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1.
Chao HP  Lee JF  Lee CK  Huang HC 《Chemosphere》2005,59(5):711-720
A method for predicting organic compound volatilization rates under turbulent liquid and gas conditions is developed. The reference compounds are classified according to their physico-chemical properties. The mass transfer coefficient (K(OL)) ratios for organic solutes to the reference compounds are constant for a wide range of environmental conditions, including liquid or air turbulence, or both at once. The obtained results indicate that when the environmental conditions are the same the determination of the volatilization rates is strongly dependent on the solute properties and the chemical structure. The presented method can more effectively estimate the volatilization rates of the solutes than the traditional one under various environmental conditions especially for low volatility solutes. The advantages and disadvantages of the traditional method are also discussed.  相似文献   

2.
Surface tension of pure and mixed aqueous solutions of both inorganic and organic species that are relevant in atmospheric droplets has been studied in a laboratory investigation. Following the Gibbsian theory of surfaces experimental data have been fitted by the Szyszkowski equation. As a function of the carbon-chain length trends in the maximum surface excess Γmax and the inverse surface activity β have been clearly identified for pure aqueous solutions of homologous series of n-alcohols and mono-carboxylic acids, while these parameters oscillate for the homologous series of di-carboxylic acids. For mixed aqueous solutions of water-soluble organic and inorganic compounds, e.g. cis-pinonic acid and sodium chloride, a further decrease in surface tension has been observed, which can be interpreted as an interaction between the inorganic and organic solutes and an enrichment of the surface-active organic compound in the surface layer. Taking this effect into account surface-tension data of real atmospheric samples become more plausible, especially when also slightly soluble or water-insoluble organic compounds having a high surface activity at low concentrations are considered.  相似文献   

3.
Improving methods for assessing the spatial and temporal resolution of organic compound concentrations in marine environments is important to the sustainable management of our coastal systems. Here we evaluate the use of ethylene vinyl acetate (EVA) as a candidate polymer for thin-film passive sampling in waters of marine environments. Log KEVA−W partition coefficients correlate well (r2 = 0.87) with Log KOW values for selected pesticides and polychlorinated biphenyls (PCBs) where Log KEVA−W = 1.04 Log KOW + 0.22. EVA is a suitable polymer for passive sampling due to both its high affinity for organic compounds and its ease of coating at sub-micron film thicknesses on various substrates. Twelve-day field deployments were effective in detecting target compounds with good precision making EVA a potential multi-media fugacity meter.  相似文献   

4.
《Chemosphere》2009,74(11):1832-1837
Sorption of nonpolar (phenanthrene and butylate) and polar (atrazine and diuron) organic chemicals to oil-contaminated soil was examined to investigate oil effects on sorption of organic chemicals and to derive oil–water distribution coefficients (Koil). The resulting oil-contaminated soil–water distribution coefficients (Kd) for phenanthrene demonstrated sorption-enhancing effects at both lower and higher oil concentrations (Coil) but sorption-reducing (competitive) effects at intermediate Coil (approximately 1 g kg−1). Rationalization of the different dominant effects was attempted in terms of the relative aliphatic carbon content which determines the accessibility of the aromatic cores to phenanthrene. Little or no competitive effect occurred for butylate because its sorption was dominated by partitioning. For atrazine and diuron, the changes in Kd at Coil above approximately 1 g kg−1 were negligible, indicating that the presently investigated oil has little or no effect on the two tested compounds even though the polarity of the oil is much less than soil organic matter (SOM). Therefore, specific interactions with the active groups (aromatic and polar domains) are dominantly responsible for the sorption of polar sorbates, and thus their sorption is controlled by available sorption sites. This study showed that the oil has the potential to be a dominant sorptive phase for nonpolar pollutants when compared to SOM, but hardly so for polar compounds. The results may aid in a better understanding of the role of the aliphatic and aromatic domains in sorption of nonpolar and polar organic pollutants.  相似文献   

