A new approach for estimating emissions of organic solutes and organic solvents under wind speeds

A new approach is developed to predict the volatilization loss of the pure liquid and the volatilization rates of organic solutes with different Henry's law constants (H) under wind speed. The tested compounds include eight volatile organic compounds for pure liquid and the forty-one organic solutes with different H compounds are divided into three groups that span seven H orders. The wind speed is set from 0 to 6.0 ms^?1. A characteristic parameter ε was established to estimate volatilization loss of pure organic compounds. The mass transfer coefficient (K_OL) ratios of the organic solutes, under both wind speed and still conditions, are applied to describe the volatilization characteristics of the selected solutes. The curve profile for K_OL ratios and ε values relative to the selected wind speed can be divided into two stages, the sharp-rise stage and the stable-linearity stage. The critical finding is the ε values for the different organic compounds under a specific wind speed approach a constant. The changes in the curve profile of the K_OL ratios are similar to the ε values of the pure organic compounds. It is also found the relatively lower H compounds exhibit a sensitive wind effect on the K_OL ratios. The K_OL ratios of the relatively higher H compounds indicate a similar linear increase with the increasing wind speed in the two stages. Accordingly, concentrations of the organic compounds at the interface are thought to the primary factor. The obtained results could be a good reference to estimate volatilization loss of the organic solutes or the organic solvents under different wind speed conditions.     

Modelling pesticide volatilization after soil application using the mechanistic model Volt'Air

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 K_h. 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.     

Effect of bubble-induced surface turbulence on gas-liquid mass transfer in diffused aeration systems.

Models that predict volatilization of organic compounds from wastewater treatment basins may underestimate emission rates if the surfaces are considered as quiescent. In reality, the water surface may be agitated by subsurface aeration, increasing mass transfer across the tank surface air-water interface. This study investigated the effect of turbulence, induced by diffused bubble aeration, on mass transfer at the water surface of a pilot aeration basin. The mass transfer of ammonia from an enclosed headspace over the basin to acidified water was measured when different diffuser types and airflow rates were applied. Oxygen-transfer tests were conducted immediately following each ammonia-transfer test. Increasing airflow rates through fine- and coarse-bubble diffusers had a significant effect on the ammonia mass-transfer rate. Experimental mass-transfer parameters (K(L)a's) for surface volatilization derived with aeration present were up to 48% higher than the K(L)a values for quiescent conditions over the range of conditions tested. No effect of diffuser type on ammonia transfer could be determined. The study results infer an effect on oxygen transfer into the water at the surface and potential transfer of volatile organic compounds, if present, from the water. The results of the ammonia mass-transfer experiments suggest that adjustments to the existing mass transfer correlations for surface volatilization from aeration basins may be in order. Such adjustments will have the greatest effect on predictions for the less volatile compounds, under conditions of low airflow rates.     

Nonvolatile,semivolatile, or volatile: Redefining volatile for volatile organic compounds

Although widely used in air quality regulatory frameworks, the term “volatile organic compound” (VOC) is poorly defined. Numerous standardized tests are currently used in regulations to determine VOC content (and thus volatility), but in many cases the tests do not agree with each other, nor do they always accurately represent actual evaporation rates under ambient conditions. The parameters (time, temperature, reference material, column polarity, etc.) used in the definitions and the associated test methods were created without a significant evaluation of volatilization characteristics in real world settings. Not only do these differences lead to varying VOC content results, but occasionally they conflict with one another. An ambient evaporation study of selected compounds and a few formulated products was conducted and the results were compared to several current VOC test methodologies: SCAQMD Method 313 (M313), ASTM Standard Test Method E 1868-10 (E1868), and U.S. EPA Reference Method 24 (M24). The ambient evaporation study showed a definite distinction between nonvolatile, semivolatile, and volatile compounds. Some low vapor pressure (LVP) solvents, currently considered exempt as VOCs by some methods, volatilize at ambient conditions nearly as rapidly as the traditional high-volatility solvents they are meant to replace. Conversely, bio-based and heavy hydrocarbons did not readily volatilize, though they often are calculated as VOCs in some traditional test methods. The study suggests that regulatory standards should be reevaluated to more accurately reflect real-world emission from the use of VOC containing products.

Implications:The definition of VOC in current test methods may lead to regulations that exclude otherwise viable alternatives or allow substitutions of chemicals that may limit the environmental benefits sought in the regulation. A study was conducted to examine volatility of several compounds and a few formulated products under several current VOC test methodologies and ambient evaporation. This paper provides ample evidence to warrant a reevaluation of regulatory standards and provides a framework for progressive developments based on reasonable and scientifically justifiable definitions of VOCs.     

