBs) and hydroxylated metabolic products (OH-PCBs) were measured in plasma collected from live-captured and released bottlenose dolphins (Tursiops truncatus) from five different locations in the Western Atlantic and the Gulf of Mexico in 2003 and 2004. In 2004, the sum (sigma) of concentration of PCBs in plasma of dolphins sampled off Charleston, SC [geometric mean: 223 ng/g of wet weight (w.w.)] was significantly higher (p<0.05) than concentrations detected in animals from the Indian River Lagoon, FL (sigmaPCBs: 122 ng/g w.w.) and the Sarasota Bay, FL (sigmaPCBs: 111 ng/g w.w.). The PCB homolog profiles were similar among locations. Concentrations of OH-PCBs were significantly higher (p<0.05) in plasma of dolphins from Charleston, SC (sigmaOH-PCBs for 2003: 126 ng/g w.w.; 2004: 138 ng/g w.w.) than animals from Florida (sigmaOH-PCBs ranged from 6 to 47 ng/g w.w.) and Bermuda (8.3 ng/g w.w.); however, concentrations in the Charleston samples did not differ from animals captured in Delaware Bay, NJ (57 ng/g w.w.). The sigmaOH-PCBs constituted 2-68% of the total PCB concentrations in plasma. Dichloro- to nonachloro-OH-PCBs were quantified using high-resolution gas chromatography mass spectrometry, but only around 20% of OH-PCBs could be identified by comparison to authentic standards. Results from this study show that OH-PCB are important environmental contaminants in dolphins and suggest that PCBs, decades after their ban, may still constitute a threat to wildlife.  相似文献   

10.
11.
Secondary organic aerosol (SOA) formation from reactions of n-alkanes with OH radicals in the presence of NOx was investigated in an environmental chamber using a thermal desorption particle beam mass spectrometer for particle analysis. SOA consisted of both first- and higher-generation products, all of which were nitrates. Major first-generation products were sigma-hydroxynitrates, while higher-generation products consisted of dinitrates, hydroxydinitrates, and substituted tetrahydrofurans containing nitrooxy, hydroxyl, and carbonyl groups. The substituted tetrahydrofurans are formed by a series of reactions in which sigma-hydroxycarbonyls isomerize to cyclic hemiacetals, which then dehydrate to form substituted dihydrofurans (unsaturated compounds) that quickly react with OH radicals to form lower volatility products. SOA yields ranged from approximately 0.5% for C8 to approximately 53% for C15, with a sharp increase from approximately 8% for C11 to approximately 50% for C13. This was probably due to an increase in the contribution of first-generation products, as well as other factors. For example, SOA formed from the C10 reaction contained no first-generation products, while for the C15 reaction SOA was approximately 40% first-generation and approximately 60% higher-generation products, respectively. First-generation sigma-hydroxycarbonyls are especially important in SOA formation, since their subsequent reactions can rapidly form low volatility compounds. In the atmosphere, substituted dihydrofurans created from sigma-hydroxycarbonyls will primarily react with O3 or NO3 radicals, thereby opening reaction pathways not normally accessible to saturated compounds.  相似文献   

12.
In this study, we report the PCDD and mineralogical results from the analyses of 27 different samples from three ball clay cores from different locations in Kentucky and Tennessee. One goal of this study was to determine if there is a correlation between the mineralogy of the ball clay samples and the PCDD concentrations and/or homologue profiles in each sample. Samples from each of the three cores exhibited the natural formation profile with extremely high PCDD concentrations with low and mostly undetectable levels of polychlorinated dibenzofurans (PCDFs). The maximum toxic equivalents (TEQs) for Cores C-E were 2500, 440, and 15,000 pg WHO-TEQ/g, respectively. Although there does not seem to be a direct correlation between mineralogy and PCDD concentrations or homologue profiles, the mineralogy of Core C is substantially different than that of Cores D and E, which may in part explain the differences in congener patterns we observed among the three cores.  相似文献   

13.
The sulphur aroma compounds produced from a phosphate-buffered solution (pH 8) of l-cysteine and l-, l-[1-13C] or l-[4-13C] ascorbic acid, heated at 140 ± 2 °C for 2 h, were examined by headspace SPME in combination with GC-MS. MS data indicated that C-1 of l-ascorbic acid was not involved in the formation of sulphur aroma compounds. The sulphur aroma compounds formed by reaction of l-ascorbic acid with l-cysteine mainly contained thiophenes, thiazoles and sulphur-containing alicyclic compounds. Among these compounds, 1-butanethiol, diethyl disulphide, 5-ethyl-2-methylthiazole, cis and trans-3,5-dimethyl-1,2,4-trithiolane, thieno[2,3-b]thiophene, thieno[3,2-b]thiophene, cis and trans-3,5-diethyl-1,2,4-trithiolane, 1,2,5,6-tetrathiocane, 2-ethylthieno[2,3-b]thiophene, 2,4,6-trimethyl-1,3,5-trithiane and cyclic octaatomic sulphur (S8) were formed solely by l-cysteine degradation, and the rest by reaction of l-ascorbic acid degradation products, such as hydroxybutanedione, butanedione, acetaldehyde, acetol, pyruvaldehyde and formaldehyde with l-cysteine or its degradation products, such as H2S and NH3. A new reaction pathway from l-ascorbic acid via its degradation products was proposed.  相似文献   

