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1.
Comparison of four methods including liquid-liquid extraction (LLE), direct aqueous injection (DAI), purge and trap (PAT) and head space (HS) were carried out in this work for determination of volatile organic compounds (VOCs) including trihalomethanes (THMs) in drinking water. This comparison is made especially to show the advantages and disadvantages and specifically the different detection limits (DL) that can be obtained for a given type of analysis. LLE is applicable only for determination of the THMs concentrations, while DAI, PAT, HS methods with different DL each of them are applicable for all VOCs, with PAT to be the most sensitive. Sampling apparatus and procedure for all these methods except of PAT are very simple and easy, but possible disadvantages for LLE and DAI are the low sensitivity and especially the detection only of THMs with LLE.  相似文献   

2.
Evidence for destruction of PCBs by the OH radical in urban atmospheres   总被引:3,自引:0,他引:3  
Evidence for reaction of polychlorinated biphenyl (PCB) congeners with the hydroxyl (OH) radical in the troposphere was observed in diurnal variations in ambient gas-phase PCB concentrations at three urban sampling sites located in the Chicago, IL; Baltimore, MD; and Jersey City, NJ urban/industrial areas. The magnitude of the depletion of individual PCB congeners decreased by about 10-20% for each additional chlorine substituent, reflecting slower reaction rates for higher MW congeners with the OH radical. Octa- and nonachlorobiphenyls, which are largely unreactive with the OH radical, were used as tracers to investigate the effects of dilution on diurnal variation. The environmental rate constants for disappearance of the PCBs range from about 1.0 day(-1) for trichlorobiphenyls to about 0.3 day(-1) for hexachlorobiphenyls. Assuming a OH radical concentration of 3 x 10(6) molecules cm (-3), the second-order rate constants for reaction of specific congeners with the OH radical are consistent with laboratory measurements. More importantly, the relative reactivity of PCB homologues agrees well with the relationship predicted by other researchers from laboratory measurements, suggesting that losses of PCBs during daytime tropospheric transport are due at least in part to reactions with the OH radical.  相似文献   

3.
Solutions and verification of a scale-dependent dispersion model   总被引:7,自引:0,他引:7  
In this paper, analytical solutions are derived for a one-dimensional scale-dependent dispersion model (SDM), considering linear equilibrium sorption and first-order degradation for continuous and pulse contaminant sources, with a constant input concentration in a semi-infinite uniform porous medium. In the SDM model, dispersivity alpha(x) is replaced with a constant epsilon multiplied by the transport distance x. The solution for a pulse source is verified experimentally in the analysis of tritium data obtained from an 8-m-long homogenous pea-gravel column with multiple sampling locations, and the results are compared with those analysed by a commonly used solution of a constant dispersion model (CDM). The SDM predicts concentrations satisfactorily at all sampling locations, while the CDM fits the experimental data well for only one location. Both models are then calibrated for each individual concentration breakthrough curve, using local values for either epsilon in the SDM or alpha(x) in the CDM. Both models give equally good fits for appropriate choices of individual epsilon and alpha(x) values, and both indicate a linear increase in alpha(x) with distance. The epsilon values tend to change little as x increases and are expected to approach a constant at relatively large distances downstream. Hence, predictions from the SDM should become more accurate as x increases.  相似文献   

4.
Cousins I  Mackay D 《Chemosphere》2000,41(9):1389-1399
A quantitative structure-property relationship (QSPR) method for the correlation of physical-chemical properties and partition coefficients, namely the 'three solubility' approach, is described and applied to a group of 22 phthalate esters. The solubilities or 'apparent-solubilities' of these substances in the liquid state are compiled and correlated against Le Bas molar volume in the three primary media of air, water and octanol. From these solubilities the air-water (K(AW)), octanol-water (K(OW)) and octanol-air (K(OA)) partition coefficients are deduced. Estimated solubilities in water and octanol-water partition coefficients are shown to compare favourably with more recent accurate measurements. A set of selected values is presented, with error limits, which is recommended for use in modelling and assessment studies. Some environmental implications are discussed of the large range in property values for this series.  相似文献   

