Partition of Volatile Organic Compounds in Activated Sludge and Wastewater

Abstract

The Henry’s law constant is important in the gas-liquid mass transfer process. Apparent dimensionless Henry’s law constant, or the gas-liquid partition coefficient (K’ _H), for both hydrophilic (methanol, isopropyl alcohol, and acetone) and hydrophobic (toluene and p-xylene) organic compounds in deionized (DI) water, a wastewater with a maximum total dissolved organic carbon (DOC) content of 700 mg/L, and DI water mixed with a maximum activated sludge suspended solid (SS) concentration of 40,000 mg/L were measured using the single equilibrium technique at 293 K.

Experimental results demonstrate that the K’ _H of any of the test volatile organic compounds varied among three situations. First, the K’_H of the hydrophilic compounds in mixed liquor with the maximum SS concentration was 9–21% higher than those in DI water. Second, those for toluene and p-xylene were 77% and 93% lower, respectively, in the mixed liquor with the maximum SS concentration. Third, the K’_H values of all of the test compounds in the wastewater were only 10% lower than those in DI water.

A model was developed to relate K’ _H with wastewater DOC and the SS concentration in the activated sludge using an organic carbon-water partition coefficient and activated sludge-water partition coefficient as model parameters. The model was verified and model parameters for test compounds estimated.     

Bio-oxidation of airborne volatile organic compounds in an activated sludge aeration tank

An activated sludge aeration tank (40 x 40 x 300 cm, width x length x height) with a set of 2-mm orifice air spargers was used to treat gas-borne volatile organic compounds (VOCs; toluene, p-xylene, and dichloromethane) in air streams. The effects of liquid depth (Z), aeration intensity (G/A), the overall mass-transfer rate of oxygen in clean water (KLaO2), the Henry's law constant of the tested VOC (H), and the influent gaseous VOC concentration (C0) on the efficiency of removal of VOCs were examined and compared with a literature-cited model. Results show that the measured VOC removal efficiencies and those predicted by the model were comparable at a G/A of 3.75-11.25 m3/m2 hr and C0 of approximately 1000-6000 mg/m3. Experimental data also indicated that the designed gas treatment reactor with KLaO2 = 5-15 hr(-l) could achieve > 85% removal of VOCs with H = 0.24-0.25 at an aerated liquid depth of 1 m and > 95% removal of dichloromethane with H = 0.13 at a 1-m liquid depth.     

Use of extant kinetic parameters to predict effluent concentrations of specific organic compounds at full-scale facilities.

To use the results of kinetic tests to predict effluent concentrations of specific contaminants in activated sludge systems, the fraction of the biomass that has an ability to degrade the test compound (i.e., competent biomass) must be estimated. A calibration procedure was developed to assess the competent biomass concentration because the chemical oxygen demand (COD) fraction tended to underestimate the degrading fraction for three of the four test compounds. Acetone, for instance, had a measured influent COD fraction of 0.08%, and the actual competent fraction was estimated to be 2.3%, based on the model calibration. Once the competent biomass fraction in the mixed liquor was determined, the extant kinetic parameters were subsequently used to predict activated sludge system performance. Predicted effluent concentrations were within 2, 5, and 16% of the average measured concentrations for acetone, linear alkylbenzene sulfonate, and furfural, respectively. Day-to-day predictions for these compounds were less accurate, possibly because of the non-steady-state nature of the activated sludge systems studied. The difference between the fraction of the influent COD contributed by the target compounds and the competent biomass fraction in the mixed liquor was found to be more significant when the target compound contributed less than 1% of the influent organic matter. The chemical structure of the target compound and chemical composition of the influent likely had an effect on the resulting competent biomass concentration. The total maximum growth rate, microX, was observed to be independent of the influent concentration of acetone and furfural, thus suggesting that the competent biomass concentration for these compounds was not affected by the changes in their influent concentrations. Consequently, a majority of competent biomass growth resulted from the degradation of other substrates, resulting in a competent biomass concentration significantly higher than predicted based on the influent COD fraction contributed by the test compound.     