Environmental copper: Behaviour when involved in physical adsorption at several interfaces

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 CuCl_2, 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.     

Effects of soil moisture and physical-chemical properties of organic pollutants on vapor-phase transport in the vadose zone

Vapor-phase transport of organic pollutants is one of the important pathways in the distribution and attenuation of volatile organic compounds in the vadose zone. In this study, the impact of vapor-phase partitioning and of the physical-chemical properties of organic pollutants on vapor-phase transport was assessed. An experimentally derived relationship to predict vapor sorption for a variety of soil types under varying soil moisture conditions was incorporated into the two-dimensional finite-element model, Vocwaste. The revised model was then used to simulate the transport of volatile organics. Vapor-phase partitioning in the model accounted for vapor uptake by sorption onto moist mineral surfaces as well as sorption at the liquid-solid interface and dissolution into soil water. Under dry conditions, vapor-phase sorption of volatile organic pollutants was shown to have a retarding effect on transport of organic vapors. However, for shallow, contaminated soils, volatilization was controlled by vapor diffusion, even under dry conditions where vapor-phase sorption was high. The influence of Henry's law constant and of the aqueous-phase (solid-liquid) partition coefficient for volatile organic pollutants was considered in the simulations. Volatilization of organic vapors was shown to be favored for contaminants with high Henry's law constants and low aqueous-phase partitioning coefficients. Because of the interdependence of these two physical-chemical properties, individual properties of the contaminant should not be considered in isolation in the evaluation of vapor transport.     

Evaluation of the OECD activated sludge,respiration inhibition test

The OECD Activated Sludge, Respiration Inhibition Test was evaluated as a method for assessing the potential impact of chemicals on wastewater treatment systems. Reproducibility of the test method was examined with respect to variation in oxygen consumption rates measured for a series of reactions set under identical conditions, and the variability in IC50 values estimated for three reference compounds. Several statistical procedures were also evaluated for analyzing activated sludge inhibition data. The test method was subsequently used to examine the effects of a wide variety of inorganic and organic chemicals on activated sludge respiration rates.     

Photodegradation and volatility of pesticides

BACKGROUND AND OBJECTIVES: Among the factors affecting the environmental fate of surface-applied pesticides several biological as well as abiotic factors, such as volatilization and photochemical transformations are of particular interest. Whereas reliable measurement methods and models for estimating direct photodegradation are already available for the compartments of water and atmosphere and individual subprocesses have already been described in detail, there is still a need for further elucidation concerning the key processes of heterogeneous photodegradation of environmental chemicals on surfaces. METHODS: In order to systematically examine the direct and indirect photodegradation of 14C-labeled pesticides on various surfaces and their volatilization behavior, a new laboratory device ('photovolatility chamber') was designed according to US EPA Guideline 161-3. Model experiments under controlled conditions were conducted investigating the impact of different surfaces, i.e. glass, soil dust and radish plants, and environmental factors, i.e. irradiation and atmospheric ozone (O3), on the photodegradation and volatilization of surface-deposited [phenyl-UL-14C]parathion-methyl (PM). RESULTS AND DISCUSSION: Depending on the experimental conditions, parathion-methyl was converted to paraoxon-methyl, 4-nitrophenol, unknown polar products and 14CO2. With respect to the direct photodegradation of PM (experiments without O3), the major products were polar compounds and 14CO2, due to the rapid photochemical mineralization of 4-nitrophenol to 14CO2. Paraoxon-methyl and 4-nitrophenol formation was mainly mediated by the combination of light, O3, and *OH radicals. In radish experiments PM photodegradation was presumably located in the cuticle compartment, which exhibited a sensitized photodegradation, as more unknown products were yielded compared to the glass and soil dust experiments. This could be explained by intensifying the inherent PM degradation in the dark with the same product spectrum. Due to photochemical product formation, which is an antagonistic process to the volatilization of parent compound, the volatilization of unaltered parathion-methyl from each surface generally decreased in the presence of light, particularly in combination with increasing O3 concentrations and *OH radical production rates. CONCLUSION: First results demonstrated that the photovolatility chamber provides a special tool for the systematic evaluation of (a) photodegradation of surface-located pesticide residues, i.e. measuring qualitative aspects of direct and indirect photodegradation together with relative photodegradation rates, and (b) volatilization of pesticides on surfaces by including and optionally varying relevant parameters such as light, atmospheric O3 concentration, surface temperature, air temperature, air flow rate. OUTLOOK: The experimental facility represents an important complement to lysimeter and field studies, in particular for experiments on the volatilization of pesticides using the wind tunnel system. With the photovolatility chamber special experiments on photodegradation, volatilization and plant uptake can be conducted to study key processes in more detail and this will lead to a better understanding of the effects of certain environmental processes on the fate of released agrochemicals contributing to an improved risk assessment.     