5.
This paper presents the design and performance of a compact dilution sampler (CDS) for characterizing fine particle emissions from stationary sources. The sampler is described, along with the methodology adopted for its use. Dilution sampling has a number of advantages, including source emissions that are measured under conditions simulating stack gas entry and mixing in the ambient atmosphere. This is particularly important for characterizing the semivolatile species in effluents as a part of particulate emissions. The CDS characteristics and performance are given, along with sampling methodology. The CDS was compared with a reference dilution sampler. The results indicate that the two designs are comparable for tests on gas-fired units and a diesel electrical generator. The performance data indicate that lower detection limits can be achieved relative to current regulatory methods for particulate emissions. Test data for the fine particulate matter (PM2.5) emissions are provided for comparison with U.S. Environment Protection Agency (EPA) Conditional Test Method 040 for filterable particulate matter (FPM) and the EPA Method 202 for condensable particulate matter. This comparison showed important differences between methods, depending on whether a comparison is done between in situ FPM determinations or the sum of such values with condensable PM from liquid filled impingers chilled in an ice bath. These differences are interpretable in the light of semivolatile material present in the stack effluent and, in some cases, differences in detection and quantification limits. Determination of emissions from combustors using liquid fuels can be readily achieved using 1-hr sampling with the CDS. Emissions from gasfired combustors are very low, requiring careful attention to sample volumes. Sampling volumes corresponding with 6-hr operation were used for the combined mass and broad chemical speciation. Particular attention to dilution sampler operation with clean dilution air also is essential for gas-fired sources.  相似文献   

6.
This paper describes a method of estimating emission fluxes of biogenic volatile organic compounds (BVOCs) based on the approach proposed by Guenther et al. (1995) and the high-resolution Corine land-cover 2000 database (1 × 1 km resolution). The computed emission fluxes for the Czech Republic (selected for analysis as being representative of a heavily cultivated, central European country) are compared with anthropogenic emissions, both for the entire country and for individual administrative regions. In some regions, BVOC emissions are as high as anthropogenic emissions; however, in most regions the BVOC emissions are approximately 50% of the anthropogenic emissions. The yearly course of BVOC emissions (represented by monoterpenes and isoprene) is presented, along with the spatial distribution of annual mean values. Differences in emission distributions during winter (January) and summer (June) are also considered.  相似文献   

7.
Rate coefficients are reported for the gas-phase reaction of the hydroxyl radical (OH) with C2HCl3 (k(1)) and C2Cl4 (k2) over an extended temperature range at 740+/-10 Torr in a He bath gas. These absolute rate measurements were accomplished using a laser photolysis/laser-induced fluorescence (LP/LIF) technique under slow flow conditions. The simple Arrhenius equation adequately describes the low temperature data for k1 (<650 K) and the entire data set for k2 and is given by (in units of cm3 molecule(-1) s(-1)): k1(291 - 650 K) = (9.73+/-1.15) x 10(-13) exp (158.7+/-44.0)/T, k2(293 - 720 K ) = (1.53+/-0.14) x 10(-12) exp (-688.2+/-67.5)/T. Error limits are 2sigma values. The room temperature values for k1 and k2 are within +/-2sigma of previous data using different techniques. The Arrhenius activation energies for k1 and k2 are a factor of 2-3 lower than previously reported values. The experimental measurements for both k1 and k2 in conjunction with transition state and variation transition state theory calculations infer an OH addition mechanism. The lack of a measurable kinetic isotope effect for k1 is consistent with this mechanism. Insight into the subsequent reactions of the chemically activated intermediate are presented in the form of potential energy diagrams derived from ab initio calculations.  相似文献   

8.
China’s strategies to control acidifying pollutants and particulate matter (PM) may be in conflict for soil acidification abatement. Acidifying pollutant emissions are estimated for 2005 and 2020 with anticipated control policies. PM emissions including base cations (BCs) are evaluated with two scenarios, a base case applying existing policy to 2020, and a control case including anticipated tightened measures. Depositions of sulfur (S), nitrogen (N) and BCs are simulated and their acidification risks are evaluated with critical load (CL). In 2005, the area exceeding CL covered 15.6% of mainland China, with total exceedance of 2.2 Mt S. These values decrease in the base scenario 2020, implying partial recovery from acidification. Under more realistic PM control, the respective estimates are 17.9% and 2.4 Mt S, indicating increased acidification risks due to abatement of acid-neutralizing BCs. China’s anthropogenic PM abatement will have potentially stronger chemical implications for acidification than developed countries.  相似文献   