Environmental hazard profile of organic chemicals: An experimental method for the assessment of the behaviour of organic chemicals in the ecosphere by means of simple laboratory tests with 14C labelled chemicals

The concept of “Environmental Hazard Profile” developed at this institute has been tested with 100 ¹⁴C-labelled organic compounds. Concentration factors in activated sludge, in algae and fish were determined. The microbial degradation of the chemicals to CO₂ in activated sludge and the decomposition to CO₂ under artificial light were determined. Ranking of compounds is given in the order of falling concentration factors and accumulation in rats respectively, and decreasing rates of decomposition. Relationship between chemical structure and accumulative and degradative behaviours is demonstrated using some selected groups of chemicals, such as benzenes, phenols, biphenyls and polyaromatic hydrocarbons. Correlations between the octanol/water partition coefficient, concentration factors and rates of decomposition could be established. Evaluation of test compounds was possible using hazard profiles obtained by the sum of single test results.     

Comparison of sludge characteristics and PCR-DGGE based microbial diversity of nanofiltration and microfiltration membrane bioreactors

The objective of this study was to compare the sludge characteristics and microbial community diversity between the submerged nanofiltration membrane bioreactor (NF MBR) and microfiltration membrane bioreactor (MF MBR) treating the same municipal wastewater. The influence of a higher concentration of organic matter and salt was investigated. The results of water qualities showed that the dissolved organic carbon (DOC), total phosphorus (T-P) and salt concentrations of the supernatant in the NF MBR were three, four and two times as high as those in the MF MBR, respectively. The specific oxygen uptake rate of the NF MBR (2.9+/-0.4 mg O(2)g(-1)MLSSh(-1)) was lower than that of the MF MBR (4.3+/-1.1 mg O(2)g(-1)MLSS h(-1)). Result of extractable extracellular polymeric substances showed that the NF MBR sludge had more protein and less polysaccharide compared to the MF MBR sludge, whereas specific amount of total organic carbon were the same in both MBRs. The median floc diameters of the NF MBR and the MF MBR were 72+/-12 microm and 59+/-12 microm, respectively, which could be attributable to the different polysaccharide concentrations between both MBR mixed liquor. A higher concentration of materials (DOC, T-P and salt) in the bioreactor, determined by the high rejection rate of the NF membrane, did not significantly affect the microbial diversity under similar operation conditions.     

A screening method for preliminary assessment of risk to groundwater from land-applied chemicals

A simple mathematical model for initial screening is presented that can aid in evaluating the relative risk to groundwater from applying nonpolar synthetic organic chemicals to soil. The basic premise is that the magnitude of the quotient of the chemical concentration of the water entering the aquifer and the maximum allowable concentration (as established by EPA or Health Departments) represents the health risk of a chemical. The chemical concentration of the soil water is estimated based on conservative, simplifying assumptions and requires only readily available data such as: basic soil properties (organic matter and saturated hydraulic conductivity), organic chemical properties (octanol-water partition coefficient and degradation rate) and environmental factors (recharge rate and depth to groundwater).The methodology was applied to assess the relative risk of organic chemicals in municipal sewage sludge and pesticides applied to agricultural land. The results are realistic.     

Fate and transport of monoterpenes through soils. Part I. Prediction of temperature dependent soil fate model input-parameters

Monoterpenes are C10H(n)O(n') compounds of natural origin and are potentially environmentally safe substitutes for traditional pesticides. Still, an assessment of their environmental behaviour is required. As a first step in a theoretical study focussing on monoterpenes applied as pesticides to terrestrial environments, soil fate model input-parameters were determined for 20 monoterpenes with widely different structural characteristics. Input-parameters are the water solubility (S(W)), vapour pressure (P), n-octanol-water partition coefficient (K(OW)), atmospheric air and bulk water diffusion coefficients (D(A)air and D(W)water), first order biodegradation rate constants (k), and their temperature dependence. Values for these parameters were estimated or taken from previous experimental work. The quality of the estimations was discussed by focussing on their statistics and by comparison with available experimental data. From these properties, the air-water partition coefficient (K(AW), Henry's Law constant), the interface-water partition coefficient (K(IW)) and the organic matter-water partition coefficient (K(OM)) could be estimated with varying levels of accuracy. In general, little experimental data turned out to be available on biodegradation rate constants and on the temperature dependence of physico-chemical parameters.     