5.
Octanol/water partition coefficients (Kow's) of organic solutes are estimated with reasonable accuracy (standard deviation ± 0.25 log Kow units) by elution from a C-18 column with 75:25 (v/v) MeOH-H2O, based on results with 37 test compounds. Changes in solute activity coefficients from water to 75% MeOH account for the slope of the log Kow-log k' plot, where k' is the HPLC capacity factor. The method is used to estimate Kow's for 25 additional organic compounds, and some disparities between the results and those calculated using group additivity-constitutive factors are noted.  相似文献   

6.
Passive air samplers (PAS) can be used to monitor semi-volatile organic compounds in the atmosphere. Polyurethane foam (PUF) disks are a popular sampling medium because they have a high retention capacity for such compounds. This paper reports a highly time-resolved uptake study, to derive uptake rate data under field conditions, and investigate the effects of using different foam densities on the uptake rate. PUF disks were deployed alongside an active sampler, for periods of up to 12 weeks. The uptake rates were measured for a range of gas- and particle-bound persistent organic pollutants (polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs)), of different properties, to explore whether gas–particle partitioning affected uptake rate. Uptake rates for two different densities of foam (0.021 and 0.035 g cm?3) were not statistically significantly different from each other. Uptake rates of light PCBs averaged ~6.5 m3 day?1, somewhat higher than in previous studies; higher wind speeds and lower temperatures in this study are the likely reason for this difference. The study showed: i) the uptake rate of the compound with lowest KOA considered in this study (PCB-28/31) declined in the later weeks, indicating an approach to equilibrium; ii) uptake rates of lighter BDEs and heavier PCBs (compounds of intermediate KOA in this study) remain similar throughout the study period, indicating that they are not approaching equilibrium during the 12-week-study; iii) uptake rates were typically: ~8 m3 day?1 for PCB-52; ~9.5 m3 day?1 for PCB-95; ~11 m3 day?1 for BDE-28 and ~2 m3 day?1 BDE-99. The latter compound has an important particle-bound component and this lowers the sampling rate compared to predicted uptake rates for compounds which are in the gas phase only. It is shown that knowledge of gas–particle partitioning is needed to correct for this effect, and to improve predicted uptake rates.  相似文献   

7.
Kim M  Kim J  Hyun S 《Chemosphere》2012,89(3):262-268
The well-known cosolvency-induced sorption model is not applicable to predict the sorption of carboxylic acids in cosolvent system. To investigate the phenomenon, sorption and solubility of chlorinated phenols (2,4-dichlorophenol (2,4-DCP) and 2,4,6-trichlorophenol (2,4,6-TCP)) and carboxylic acids (benzoic acid and 2,4-dichlorophenoxyacetic acid (2,4-D)) were measured in soil-methanol mixture with various ionic strengths. The sorption (Km) of chlorinated phenols was explained by a cosolvency-induced sorption model; the inverse log-linear relationship between the Km and methanol volume fraction (fc). However, the Km of carboxylic acids increased with increasing fc. This discrepancy was attributed to the effect of the carboxylic moiety. To explain the effect, solubility was measured for benzoic acid and 2,4,6-TCP from various liquid conditions. For both solutes, the cosolvency power (σ) increased with CaCl2 concentrations and the salting constant (Ks) became smaller as fc increased. However, the σ value at a given salt concentration and the Ks value at a given fc were greater for 2,4,6-TCP than for benzoic acid, both of which were due to the greater hydrophobicity of the former. Overall, the solubility profiles of the both solutes on combination of fc and CaCl2 concentration evidenced no specific role of the carboxylic moiety. Therefore, it can be reasonably concluded that the positive relationship between Km and fc for carboxylic organic acid can be attributed to the modification of the activity coefficient occurred in the solid phase, which cannot be traceable by cosolvency-based model.  相似文献   