9.
In order to comply with the ammonia (NH(3)) emission reduction assigned to the Netherlands development of new measures are needed, which should be supported by fast and accurate measurements to arrive at new estimates of the NH(3) emission from each agricultural source. This paper gives an overview of the current methods used in the Netherlands to measure NH(3) emissions from animal houses, and provides alternative methods for some particular situations. For mechanically ventilated animal houses, passive flux samplers placed in the ventilation shafts of the animal house are presented as alternative to measure a larger number of animal houses (replicates) with the same housing system at a low price. For naturally ventilated animal houses, when mixing in the animal house is not good enough to allow measurements within the animal house (internal tracer gas ratio method), two measurement methods are discussed: the Gaussian plume dispersion model, which is usually not suitable for agricultural situations, and the flux frame method, which is not always applicable because of distortion of the flow around the building. Finally, for animal houses with outside yards for the animals, there are at this moment no methods available to measure the NH(3) emissions from these complex situations, although quick box methods (for the outside yards) and a combination of a backward Lagrangian stochastic model with open-path concentration measurements with a tunable diode laser (TDL), look promising.  相似文献   

10.
Dust events are common air pollution events in parts of the world with arid, semi-arid, or desert areas. There is little research on the association between respiratory and cardiovascular health and dust events in places which are close to the deserts. The aim of this study is to evaluate the health effects of dust events in a location where traffic and industry are underdeveloped and dust events are most frequent in China. The setting allows the opportunity to reduce confounding by anthropogenically derived particulate matter and to confirm the health effects of dust events. The present study was done using daily counts of hospitalizations in Minqin (1994–2003) for respiratory and cardiovascular diseases (International Classification of Diseases, Tenth revision) for males and females. Using a semi-parametric generalized additive model and controlling for long-term temporal trends, day of the week, meteorological factors, and seasonal influence, counts of hospitalization were analyzed for dust events in a Poisson regression.Relative risks (RRs) were used to estimate the risk of dust events for respiratory and cardiovascular hospitalizations. In the year-round model, dust events with a lag of 3 days were significantly associated with total respiratory hospitalization for males and females, with RRs of 1.14 (95% confidence interval (CI) 1.01–1.29) and 1.18 (95% CI 1.00–1.41); dust events with a lag of 4 days were significantly associated with upper respiratory tract infection (URTI) in males (RR 1.28, 95% CI 1.04–1.59), and dust events with a lag of 6 days were significantly associated with pneumonia in males, with an RR of 1.17 (95% CI 1.00–1.38). A significant association between dust events with a lag of 3 days and hypertension in males was also found (RR 1.30, 95% CI 1.03,1.64). In the seasonal analysis model, the associations between the dust events and respiratory and cardiovascular hospitalizations were stronger in spring and in winter, respectively.The results show the health effects of dust events on respiratory and cardiovascular hospitalizations, and the characteristic seasonal distribution of the health effects. In addition, the health effects of dust events are consistent with recent animal and human data showing the respiratory and cardiovascular effects of particulate matter.  相似文献   

11.
Kar S  Roy K 《Chemosphere》2012,87(4):339-355
Different regulatory agencies in food and drug administration and environmental protection worldwide are employing quantitative structure-activity relationship (QSAR) models to fill the data gaps related with properties of chemicals affecting the environment and human health. Carcinogenicity is a toxicity endpoint of major concern in recent times. Interspecies toxicity correlations may provide a tool for estimating sensitivity towards toxic chemical exposure with known levels of uncertainty for a diversity of wildlife species. In this background, we have developed quantitative interspecies structure-carcinogenicity correlation models for rat and mouse [rodent species according to the Organization for Economic Cooperation and Development (OECD) guidelines] based on the carcinogenic potential of 166 organic chemicals with wide diversity of molecular structures, spanning a large number of chemical classes and biological mechanisms. All the developed models have been assessed according to the OECD principles for the validation of QSAR models. Consensus predictions for carcinogenicity of the individual compounds are presented here for any one species when the data for the other species are available. Informative illustrations of the contributing structural fragments of chemicals which are responsible for specific carcinogenicity endpoints are identified by the developed models. The models have also been used to predict mouse carcinogenicities of 247 organic chemicals (for which rat carcinogenicities are present) and rat carcinogenicities of 150 chemicals (for which mouse carcinogenicities are present). Discriminatory features for rat and mouse carcinogenicity values have also been explored.  相似文献   