Salting-in and salting-out effects of ionic and neutral osmotica on limonene and linalool Henry's law constants and octanol/water partition coefficients

Foliar emission rates of plant-generated volatile monoterpenes depend on monoterpene partitioning between air, aqueous and lipid-phases in the leaves. While Henry's law constants (H pc, equilibrium gas/water partition coefficient) and octanol/water partition coefficients (K OW) for pure water have been previously used to simulate monoterpene emissions from the leaves, aqueous phase in plants is a complex solution of electrolytes and neutral osmotica. We studied the effects of dissociated compounds KCl and glycine and sugars glucose, sorbitol and sucrose with concentrations between 0 and 1M on H pc and K OW values for limonene and linalool. Linalool with ca. 1500-fold lower H(pc) (2.62 Pa m(3)mol(-1) for pure water at 30 degrees C) and ca. 30-fold lower K OW (955 mol mol(-1) for pure water at 25 degrees C) is the more hydrophilic compound of the two monoterpenes. H pc of both monoterpenes increased with increasing concentration of both ionic compounds and sorbitol, but decreased with increasing glucose and sucrose concentrations. The salting-out coefficients for H pc (kH) were ca. an order of magnitude larger for more hydrophilic compound linalool than for more hydrophobic limonene. For linalool, co-solutes modified H pc by 30-50% at the highest concentration (1M) tested. The effect of temperature on the salting-out coefficient of KCl was minor. As with H pc, K OW increased with increasing the concentration of KCl, glycine and sorbitol, and decreased with increasing glucose and sucrose concentrations. For limonene, co-solutes modified K OW by 20-50% at the highest concentration used. For linalool, the corresponding range was 10-35%. Salting-out coefficients for H pc and K OW were correlated, but the lipid-solubility was more strongly affected than aqueous solubility in the case of limonene. Overall, these data demonstrate physiologically important effects of co-solutes on H pc and K OW for hydrophilic monoterpenes and on K OW for hydrophobic monoterpenes that should be included in current emission models.     

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.     

污泥含炭吸附剂对挥发性有机废气吸附实验研究

研究了污泥含炭吸附剂对挥发性有机污染物的吸附特性。结果表明,污泥含炭吸附剂对苯系物的吸附为典型的物理吸附,其吸附甲苯等温线的类型系优惠型吸附等温线,表明具有良好的吸附能力;在吸附反应温度为20℃,气体流量为500 mL/m in(停留时间为0.424 s),甲苯浓度为2 700 mg/m3时,甲苯的饱和吸附容量为150.0 mg/g;同时,研究表明污泥含炭吸附剂对苯系物的饱和吸附容量和吸附强弱次序为二甲苯甲苯苯。结果表明污泥含炭吸附剂适合对中低浓度有机废气的吸附净化。     

Distribution of PAHs and PCBs to dissolved organic matter: high distribution coefficients with consequences for environmental fate modeling

Dissolved organic carbon/water distribution coefficients (K(DOC)) were measured for a selection of PCBs with octanol/water partition coefficients (K(OW)) ranging from 10(5.6) to 10(7.5). A solid phase dosing and sampling technique was applied to determine K(DOC) to Aldrich humic acid. This technique is in particular suitable for determining the distribution of very hydrophobic chemicals to complex matrices like humic acids. The K(DOC) values were calculated from the experimental data using a linear model. Determined K(DOC)'s were evaluated in relation to octanol/water partition coefficients of the test compounds, and compared to literature data. Measured K(DOC) values were somewhat higher than literature data, which can probably be attributed to the overestimation of freely dissolved aqueous concentration as a result of incomplete phase separation in other studies, and to the unique character of Aldrich humic acid as a "sorbent" or co-solute or to the fact that Aldrich humic acid is not a typical DOC, and other (adsorption) processes can occur. This study reports DOC distribution coefficients that belong to the highest ones ever measured. In addition, the DOC distribution was discussed in relation to current risk assessment modeling.     

Tunnel study of on-road vehicle emissions and the photochemical potential in Taiwan

Motor vehicle emission factors of carbon monoxide (CO) and non-methane volatile organic compounds (NMVOCs) were calculated inside the Chung-Cheng Tunnel of Kaohsiung in Taiwan. The results were compared with those model predictions from the Mobile Taiwan 2.0 model. Individual concentrations of 21 species of NMVOCs were also determined. Photochemical potential of NMVOCs was evaluated by using the maximum incremental reactivity (MIR). Field data showed that the integrated emission factors of CO and NMVOCs for actual fleet were 6.3 and 1.5 g/veh km, respectively. The error range of these factors may be up to 45%. The predicted values by the Mobile Taiwan 2.0 model closely matched the observed data. Concentrations of isopentane, 2-methylpentane, toluene and m,p-xylene were the dominant species of NMVOCs. The ratio of maximum incremental reactivity to NMVOCs concentration was 3.9, similar to those of the studies in the US Fort McHenry and Tuscarora Tunnel.     