8.
The chemical composition and size distribution of submicron aerosols were analyzed at a suburban site at Saitama, Japan, in the winter of 2004/2005, using an Aerodyne aerosol mass spectrometer. Although organics and nitrate were the dominant species during the sampling period, a large fraction of sulfate was observed at the accumulation mode when mass loading was low and wind speed was high. The size distributions of m/z 44 (mostly CO2+) and sulfate aerosols during periods of high wind speed showed remarkable similarities in the accumulation mode, indicating that oxygenated organics were aged aerosols and internally mixed with sulfate. Ozone concentrations were also increased during these high wind speed periods although nighttime (e.g., 12/17 2004), indicating that the oxygenated compounds were strongly influenced by transported and aged air masses. The diurnal profiles of ultrafine-mode organics and hydrocarbon-like organic aerosols (HOA) were similar to NOX derived from traffic and other combustion sources. The temporal variation of oxygenated organic aerosols (OOA) agreed well with that of nitrate as a secondary aerosol tracer, and the diurnal profile of the OOA fraction of organics increased during the day associated with higher UV light intensity. The result of time and size-resolved chemical composition of submicron particles indicated that the OOA is associated with both photochemical activity and transboundary pollution, and ultrafine-mode organic and HOA aerosols are mainly associated with combustion sources.  相似文献   

9.
Partitioning of hydrophobic organic compounds to the interface between water and air may significantly affect the distribution and transfer of many xenobiotic chemicals between vapor and aqueous phases. The fluorescent probe, 1-methylperylene, was used to investigate the affinity of hydrophobic compounds for the water–air interface by varying the ratio of interfacial surface area to water volume in a fused-quartz cuvette. We found that the water–air/water interface partitioning coefficient [Kw−awi=1.2 mol cm-2awi/(mol ml-1w)] for this polycyclic aromatic hydrocarbon (PAH) was quantitatively consistent with partitioning to the same interface but from the airside, recently reported in the literature for less hydrophobic PAHs. Our results demonstrate significant partitioning from bulk water to the water/air interface for a hydrophobicity range relevant to many xenobiotic compounds. Anticipated implications of this process for the environmental chemistry of hydrophobic compounds include retarded gas-phase transport in unsaturated soils, bubble-mediated transport in water, droplet-mediated transport in the atmosphere, and photochemical reactions.  相似文献   

10.
Bioaccumulation models take various elimination and uptake processes into account, estimating rates from chemical lipophilicity, expressed as the octanol-water partition ratio (Kow). Here, we focussed on metabolism, which transforms parent compounds into usually more polar metabolites, thus enhancing elimination. The aim of this study was to quantify the change in lipophilicity of relevant organic pollutants undergoing various biotransformation reactions in mammals. We considered oxidation reactions catalyzed by three enzyme groups: cytochrome P450 (CYP), alcohol dehydrogenase (ADH), and aldehyde dehydrogenase (ALDH). Estimated log Kow values of a selected dataset of parent compounds were compared with the log Kow of their first metabolites. The log Kow decreased by a factor that varies between 0 and −2, depending on the metabolic pathway. For reactions mediated by CYP, the decrease in Kow was one order of magnitude for hydroxylated and epoxidated compounds and two orders of magnitude for dihydroxylated and sulphoxidated xenobiotics. On the other hand, no significant change in lipophilicity was observed for compounds N-hydroxylated by CYP and for alcohols and aldehydes metabolized by ADH and ALDH. These trends could be anticipated by the calculus method of log Kow. Yet, they were validated using experimental log Kow values, when available. These relationships estimate the extent to which the elimination of pollutants is increased by biotransformation. Thus, the quantification of the Kow reduction can be considered as a first necessary step in an alternative approach to anticipate biotransformation rates, which are hard to estimate with existing methods.  相似文献   

11.
Chen H  Chen S  Quan X  Zhao H  Zhang Y 《Chemosphere》2008,73(11):1832-1837
Sorption of nonpolar (phenanthrene and butylate) and polar (atrazine and diuron) organic chemicals to oil-contaminated soil was examined to investigate oil effects on sorption of organic chemicals and to derive oil–water distribution coefficients (Koil). The resulting oil-contaminated soil–water distribution coefficients (Kd) for phenanthrene demonstrated sorption-enhancing effects at both lower and higher oil concentrations (Coil) but sorption-reducing (competitive) effects at intermediate Coil (approximately 1 g kg−1). Rationalization of the different dominant effects was attempted in terms of the relative aliphatic carbon content which determines the accessibility of the aromatic cores to phenanthrene. Little or no competitive effect occurred for butylate because its sorption was dominated by partitioning. For atrazine and diuron, the changes in Kd at Coil above approximately 1 g kg−1 were negligible, indicating that the presently investigated oil has little or no effect on the two tested compounds even though the polarity of the oil is much less than soil organic matter (SOM). Therefore, specific interactions with the active groups (aromatic and polar domains) are dominantly responsible for the sorption of polar sorbates, and thus their sorption is controlled by available sorption sites. This study showed that the oil has the potential to be a dominant sorptive phase for nonpolar pollutants when compared to SOM, but hardly so for polar compounds. The results may aid in a better understanding of the role of the aliphatic and aromatic domains in sorption of nonpolar and polar organic pollutants.  相似文献   