A standardized method for assessment of oxidative transformations of brominated phenols in water

The term persistence has been used to confusion since it is used as a conceptual parameter without a uniform definition. Work is therefore being done in order to unite ideas and describe persistence based on the chemical reactivity and chemico-physical properties of compounds via investigation of the main degradation pathways in the environment; photolysis, hydrolysis-substitution-elimination (hse), oxidation, reduction and radical reactions. The present work is focused on developing a method to determine oxidative degradation rates of chemicals and thereby measurement of their susceptibility to undergo oxidation reactions. The method based on potassium permanganate works well for water soluble compounds and is easy, robust, inexpensive and reproducible. By using the method and varying the analysed substances, the degradation rates for brominated phenols, two chlorinated phenols and high volume production compounds such as tetrabromobisphenol A (TBBPA), tetrachlorobisphenol A (TCBPA) and bisphenol A (BPA) have been determined at pH 7.6+/-0.2. The reaction rates of the two halogenated BPA's are particularly fast, giving half-lives in seconds. The other test compounds have slower reaction rates but easily measured under the reaction conditions applied. The reactions are temperature dependent. There is evidence that pK(a) and the substitution pattern of the halogens affects the rate of the reactions. The method is robust and applicable for reaction rate constant measurements of present and potential future environmental contaminants.     

Volatilization rates of intermediate and low volatility chemicals from water

This paper reports laboratory methods for measuring the gas and liquid phase mass transfer coefficients and volatilization rate constants of intermediate and low volatility compounds and proposes a method for calculating the volatilization rate constants of these types of compounds in the environment.     

Sorption of heterocyclic compounds from a complex mixture of coal-tar compounds on natural clayey till

The sorption and desorption of heterocyclic organic compounds in a complex multisolute system to a natural clayey till was investigated. The composition of the solutes reflect a simplified composition of an aqueous phase in contact with coal tar. Sorption was studied for two ratios (s:l) of clayey till (solid) to aqueous phase (liquid). The effect of the complex mixture of solutes on sorption of the four heterocyclic compounds: benzofuran, dibenzofuran, benzothiophene, and dibenzothiophene is evaluated by comparison with their sorption measured in single-solute systems. Sorption of the four compounds is affected by the complex mixture, with sorption decreases for all four compounds at high s:l ratio indicating competitive sorption. The effect on sorption of the individual compounds is not related to solubility or hydrophobicity of the compounds. Freundlich-type isotherms are observed for all compounds in the high s:l-ratio experiments, but for the most hydrophobic compounds isotherms are close to linear. The sorption of N-compounds and benzofuran is apparently influenced by cation exchange and dipole–dipole attraction to clay minerals. At high concentrations a dramatic increase in the sorption of the most strongly sorbing compounds is observed in the low s:l-ratio experiment. The dramatic increase in sorption appears to be a result of multimolecular layer sorption or condensation on surfaces in the clayey till at high surface density of organic compounds, and the data are fitted by BET (Brunauer, Emmet, and Teller) type 2 isotherms. The increase may or may not be induced by the presence of N-heterocyclic compounds sorbed by cation exchange and dipole–dipole attraction. The desorption of the compounds was studied for the low s:l ratio where multimolecular layer formation apparently had occurred. Partially irreversible sorption, hysteric Langmuir type desorption with isotherms of very high K_l coefficient, or behaviour reflecting dissolution of a condensed phase is observed.     

Models for estimating organic emissions from building materials: Formaldehyde example

One important source of chronic exposure to low levels of organic compounds in the indoor environment is emissions from building materials. Because removal of offending products may be costly or otherwise impractical, it is important that the emissions of organic pollutants be understood prior to incorporation of these materials into buildings. Once the organic pollutants of concern are identified, based on potential health effects and emission potential from the building material, it is necessary that an emission model be developed to predict the behavior of emission rates under various indoor conditions. Examples of the type of requirements that must be addressed in developing models for estimating organic emissions from building materials into the indoor environment are presented. Important factors include the products' characteristic source strengths at standard test conditions, impact of variations in environmental conditions (such as temperature and humidity), concentrations of the modeled organic pollutants in indoor environments and product ages. Ideally, emission models should have physical/chemical bases so that the important physical factors can be identified and their relative importance quantified. Although a universal model describing organic emissions from all building materials may not be feasible due to the tremendous variety of organic products and building materials in use, the most studied of the volatile organic compounds from building materials, formaldehyde, is used to illustrate an approach to the development of a specific model for organic emissions.     