14.
The effect of modified atmosphere packaging (MAP) on the germination and growth of toxin producing psychrotolerant Bacillus spp is not well described. A model agar system mimicking a cooked meat product was used in initial experiments. Incubation at refrigeration temperature of 8 °C for 5 weeks of 26 Bacillus weihenstephanensis including two emetic toxin (cereulide) producing strains showed that B. weihenstephanensis is sensitive to MAP containing CO2. The sensitivity to 20% CO2 was dependent on strain and oxygen level, being increased when oxygen was excluded from the MAP. Growth from spores was observed at the earliest within 2 weeks when 20% CO2 was combined with 2% O2 and in 3 weeks when combined with “0”% O2 (the remaining atmosphere was made up from N2). Results were validated in a cooked meat sausage model for two non-emetic and one emetic B. weihenstephanensis strain. The packaging film oxygen transfer rates (OTR) were 1.3 and 40 ml/m2/24 h and the atmospheres were 2% O2/20% CO2 and “0”% O2/20% CO2. Oxygen availability had a large impact on the growth from spores in the MAP meat sausage, only the most oxygen restricted condition (OTR of 1.3 ml/m2/24 h and “0”% O2/20 % CO2) inhibited growth of the three strains during 4 weeks storage at 8 °C. Cereulide production was undetectable during storage at 8 °C irrespective of choice of the MAP (quantified by liquid chromatography mass spectrometry/mass spectrometry). MAP storage at 8 °C for 1 and 3 weeks followed by opening of packages and temperature abuse for 1.5 h daily at 20 °C during 1 week resulted in increased cell counts and variable cereulide production in the meat sausage. A pre-history at 8 °C for 1 week in MAP with OTR of 1.3 or 40 ml/m2/24 h and 2% O2 resulted in cereulide concentrations of 0.816 – 1.353 µg/g meat sausage, while a pre-history under the most oxygen restricted condition (OTR of 1.3 ml/m2/24 h, “0”% O2/20 % CO2) resulted in minimal cereulide production (0.004 µg/g meat sausage) at abuse condition. Extension of MAP storage at 8 °C for 3 weeks followed by abuse resulted in a substantially reduced cereulide production.Data demonstrates that MAP can be used to inhibit growth of a psychrotolerant toxin producing Bacillus spp. during chill storage at 8 °C, and substantially reduce the risk of emetic food poisoning at abuse condition. Results are of relevance for improving safety of ready to eat processed chilled foods of extended durability.  相似文献   

15.
The suitability of using an X-ray technique to study pre-emergent stages of Sitophilus oryzae (L.) developing in Manitoba wheat was investigated. A sample of grain was radiographed once every other working day subsequent to exposure to adult S. oryzae for 24 hr, until the emergence of the F1 generation. Eggs and small larvae were not detected in this manner, but after 13 days larvae were detected with increasing efficiency. Pupae and adults within the grain could be detected and were easily distinguished from larvae and pupae.The development of S. oryzae in individual wheat grains was investigated by sticking each grain of wheat to the Sellotape base of an aluminium cell prior to exposure to one female S. oryzae adult, and subsequently radiographing every other day for 23 days. Larvae were positively identified in grains as early as 9 days after oviposition by tracing back their development in the developed X-ray films, and seven suspected (although not positively identified) eggs were seen on the first day after oviposition.A quantity of grain was X-rayed immediately prior to fumigation and at intervals after fumigation. The efficiency with which dead insects were detected decreased with time after fumigation.  相似文献   

16.
This article reviews a beneficial effect of technology transfer from Electrical Engineering to Food Sensory Science. Specifically, it reviews the recent adoption in Food Sensory Science of the receiver operating characteristic (ROC) curve, a tool that is incorporated in the theory of signal detection. Its use allows the information processing that takes place in the brain during sensory difference testing to be studied and understood. The review deals with how Signal Detection Theory, also called Thurstonian modeling, led to the adoption of a more sophisticated way of analyzing the data from sensory difference tests, by introducing the signal-to-noise ratio, d', as a fundamental measure of perceived small sensory differences. Generally, the method of computation of d' is a simple matter for some of the better known difference tests like the triangle, duo-trio and 2-AFC. However, there are occasions when these tests are not appropriate and other tests like the same-different and the A Not-A test are more suitable. Yet, for these, it is necessary to understand how the brain processes information during the test before d' can be computed. It is for this task that the ROC curve has a particular use.  相似文献   