Heavy metal binding by the polymeric organic fractions of sewage sludges

Organic complexes in sewage sludge play an important role in the speciation and transformation of metals into potentially more toxic and bioavailable forms. Two organic fractions, bacterial extracellular polymer and fulvic acid, were extracted from mixed liquor and digested sewage sludge by methods established as the most appropriate. The homogeneity of the extracts was verified using gel permeation chromatography. Conditional stability constants and complexation capacities of the organic fractions from the sludges with copper, cadmium, nickel and zinc have been determined using equilibrium dialysis titration. Organic fractions extracted from digested sludge demonstrated a greater capacity to complex metals over mixed liquor extracts. Copper formed stronger complexes than nickel with the mixed liquor biomass and cadmium exhibited the greatest affinity for digested sludge organic matter.     

Persistent organic pollutants (POPs) in the conventional activated sludge treatment process: model predictions against experimental values

The FATE and treatibility estimator (FATE) model, developed by the United States Environmental Protection Agency was used for the prediction of the FATE of 26 persistent organic pollutants (POPs), i.e. 7 PCBs and 19 organochlorine compounds (OCs), during the conventional activated sludge treatment process applied in the waste water treatment plant (WWTP) of Thessaloniki, Greece. The removal rates predicted by the model for the primary and the secondary treatment stages were found to differ substantially from those experimentally measured. When the overall treatment was considered, the differences between measured and model predicted removals were within acceptable limits of confidence. Possible reasons that might cause deviations from experimental values were suggested to be the wastewater content in dissolved organic carbon (DOC), and/or the low concentrations of POPs in untreated wastewater.     

Improved computational model (AQUIFAS) for activated sludge, integrated fixed-film activated sludge, and moving-bed biofilm reactor systems, part III: analysis and verification

Research was undertaken to analyze and verify a model that can be applied to activated sludge, integrated fixed-film activated sludge (IFAS), and moving-bed biofilm reactor (MBBR) systems. The model embeds a biofilm model into a multicell activated sludge model. The advantage of such a model is that it eliminates the need to run separate computations for a plant being retrofitted from activated sludge to IFAS or MBBR. The biofilm flux rates for organics, nutrients, and biomass can be computed by two methods-a semi-empirical model of the biofilm that is relatively simpler, or a diffusional model of the biofilm that is computationally intensive. Biofilm support media can be incorporated to the anoxic and aerobic cells, but not the anaerobic cells. The model can be run for steady-state and dynamic simulations. The model was able to predict the changes in nitrification and denitrification at both pilot- and full-scale facilities. The semi-empirical and diffusional models of the biofilm were both used to evaluate the biofilm flux rates for media at different locations. The biofilm diffusional model was used to compute the biofilm thickness and growth, substrate concentrations, volatile suspended solids (VSS) concentration, and fraction of nitrifiers in each layer inside the biofilm. Following calibration, both models provided similar effluent results for reactor mixed liquor VSS and mixed liquor suspended solids and for the effluent organics, nitrogen forms, and phosphorus concentrations. While the semi-empirical model was quicker to run, the diffusional model provided additional information on biofilm thickness, quantity of growth in the biofilm, and substrate profiles inside the biofilm.     

The role of dissolved organic carbon in the mobility of Cd, Ni and Zn in sewage sludge-amended soils

A pot experiment was conducted to investigate the effect of application of naturally derived dissolved organic compounds (DOC) on the uptake of Cd, Ni and Zn by Lolium perenne L. from mixtures of soil and sewage sludge and on their extractability with CaCl2. DOC was applied at concentrations of 0, 285 and 470 mg l(-1) to a loamy sand (LS) and a sandy clay loam (SCL) soil mixed with sewage sludge at rates equivalent to 0, 10 and 50 t ha(-1). DOC applications significantly increased the extractability of metals and also their uptake by ryegrass, but the increase was greater where sludge was applied at 50 t ha(-1). It is suggested that DOC in soils significantly increased the availability of the metals to plants. This was especially the case in the LS soil, where DOC had less competition with surface sorption than in the SCL soil.     