Fate of the herbicide 14C-terbuthylazine in Brazilian soils under various climatic conditions

14C-terbuthylazine was applied to three Brazilian soils in closed aerated laboratory microcosms, both under standardized and under natural Brazilian climate conditions. Volatilization from soil to air, leaching from soil to percolate water, and transport from upper to deeper soil layers were higher in sandy soil than in clay soil and in organic soil. Mineralization of 14C-terbuthylazine to 14CO2 was higher in sandy soil than in clay and organic soils under standardized climatic conditions, whereas it was higher in organic soil than in sandy soil under Brazilian summer conditions. Under natural Brazilian summer conditions, leaching as well as vertical transport within the soil were enhanced as compared to standardized climate conditions comprising lower precipitation rates; volatilization was strongly reduced under high irrigation conditions.     

A comparison of gas- and liquid-loaded sorbent standards for the calibration of measurements of volatile organic compounds

The monitoring of volatile organic compounds (VOCs) at environmental levels is commonly carried out in the field using Perkin-Elmer-type sorbent-based passive or active samplers. Measurements of important trace species, such as benzene, toluene and xylenes, are often calibrated using thermal desorption standards that are liquid loaded onto the sorbent. This method is normally adopted over the method of gas loading of standards, on the grounds of ease of application and cost. We report a comparison between sorbent standards prepared by both methods using the sorbent Carbopack X and show that under the conditions used here the two show good agreement with each other. We also present work using liquid-loaded standards on the sorbents Tenax and Chromosorb-106, prepared with the solvents cyclohexane and methanol. The results indicate that, to obtain 100% recovery of the determinands from the desorbed samplers, issues such as type of solvent and sorbent combination together with purge flow should be considered.     

Estimation of the aqueous solubility of complex organic compounds

The aqueous solubility of organic compounds depends on two contributing parameters: the ideal solubility and the activity coefficient. The methods available for the prediction of aqueous solubility have the ideal solubility term in common. They differ in the way they account for the activity coefficient. Various empirical and theoretical methods for predicting activity coefficients are compared in this report. The methods were first used with a Training Set of solutes. The same methods were then applied to a Test Set of solutes, which consisted of a series of compounds of pharmaceutical and environmental relevance. The Test Set encompassed a wide variety of chemical structures and high degree of structural complexity. Only those methods with a sound theoretical rationale are useful for both the Training and Test sets. A comparative evaluation of the methods tested was made through the quantification of the accuracy of their predictions and their range of applicability.     

A reactive transport model for mercury fate in soil—application to different anthropogenic pollution sources

Soil systems are a common receptor of anthropogenic mercury (Hg) contamination. Soils play an important role in the containment or dispersion of pollution to surface water, groundwater or the atmosphere. A one-dimensional model for simulating Hg fate and transport for variably saturated and transient flow conditions is presented. The model is developed using the HP1 code, which couples HYDRUS-1D for the water flow and solute transport to PHREEQC for geochemical reactions. The main processes included are Hg aqueous speciation and complexation, sorption to soil organic matter, dissolution of cinnabar and liquid Hg, and Hg reduction and volatilization. Processes such as atmospheric wet and dry deposition, vegetation litter fall and uptake are neglected because they are less relevant in the case of high Hg concentrations resulting from anthropogenic activities. A test case is presented, assuming a hypothetical sandy soil profile and a simulation time frame of 50 years of daily atmospheric inputs. Mercury fate and transport are simulated for three different sources of Hg (cinnabar, residual liquid mercury or aqueous mercuric chloride), as well as for combinations of these sources. Results are presented and discussed with focus on Hg volatilization to the atmosphere, Hg leaching at the bottom of the soil profile and the remaining Hg in or below the initially contaminated soil layer. In the test case, Hg volatilization was negligible because the reduction of Hg²⁺ to Hg⁰ was inhibited by the low concentration of dissolved Hg. Hg leaching was mainly caused by complexation of Hg²⁺ with thiol groups of dissolved organic matter, because in the geochemical model used, this reaction only had a higher equilibrium constant than the sorption reactions. Immobilization of Hg in the initially polluted horizon was enhanced by Hg²⁺ sorption onto humic and fulvic acids (which are more abundant than thiols). Potential benefits of the model for risk management and remediation of contaminated sites are discussed.     