17.
Lactic acid bacteria have been paid increasing attention as a probiotics, but their viability is affected by the various digestive processes of their host such as the acidic stomach solution and bile acids. The protection of Lactobacillus acidophilus JCM 1132 against the cytotoxic bile acids was examined by incorporating the bacteria in the inner-water phase of a W/O/W emulsion. Sodium glycodeoxycholate and sodium glycochenodeoxycholate (6 mmol/l each) significantly decreased the cell viability from 5.2×106 cfu/ml to 4.0×103 and 1.3×102 cfu/ml, respectively, when the bacteria were directly dispersed in the solutions at pH 7 for 2 h. However, their incorporation in the inner-water phase of the W/O/W emulsion improved the viabilities to 1.6×106 and 2.3×104 cfu/ml, respectively. This improvement was ascribed to the inclusion of the bacteria in the emulsion because the viability of the bacteria, which were dispersed with the emulsion containing no bacteria in the solution, was very low. Although sodium deoxycholate decreased the viability of the cells included in the W/O/W emulsion, the inclusion significantly improved the cell viability against primary and secondary bile acids.  相似文献   

18.
The evolution of the phenolic content, as measured by spectrophotometric methodologies [total polyphenols (TP), low-polymerized polyphenols (LPP), total anthocyanins (TA), catechins (CAT), proanthocyanidins (PRO) and o-diphenols (OD)], was studied in young red wines from Vitis vinifera L. cv Tempranillo, Graciano and Cabernet Sauvignon during 26 months of ageing in bottle. Although the wines showed differences in their initial phenolic profiles, the evolution trend of the different families of phenolic compounds was similar in the wines from the three grape varieties. TA markedly decreased during ageing in bottle (43% for Tempranillo, 65% for Graciano and 66% for Cabernet Sauvignon), following a first-order kinetic. Calculation of the kinetic parameters revealed that the disappearance rate of TA was 2-fold lower for Tempranillo wine than for Graciano and Cabernet Sauvignon wines, which exhibited similar kinetics. This decrease in TA (due to the disappearance of monomeric anthocyanins), together with a increase registered in CAT and PRO (due to the cleavage of proanthocyanidins and their structural tranformations), was consistent with a decrease in LPP, suggesting the occurrence of condensation reactions during ageing in bottle. The evolution trends observed for TP and OD during ageing in bottle were the results of changes in the different groups of phenolic compounds involved in both determinations. Global phenolic determinations, usually performed in wineries, provided useful information in relation to the evolution of wine polyphenols during ageing in bottle.  相似文献   

19.
Secondary organic aerosol (SOA) forms in the atmosphere when volatile parent compounds are oxidized to form low-volatility products that condense to yield organic particulate matter (PM). Under conditions of intense photochemical smog, from 40 to 80% of the particulate organic carbon can be secondary in origin. Because describing multicomponent condensation requires a compound-by-compound identification and quantification of the condensable compounds, the complexity of ambient SOA has made it difficult to test the ability of existing gas/particle (G/P) partitioning theory to predict SOA formation in urban air. This paper examines that ability using G/P data from past laboratory chamber experiments carried out with five parent hydrocarbons (HCs) (four monoterpenes at 308 K and cyclohexene at 298 K) in which significant fractions (61-100%) of the total mass of SOA formed from those HCs were identified and quantified by compound. The model calculations were based on a matrix representation of the multicomponent, SOA G/P distribution process. The governing equations were solved by an iterative method. Input data forthe model included (i) deltaHC (microg m(-3)), the amount of reacted parent hydrocarbon; (ii) the alpha values that give the total concentration T (gas + particle phase, ng m(-3)) values for each product i according to Ti = 10(3) alphaideltaHC; (iii) estimates of the pure compound liquid vapor pressure pL(degrees) values (at the reaction temperature) for the products; and (iv) UNIFAC parameters for estimating activity coefficients in the SOA phase for the products as a function of SOA composition. The model predicts the total amount Mo (microg m(-3)) of organic aerosol that will form from the reaction of deltaHC, the total aerosol yield Y(= Mo/deltaHC), and the compound-by-compound yield values Yi. An impediment in applying the model is the lack of literature data on PL(degrees) values for the compounds of interest or even on pL(degrees) values for other, similarly low-volatility compounds. This was overcome in part by using the G/P data from the alpha-pinene and cyclohexene experiments to determine pL(degrees) values for use (along with a set of 14 other independent polar compounds) in calculating UNIFAC vapor pressure parameters that were, in turn, used to estimate all of the needed pL(degrees) values. The significant degree of resultant circularity in the calculations for alpha-pinene and cyclohexene helped lead to the good agreement that was found between the Yi values predicted by the model, and those measured experimentally for those two compounds. However, the model was also able to predict the aerosol yield values from beta-pinene, sabinene, and delta3-carene, for which there was significatly less circularity in the calculations, thereby providing evidence supporting the idea that given the correct input information, SOA formation can in fact be accurately modeled as a multicomponent condensation process.  相似文献   

20.
The effects of a tea polyphenols (TP) dip treatment on quality changes of silver carp (Hypophthalmicthys molitrix) during iced storage were examined over a period of 35 days. TP (0.2%, w/v) solution was used for the dip treatment. The control and the treated fish samples were analysed periodically for microbiological (total viable count), chemical (pH, TVB-N, TBA, K-value), and sensory characteristics. The results indicated that the effect of the TP dip treatment on the fish samples was to enable the good quality characteristics to be retained for longer and to extend the shelf life during the iced storage.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号