12.
The degradation of organic matter in peat bogs is complex and not yet well understood. Recent investigations of the trace gases CO2 and CH4 focussed on the impact of these greenhouse gases on global warming. However, there have to be metabolic intermediates between complex organic structures (i.e., humic acids) and gaseous end products (CH4, CO2, N2, NOx and H2S) other than water-soluble substances (i.e., aromatic acids, amino acids, fatty acids). Deoxygenation during microbial decomposition of plant material also produces anoxic conditions that favor the formation of kinetically stable hydrocarbons. In this study, volatile organic substances (VOS) in peat bogs were investigated using two techniques: purge-and-trap and closed-loop stripping. Coupled gas chromatography–mass spectroscopy analysis revealed mainly branched hydrocarbons (C8H18) in concentrations up to 260 nM in peat pore-water. Additionally, alkylated benzenes were found in concentrations of up to 464 nM, in the peat pore-water, and up to 23 pptv in the headspace of peat cores. However, one-third of all the compounds in the complex VOS-fraction extracted from the peat system remain to be identified, especially those substances containing oxygen.  相似文献   

13.
Gas/particle distributions of atmospheric semi-volatile organic compounds (SOCs) are often measured using filter/sorbent samplers. Unfortunately, the adsorption of gaseous SOCs onto a filter can cause positive biases in the measured particle-phase concentrations, and negative biases in the measured gas-phase concentrations. When quartz fiber filters (QFFs) are used, surface-area-normalized gas/quartz partition coefficient (Kp,s, m3 m−2) values will be useful when estimating the magnitudes of these errors. Gas/QFF Kp,s values have been reported in the literature only for polycyclic aromatic hydrocarbons (PAHs) and n-alkanes. Gas/QFF Kp,s values were measured here for a series of polychlorinated dibenzodioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs), and also for a range of PAHs. Within each of the three individual compound classes, plots of log Kp,s vs. log pLo (sub-cooled liquid vapor pressure) were found to be linear with slopes of approximately −1. At relative humidity (RH)=25%, the pooled log Kp,s data at 25°C for the three compound classes were correlated with log pLo nearly as well (r2=0.95) as were the data for the individual compound classes (r2≈0.97). In general, the Kp,s values for the PAHs and PCDD/PCDFs studied were found to be about a factor of 2 larger for partitioning to clean QFFs at RH=25% than for TMFs at RH=21–52%. Backup QFFs used in filter/sorbent sampling in a suburban area yielded Kp,s values for PAHs at RH=37% that were significantly lower than for clean QFFs at the same RH. (This may have been the result of the adsorption of ambient organic compounds that at least partially blocked the direct adsorption of the SOCs to the QFF surface). Therefore, when QFFs are used to separate atmospheric gas- and particle-phase SOCs, corrections for compound-dependent gas adsorption artifacts for QFFs may need to be carried out using Kp,s values that were obtained with ambient backup QFFs.  相似文献   

14.