A pesticide emission model (PEM) Part II: model evaluation

In the first part of the paper, the development of a numerical pesticide emission model (PEM) is described for predicting the volatilization of pesticides applied to agricultural soils and crops through soil incorporation, surface spraying, or in the furrow at the time of planting. In this paper the results of three steps toward the evaluation of PEM are reported. The evaluation involves: (i) verifying the numerical algorithms and computer code through comparison of PEM simulations with an available analytical solution of the advection/diffusion equation for semi-volatile solutes in soil; (ii) comparing hourly heat, moisture and emission fluxes of trifluralin and triallate modeled by PEM with fluxes measured using the relaxed eddy-accumulation technique; and (iii) comparison of the PEM predictions of persistence half-life for 29 pesticides with the ranges of persistence found in the literature. The overall conclusion from this limited evaluation study is that PEM is a useful model for estimating the volatilization rates of pesticides from agricultural soils and crops. The lack of reliable estimates of chemical and photochemical degradation rates of pesticide on foliage, however, introduces large uncertainties in the estimates from any model of the volatilization of pesticide that impacts the canopy.     

Gas chromatographic analysis of organic marker compounds in fine particulate matter using solid-phase microextraction

A gas chromatographic method that uses solid-phase microextraction for analysis of organic marker compounds in fine particulate matter (PM2.5) is reported. The target marker compounds were selected for specificity toward emission from wood smoke, diesel or gasoline combustion, or meat cooking. Temperature-programmed volatilization analysis was used to characterize the thermal stabilities and volatile properties of the compounds of interest. The compounds were thermally evaporated from a quartz filter, sorbed to a solid phase microextraction (SPME) fiber, and thermally desorbed at 280 degrees C in a gas chromatograph injection port connected via a DB 1701 capillary separating column. Various experimental parameters (fiber type, time, and temperature of sorption) were optimized. It was found that high extraction yield could be achieved using a polyacrylate fiber for polar substances, such as levoglucosan, and a 7-microm polydimethylsiloxane (PDMS)-coated fiber for nonpolar compounds, such as hopanes and polyaromatic hydrocarbon. A compromise was made by selecting a carboxen/PDMS fiber, which can simultaneously extract all of the analytes of interest with moderate-to-high efficiency at 180 degrees C within a 30-min accumulation period. The optimized method was applied to the determination of levoglucosan in pine wood combustion emissions. The simplicity, rapidity, and selectivity of sample collection with a polymer-coated SPME coupled to capillary gas chromatography (GC) made this method potentially useful for atmospheric chemistry studies.     

Modeling effects of moisture content and advection on odor causing VOCs volatilization from stored swine manure

Two models for evaluating the contents and advection of manure moisture on odor causing volatile organic compounds (VOC-odor) volatilization from stored swine manure were studied for their ability to predict the volatilization rate (indoor air concentration) and cumulative exposure dose: a MJ-I model and a MJ-II model. Both models simulating depletion of source contaminant via volatilization and degradation based on an analytical model adapted from the behavior assessment model of Jury et al. In the MJ-I model, manure moisture movement was negligible, whereas in the MJ-II model, time-dependent indoor air concentrations was a function of constant manure moisture contents and steady-state moisture advection. Predicted indoor air concentrations and inhaled doses for the study VOC-odors of p-cresol, toluene, and p-xylene varied by up to two to three orders of magnitude depending on the manure moisture conditions. The sensitivity analysis of both models suggests that when manure moisture movement exists, simply MJ-I model is inherently not sufficient to represent a more generally volatilization process, which can even become stringent as moisture content increases. The conclusion illustrates how one needs to include a wide variety of manure moisture values in order to fully assess the complex volatilization mechanisms that are present in a real situation.     

Quantifying the sorption of organic chemicals on sediments

The use of a reference compound to quantify the sorption of nonpolar organic chemicals is proposed. This is because organic carbon normalized sorption coefficients (K_OC) do appear to be dependent on the type of sediment, and are thus not generally applicable to characterize the sorption properties of chemicals. Therefore, in this paper the hypothesis that nonpolar chemicals sorb in a constant ratio, independent of the sediment, has been investigated. Evidence for this hypothesis is shown with data from the literature. This enables one to compare sorption properties of nonpolar compounds on different sediments, if the differences between the sediments are normalized with a reference chemical rather than with the organic carbon content. Sediments with an organic carbon content of less than 0.1% seem to be unsuitable, because the compounds do not sorb mainly on the organic carbon, but also on other parts of the sediment. Sorption coefficients of compounds with aqueous solubilities in the μg per liter range or octan-1-ol water partition coefficients of more than 10⁵ are strongly influenced by the experimental techniques used. For these compounds the sorption coefficients measured by different techniques are less comparable. To enable comparison of sorption coefficients of hydrophobic chemicals, the use of a chlorobenzene as a reference compound in sorption experiments is suggested.