12.
There are different methods to estimate and predict effects of chemical elements and corresponding speciation forms in biochemistry and toxicology, including statements on essentiality and antagonisms. Two approaches are given here: (1) "identity cards" describing biologically fundamental aspects of element chemistry and (2) qualitative discussions which assume the existence of (indirect ways into) chemical autocatalysis to be essential for maintaining life and permitting reproduction. The latter method, developed by the present authors, draws upon Stoichiometric Network Analysis, a safe procedure for complexity reduction in feedback networks) and provides estimates of concentration regimes for different elements suitable for survival and reproduction. The biochemical hierarchy level considered here is that of (metallo-)proteins. Thermodynamic toxicity aspects are given in correlations with DMSO solvent affinities and thiocyanate bonding modes. Effects of antagonists and of ion substitution within metalloenzymes or of metabolic simplification can be dealt with, likewise increased sensitivities within symbiotic relationships and within carcinomas are explained which are relevant for environmental monitoring and tumour therapy, respectively.  相似文献   

13.
Lindell MJ  Bremle G  Broberg O  Larsson P 《Ambio》2001,30(8):545-551
Lake V?ttern in southern Sweden is a large oligotrophic lake with high surface to catchment area ratio (ca. 0.4) and a water residence time of 60 years. The lake combines sensitivity to atmospheric POP-pollution with general susceptibility for effects of POPs and slow concentration decline. Time series, from the 1960s until 1996, of PCBs and DDT in fish and data on TCDD in sediment of L. V?ttern are presented and compared to other large lakes. The long time dataset of POPs in Arctic char (Salvelinus salvelinus) shows a significant annual decline of about 5% for PCBs and 13% for DDT. These rates are in agreement with other studies. Nutrients as well as biological effects and factors affecting the fate of POPs in oligotrophic lakes with long residence times are discussed. We propose that oligotrophic clear lakes are important ecosystems for monitoring POPs in biota.  相似文献   

14.
Zhao YY  Tao FM  Zeng EY 《Chemosphere》2008,70(5):901-907
Density functional theory calculations at the B3LYP/6-31+G(d) and B3LYP/aug-cc-pVDZ levels were performed to obtain the equilibrium structures, thermodynamic properties, and electron affinities (EA) of 14 polybrominated diphenyl ether (PBDE) congeners in the gas phase. All congeners except for those of symmetric BDE are found to have two or more conformational isomers. The optimized geometries of the most stable conformational isomers are in agreement with recently published X-ray crystallographic data. The thermodynamic properties of the congeners with a given number of bromine substitutions are strongly dependent on the substitution pattern, whereas the EA values also depend on the number of bromine substitutions. The vertical electron affinities (EA(Ver)) calculated for the selected BDE congeners at the B3LYP/aug-cc-pVDZ level are all positive except for di-BDEs, and are correlated with the initial reductive debromination rate constants obtained recently [Keum, Y.-S., Li, Q.X., 2005. Reductive debromination of polybrominated diphenyl ethers by zerovalent iron. Environ. Sci. Technol. 39, 2280]. All adiabatic electron affinities (EA(Ada)) are positive, and suggest that the BDE congeners act as electron acceptors when reacting with receptors in living cells. The calculated EA(Ada) values differ considerably from those of EA(Ver) because of the large geometrical relaxation from the neutral to the anionic BDE congeners, highlighted by the lengthening of a C-Br bond. The elongated C-Br bond, which occurs at the alpha position, is directly involved in the debromination of n-bromodiphenyl to (n-1)-bromodiphenyl ethers in the reductive debromination experiments.  相似文献   