Phosphate, as an additive to composting, could significantly reduce ammonia emission and nitrogen loss but may also cause adverse effects on the degradation of organic matter. However, there is little information about the influence of pH change, salt content, and phosphate on different organic fraction degradation during composting with the addition of phosphate at a higher level. In this study, the equimolar phosphoric acid (H3PO4), sulfuric acid (H2SO4), and dipotassium phosphate (K2HPO4) were added into pig manure composting with 0.25 mol mass per kilogram of dry matter basis addition amount to evaluate the effect of H+, PO43?, and salinity on carbon component transformation and organic matter degradation. The results showed that both H3PO4 and K2HPO4 additives could lead to shorter duration in the thermophilic phase, lower degradation of lignocellulose, and lesser carbon loss compared to CK, even though had different pH, i.e., acidic and alkaline conditions, respectively. Besides, the addition of H3PO4, H2SO4, and K2HPO4 could increase the degradation of soluble protein and lipid during composting. Redundancy analysis demonstrated that the variation in different organic carbon fractions was significantly correlated with the changes of pH and the presence of PO43?, but not with SO42? and electrical conductivity, suggesting that pH and phosphate were the more predominant factors than salinity for the inhibition of organic matter degradation. Taken together, as acidic phosphate addition produces a true advantage of controlling nitrogen loss and lower inhibition of organics transformation during composting, the expected effects may result in more efficient composting products.

  相似文献   

15.
According to regulations, sows with piglets on organic farms must graze on pastures. Volatilization of ammonia (NH3) from urine patches may represent a significant source of nitrogen (N) loss from these farms. Inputs of N are low on organic farms and losses may reduce crop production. This study examined spatial variations in NH3 volatilization using a movable dynamic chamber, and the pH and total ammoniacal nitrogen (TAN) content in the topsoil of pastures with grazing sows was measured during five periods between June 1998 and May 1999. Gross NH3 volatilization from the pastures was also measured with an atmospheric mass balance technique during seven periods from September 1997 until June 1999. The dynamic chamber study showed a high variation in NH3 volatilization because of the distribution of urine; losses were between 0 and 2.8 g NH3–N m−2 day−1. Volatilization was highest near the feeding area and the huts, where the sows tended to urinate. Ammonia volatilization rate was linearly related to the product of NH3 concentration in the boundary layer and wind speed. The NH3 in the boundary layer was in equilibrium with NH3 in soil solution. Gross NH3 volatilization was in the range 0.07–2.1 kg NH3–N ha−1 day−1 from a pasture with 24 sows ha−1. Ammonia volatilization was related to the amount of feed given to the sows, incident solar radiation and air temperature during measuring periods, and also to temperature, incident solar radiation and rain 1–2 days before measurements. Annual ammonia loss was 4.8 kg NH3–N sow−1.  相似文献   

16.
Multifunctional organic compounds are thought to constitute a major component of the organic matter found in atmospheric particles. Their partitioning into the organic matter depends on their structure, their chemical properties and the properties of the absorbing matrix. It was recently shown that octanol is a suitable surrogate for organic particles and the octanol–air partition coefficient (KOA) was suggested as a useful tool for estimating the partitioning of organic compounds into atmospheric particles that contain high organic mass fractions. In this paper, we present a new and simple technique for the determination of KOA using solid phase microextraction (SPME) relative to a known Henry's law constant. We apply the technique for the determination of KOA of β-, γ- and δ-C3–C5 hydroxy alkyl nitrates. The temperature dependence of KOA for some of the compounds is also measured. It is shown that the solubility constants of these compounds are higher in octanol than in water and that the solubility in octanol increases with the length of the hydrophobic chain and with increasing distance between the hydroxy and the nitrooxy groups. Partition coefficients between the gas and particulate phase (Kp) are calculated using the determined KOA values and their atmospheric implications are discussed.  相似文献   