Effect of substrate Henry's constant on biofilter performance

Butanol, ether, toluene, and hexane, which have Henry's constants ranging from 0.0005 to 53, were used to investigate the effects of substrate solubility or availability on the removal of volatile organic compounds (VOCs) in trickle-bed biofilters. Results from this study suggest that, although removal of a VOC generally increases with a decrease in its Henry's constant, an optimal Henry's constant range for biofiltration may exist. For the treatment of VOCs with high Henry's constant values, such as hexane and toluene, the transfer of VOCs between the vapor and liquid phases or between the vapor phase and the biofilm is a rate-determining step. However, oxygen (O2) transfer may become a rate-limiting step in treating VOCs with low Henry's constants, such as butanol, especially at high organic loadings. The results demonstrated that in a gas-phase aerobic biofilter, nitrate can serve both as a growth-controlling nutrient and as an electron acceptor in a biofilm for the respiration of VOCs with low Henry's constants. Microbial communities within the biofilters were examined using denaturing gradient gel electrophoresis to provide a more complete picture of the effect of O2 limitation and denitrification on biofilter performance.     

Vapour pressures, aqueous solubilities, Henry's law constants, partition coefficients between gas/water (Kgw), n-octanol/water (Kow) and gas/n-octanol (Kgo) of 106 polychlorinated diphenyl ethers (PCDE)

Modelling the environmental fate of persistent organic pollutants like polychlorinated diphenyl ethers (PCDE) requires the knowledge of a number of fundamental physico-chemical properties of these compounds. We report here the physico-chemical properties of 106 PCDEs, which are over 50% of all possible congeners. Vapour pressures P(OL), water solubilities S(H2O), and n-octanol/water partition coefficients K(OW) were determined with chromatographic methods. With these experimental data the Henry's law constants H, gas/water K(GW) and gas/n-octanol K(GO) partition coefficients were calculated. Vapour pressures and water solubilities and n-octanol/water partition coefficients of the PCDEs are close to those of similar groups of organochlorine compounds like polychlorinated biphenyls (PCBs) and dibenzofurans (PCDFs). A similar environmental fate can be predicted and was partially already been observed.     

Pyrolysis kinetics and residue characteristics of petrochemical industrial sludge

This study investigated the pyrolysis characteristics of sludge from wastewater treatment plants in the petrochemical industry and focused on the pyrolysis kinetics, elemental composition of residue, and volatile organic compounds (VOCs) of exhaust gas. As pyrolysis temperature increased to 773 K, the increasing rate of crude oil production tended to a stable condition. The result indicated that the optimal temperature of crude oil and water mixed production was 773 K. When pyrolysis temperature increased from 673 to 973 K, carbon, oxygen, nitrogen, and hydrogen concentrations of residue decreased and the sulfur concentration of residue increased. The concentrations of benzene, toluene,ethylbenzene, and styrene increased by the increasing pyrolysis temperature. We found that the reaction order of sludge pyrolysis was 2.5 and the activation energy of the reaction was 11.06 kJ/mol. We believe that our pyrolysis system is transitional between devolatilization and combustion.     

Mechanism of effective nocardioform foam control measures for non-selector activated sludge systems.

Solids retention time (SRT), biological scum trapping and recycle, and the dynamic equilibrium between Nocardioform populations in the foam and the mixed liquor are the controlling factors in activated sludge foaming events caused by Nocardioform bacteria. For the operating modes described in this paper, a cured mixed liquor foaming condition (filament counts of approximately 10(5) intersections/g volatile suspended solids) was only achieved when SRT control, selective wasting, and polymer addition were in effect. Solids retention time control, with the SRT remaining below 1.5 days, and selective wasting will cure a severely foaming mixed liquor, but effects will only be observed after 3 or 4 months after implementation. The combined wastage of Nocardioform bacteria from selective wasting and SRT control can ensure long-term foam control to the operation of a pure-oxygen activated sludge system with foam-trapping features. An SRT of 0.3 days will result in the complete washout of Nocardioform bacteria from the activated sludge system, which can then operate at an SRT of 3 days free of Nocardioform. Polymer addition to mixed liquor is only effective for foam control when a large portion of the system biomass exists as a heavy layer of foam above the mixed liquor.