15.
According to the European legislation, REACH, organic compounds are considered as substances of very high concern (SVHC) if they are persistent, bioaccumulative and toxic (PBT). A substance's long-range transport potential (LRTP) may also pose a risk to remote regions. This is, however, not yet explicitly included. For identification of compounds, which are not PBT according to REACH criteria, but show LRTP, we investigated 22,438 compounds from the Canadian Domestic Substance List (CDSL). The CDSL was searched for organic, neutral compounds. Substance properties were estimated with EPI Suite v4.00. Next, the substance list was edited in two ways: (1) The half-life criterion in air for LRTP as defined in the Stockholm Convention was applied. (2) For all compounds, indicators for persistence and LRTP were calculated with the multimedia model ELPOS v2.2. Applying the half-life criterion, we identified 594 substances, which are prone to LRT but are not PBT (non-PBT-L substances). In contrast, investigations with ELPOS lead to a shorter list of 188 substances, which are non-PBT-L substances. Finally, the list was compared with potential Arctic contaminants identified in previous literature. Our results show that there is a large number of organic chemicals which would not be considered as SVHC since they are not, at the same time, persistent, bioaccumulative and toxic according to REACH criteria. Nevertheless, they show LRTP according to different screening approaches and thus a potential hazard to remote regions.  相似文献   

16.
The sensitivity of mesoscale simulations of land and sea breeze circulation on the south east coast in the Chennai region of India to boundary layer turbulence parameterizations is studied using the community based PSU/NCAR mesoscale model MM5. High-resolution simulations are carried out with nested domains. Four widely used boundary layer turbulence parameterization schemes are selected for the study. Two of these schemes (Blackadar (BK) and medium range forecast (MRF)) are simple first-order non-local schemes and the other two (Mellor–Yamada (MY) Eta planetary boundary layer (PBL) and Gayno–Seaman (GS)) are more complex 1.5 order local schemes that include a prognostic equation for turbulence kinetic energy. The other physics used in the model are identical. The micro-meteorological tower and flux observations, GP sonde and radiosonde observations from the study region are used to compare the simulated mean variables. In spite of differences in complexity, all the schemes show similar capability in simulating the boundary layer temperature, humidity and winds. The land–sea breeze circulation and internal boundary layer formation, which are special phenomena at the coastal site, could be simulated by all the schemes. The BK, MRF schemes produced boundary layers that are more mixed than those produced with the MY and GS schemes. While all the schemes underestimated surface sensible heat fluxes during stable night conditions they are reasonably simulated during daytime by MRF and BK schemes. Among the tested schemes, the BK scheme has reasonably produced the PBL height, humidity, wind fields and proves suitable for operational forecasting. The results suggest that there is little improvement in overall accuracy of predictions with more complex turbulence parameterizations.  相似文献   

17.
Soil column experiments are used to investigate the fate of three pesticides of high, intermediate, and low solubility in groundwater: N- phosphonomethyl glycine (glyphosate); O,O-diethyl-S-[(ethylthio)methyl]phosphorodithioate (phorate); (2,4-dichlorophenoxy)acetic acid (2,4-D). Feed solutions are prepared by adding each pesticide (100 mg/L glyphosate, 50 micro g/L phorate, 50 mg/L 2,4-D) along with conservative tracer, KBr, in synthetic groundwater. The concentration of the pesticides in effluents is detected by ion chromatography (glyphosate, 2,4-D) and GC-FID (phorate). The Br(-) breakthrough curves are employed to estimate the dispersion coefficient and mean pore velocity in each column. Solute transport and reactive models accounting for equilibrium/non-equilibrium sorption and biodegradation are coupled with inverse modeling numerical codes to estimate the kinetic parameters for all pesticides.  相似文献   