17.
Volatilization of pesticides participates in atmospheric contamination and affects environmental ecosystems including human welfare. Modelling at relevant time and spatial scales is needed to better understand the complex processes involved in pesticide volatilization. Volt'Air-Pesticides has been developed following a two-step procedure to study pesticide volatilization at the field scale and at a quarter time step. Firstly, Volt'Air-NH3 was adapted by extending the initial transfer of solutes to pesticides and by adding specific calculations for physico-chemical equilibriums as well as for the degradation of pesticides in soil. Secondly, the model was evaluated in terms of 3 pesticides applied on bare soil (atrazine, alachlor, and trifluralin) which display a wide range of volatilization rates. A sensitivity analysis confirmed the relevance of tuning to Kh. Then, using Volt'Air-Pesticides, environmental conditions and emission fluxes of the pesticides were compared to fluxes measured under 2 environmental conditions. The model fairly well described water temporal dynamics, soil surface temperature, and energy budget. Overall, Volt'Air-Pesticides estimates of the order of magnitude of the volatilization flux of all three compounds were in good agreement with the field measurements. The model also satisfactorily simulated the decrease in the volatilization rate of the three pesticides during night-time as well as the decrease in the soil surface residue of trifluralin before and after incorporation. However, the timing of the maximum flux rate during the day was not correctly described, thought to be linked to an increased adsorption under dry soil conditions. Thanks to Volt'Air's capacity to deal with pedo-climatic conditions, several existing parameterizations describing adsorption as a function of soil water content could be tested. However, this point requires further investigation. Practically speaking, Volt'Air-Pesticides can be a useful tool to make decision about agricultural practices such as incorporation or for the estimation of overall pesticide volatilization rates, and it holds promise for time specific dynamics.  相似文献   

18.
Ten rain samples were collected at west Los Angeles, California, during two precipitation events. The samples were extracted with CH2Cl2 using a separatory funnel followed by continuous steam distillation extraction. Extracts were analyzed for n-alkanes, UCM of hydrocarbons, PAHs, FAs, benzoic acids and phenols using capillary gas chromatography (see Table 1 for definition of acronyms). The concentrations of some compounds decreased with time, whereas those of other compounds increased during the precipitation. Fluctuations of organic concentrations with time are interpreted as being due to washout effect and transient input of organic matter during the precipitation event. The major factor controlling the inputs is suggested to be wind which carries the organic constituents from biogenic and/or anthropogenic (motor vehicle) sources. These results indicate that the origins of air masses scavenged during a rain event may be traced by analysis of the organic constituents in the rain water.  相似文献   

19.
From a literature-based assessment of the current knowledge about both the toxic or salutary properties of copper, this study focused on the determination, at 25 °C, of the interfacial properties of CuCl2, either alone or in mixture with carbofuran used, here, as a model of organics and/or pesticide. The interfaces under study were: i) the air/solution interface and ii) the silica/solution interface. The former is considered as a path for volatilization, whereas the latter permits a modelling of physical adsorption upon solids, which is the first and unavoidable step in any adsorption process. One should note that it can also mimic adsorption on some sandy soils. Coadsorption was clearly identified as implicated in an enhancement of the surface content of both solutes at both interfaces. However, at the two interfaces under study, the way the surface became structured led to opposite adsorption mechanisms for the organic compounds and the salt. A rough theory about ionic adsorption is also proposed.  相似文献   

20.
Chen HW  Chen CY  Wang GS 《Chemosphere》2011,85(4):591-597
The presence of various organic contaminants in water sources is of concern due to their direct threats to human health and potential to react with disinfectants to form carcinogenic byproducts including trihalomethanes, haloacetic acids and nitrosamines in finished water. This study applied both medium-pressure and low-pressure ultraviolet light coupled with hydrogen peroxide (UV/H2O2) to evaluate its efficacy for degradation of selected nitrogenous organic compounds and corresponding disinfection byproduct (DBP) formation. Six organic compounds were chosen as target precursors based on their nitrogen contents and molecular structures. The results showed that higher oxidation capacity resulted in better reduction of organic matters and DBP formation potentials (DBPFPs). However, insufficient contact time and oxidant doses could lead to a rise of DBPFPs in the early stages of UV/H2O2 reactions. A greater percentage removal was achieved for organic carbon than organic nitrogen after UV/H2O2 treatment, especially for compounds with complicated structure such as diltiazem. During the UV/H2O2 treatment, the intermediate products include tertiary amine, dimethyl amine (DMA) or DMA-like structures, which are N-nitrosodimethylamine (NDMA) precursors after chlorination or chloramination. Furthermore, it was observed that using dissolved organic nitrogen and DMA to predict NDMAFP could lead to biased conclusions because of the complex nature of nitrogenous matters in aqueous environments.  相似文献   

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