18.
This work is focused on measuring the concentration distribution of a conservative tracer in a homogeneous synthetic porous material and in heterogeneous natural sandstone using MRI techniques, and on the use of spatially resolved porosity data to define spatially variable diffusion coefficients in heterogeneous media. The measurements are made by employing SPRITE, a fast MRI method that yields quantitative, spatially-resolved tracer concentrations in porous media. Diffusion experiments involving the migration of H(2)O into D(2)O-saturated porous media are conducted. One-dimensional spatial distributions of H(2)O-tracer concentrations acquired from experiments with the homogeneous synthetic calcium silicate are fitted with the one-dimensional analytical solution of Fick's second law to confirm that the experimental method provides results that are consistent with expectations for Fickian diffusion in porous media. The MRI-measured concentration profiles match well with the solution for Fick's second law and provide a pore-water diffusion coefficient of 1.75×10(-9)m(2)s(-1). The experimental approach was then extended to evaluate diffusion in a heterogeneous natural sandstone in three dimensions. The relatively high hydraulic conductivity of the sandstone, and the contrast in fluid density between the H(2)O tracer and the D(2)O pore fluid, lead to solute transport by a combination of diffusion and density-driven advection. The MRI measurements of spatially distributed tracer concentration, combined with numerical simulations allow for the identification of the respective influences of advection and diffusion. The experimental data are interpreted with the aid of MIN3P-D - a multicomponent reactive transport code that includes the coupled processes of diffusion and density-driven advection. The model defines local diffusion coefficients as a function of spatially resolved porosity measurements. The D(e) values calculated for the heterogeneous sandstone and used to simulate diffusive and advective transport range from 5.4×10(-12) to 1.0×10(-10)m(2)s(-1). These methods have broad applicability to studies of contaminant migration in geological materials.  相似文献   

19.
Wu WZ  Schramm KW  Xu Y  Kettrup A 《Chemosphere》2001,43(4-7):633-641
The present study monitored fish from sites contaminated for many years, and the data reflected the results of actual, long-term environmental exposure. The sum concentrations and TEQs of PCDD/F in the muscle of common carp (Cyprinus carpio (linnaeus)) and big head (Aristichthys nobilis) from the different site of a heavily polluted lake in China are decreased with decrease of PCDD/F concentration in sediment and water. Concentration in fish can be highly variable, but the concentration is comparable in muscle between different species of fish if the concentrations are normalized by lipid content. PCDD/F accumulate in certain tissues with the highest proportions found in the liver of fish. The concentrations and TEQs in livers were also decreased with concentrations of sediments and water. The concentrations of PCDD/F in muscle are significantly correlated with those in liver. BCFs of 2,3,7,8-substituted PCDD/F calculated directly from water were consistent with that calculated indirectly from sediment. PCDD/F concentrations in sediment are much higher than that in water, therefore the measurement is much easier and the results are more accurate. Estimated BCFs for superhydrophobic chemicals derived from sediment may also serve as acceptable surrogates for "true" bioaccumulation potential.  相似文献   

20.
Dispersion and subsequent deposition of SO(2) downwind from a stationary point source are affected by several transport processes: buoyancy at the source, advection, and air turbulence en route from the source to the area of impact. In this paper, SO(2) transport processes are simulated by way of Lagrangian air parcel trajectory simulations. In these simulations, the source releases air parcels in puffs. The calculations cover both daytime and night-time conditions and take into account: (i) solar geometry, (ii) diurnal variations of wind speed and air turbulence, (iii) resistance to the transfer of SO(2) from the air to the land, and (iv) flat terrain. Deposition to the forest is determined by calculating the rate of SO(2) flux from individual air parcels to the land according to the parcel's velocity and an assumed air-to-surface SO(2) transfer coefficient. Daily cumulative SO(2) deposition rates are calculated by summing the simulated diffusional fluxes of SO(2) from air to land over each simulated time step. Daily cumulative SO(2) amounts are calculated for downwind distances from 0 to 42 km, for smokestack heights from 30 to 200 m, and for each day of the year according to historical year-round and local weather patterns representative of days with neutral conditions and days with transitions from stable to unstable conditions. Annual per hectare rates of SO(2) deposition are calculated by way of Monte Carlo simulations, according to historical patterns for daily wind, atmospheric stability, and precipitation. These simulations are calibrated for the area surrounding a coal-burning power generator at Grand Lake in south-central New Brunswick, Canada. Calculated concentrations for SO(2) were similar to those obtained with a mobile SO(2) detection unit and a SO(2)-monitoring unit 42 km NE from the emission source. Cumulative SO(2) deposition rates were reasonably similar to those obtained with PbO(2) sulfation plates. A detailed comparison revealed topography was an important factor in modifying actual cumulative SO(2) deposition rates.  相似文献   

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