Evolution rates and PCB content of surface films that develop on impervious urban surfaces

Surface films on impervious surfaces mediate the fate of organic contaminants in urban areas. Using sheltered 3-mm diameter glass beads as a surrogate impervious urban surface, studies in downtown Toronto showed that surface films developed at a consistent rate of 1.6–2.6 nm day⁻¹. Linear film growth was observed up to and including the last day of three studies of 89-, 273-, and 84-day duration. Total PCB content (sum of 15 PCB congeners) also increased linearly, at a similar rate as the surface film. A complementary study using unsheltered beads showed that up to 80% of film mass and PCB content were removed by film wash-off during rain events. The film growth rate on beads exposed at a rural site, 200 km northeast of Toronto, was 12–20 times lower with PCB burdens that were 7–22 times lower compared to Toronto. Based on these findings, it is estimated that approximately 56–226 g of PCBs are captured by a 70 nm thick film covering just the horizontal surface area of Toronto. This is a substantial quantity of PCB that is available for rapid surface–air exchange and wash-off.     

Evaluation of methods for the physical characterization of the fine particle emissions from two residential wood combustion appliances

The fine particle emissions from a U. S. certified non-catalytic wood stove and a zero-clearance fireplace burning Quercus rubra L. (northern red oak) and Pseudotsuga menziesii (Douglas fir) cordwood each at two different moisture levels were determined. Emission testing was performed using both time-integrated and continuous instrumentation for total particle mass, particle number, particle size distribution, and fixed combustion gases using an atmospheric wind tunnel, full-flow laboratory dilution tunnel, and dilution stack sampler with a comparison made between the three dilution systems and two sampling filter types. The total mass emission factors (EFs) for all dilution systems and filter media are extremely variable ranging from <1 to 55 g kg⁻¹ of dry wood depending on the combination of appliance type, wood species and moisture content, filter medium, and dilution system. For Teflon filter sampling of stove emissions in the wind tunnel, the total mass EFs varied from 2 to 8 g kg⁻¹ of dry fuel depending on wood type whereas the equivalent fireplace emissions burning wet oak averaged 11 g kg⁻¹. A substantial number of ultrafine particles in the accumulation size range were also observed during all tests as determined by an Electrical Low Pressure Impactor (ELPI) and Scanning Mobility Particle Sizer. The PM-2.5 (particles ≤2.5 μm in aerodynamic diameter) fractions determined from the ELPI electrometer data ranged from 93 to 98% (mass) depending on appliance type as reported previously by Hays et al. (Aerosol Science, 34, 1061, 2003).     

Oxidative properties of ambient PM2.5 and elemental composition: Heterogeneous associations in 19 European cities

We assessed the extent to which constituents of PM_2.5 (transition metals, sodium, chloride) contribute to the ability to generate hydroxyl radicals (OH) in vitro in PM_2.5 sampled at 20 locations in 19 European centres participating in the European Community Respiratory Health Survey. PM_2.5 samples (n = 716) were collected on filters over one year and the oxidative activity of particle suspensions obtained from these filters was then assessed by measuring their ability to generate OH in the presence of hydrogen peroxide. Associations between OH formation and the studied PM constituents were heterogeneous. The total explained variance ranged from 85% in Norwich to only 6% in Albacete. Among the 20 centres, 15 showed positive correlations between one or more of the measured transition metals (copper, iron, manganese, lead, vanadium and titanium) and OH formation. In 9 of 20 centres OH formation was negatively associated with chloride, and in 3 centres with sodium. Across 19 European cities, elements which explained the largest variations in OH formation were chloride, iron and sodium.     

Simultaneous E. coli inactivation and NOM degradation in river water via photo-Fenton process at natural pH in solar CPC reactor. A new way for enhancing solar disinfection of natural water

Bacteria inactivation and natural organic matter oxidation in river water was simultaneously conducted via photo-Fenton reaction at “natural” pH (6.5) containing 0.6 mg L⁻¹ of Fe³⁺ and 10 mg L⁻¹ of H₂O₂. The experiments were carried out by using a solar compound parabolic collector on river water previously filtered by a slow sand filtration system and voluntarily spiked with Escherichia coli. Fifty five percent of 5.3 mg L⁻¹ of dissolved organic carbon was mineralized whereas total disinfection was observed without re-growth after 24 h in the dark.     

Converging hydrostatic and hydromechanic concepts of preferential flow definitions

The boundary between preferential flow and Richards-type flow is a priori set at a volumetric soil water content θ at which soil water diffusivity D (θ) = η (= 10^− 6 m² s^− 1), where η is the kinematic viscosity. First we estimated with a hydrostatic approach from soil water retention curves the boundary, θ^K, between the structural pore domain, in which preferential flow occurs, and the matrix pore domain, in which Richards-type flow occurs. We then compared θ^K with θ that was derived from the respective soil hydrological property functions of same soil sample. Second, from in situ investigations we determined 96 values of θ^G as the terminal soil water contents that established themselves when the corresponding water-content waves of preferential flow have practically ceased. We compared the frequency distribution of θ^G with the one of θ that was calculated from the respective soil hydrological property functions of 32 soil samples that were determined with pressure plate apparatuses in the laboratory. There is support of the notion that θ^K ≈ θ^G ≈ θ, thus indicating the potential of θ to explain more generally what constitutes preferential flow. However, the support is assessed as working hypothesis on which to base further research rather than a procedure to a clear-cut identification of preferential flow and associated flow paths.     

Spatial disaggregation of traffic emission inventories in large cities using simplified top–down methods

Simple, inexpensive and accurate methods for assessing the spatial distribution of traffic emissions are badly needed for the environmental management in South American cities. In this study, various spatial disaggregation methods of traffic emissions of carbon monoxide are presented and evaluated for a large city (Santiago de Chile). Previous methods have used a simplified road network as a proxy for deriving spatial patterns of emissions. However, these approaches resulted in underestimation of emissions in urban centers, industrial zones and highly loaded roads, as well as overestimation in residential zones. Here we modify these methods by adding data correlated with the emissions (e.g. traffic counts, vehicles mean speed, road capacity) solving partially or completely the indicated problems. After an accuracy-simplicity analysis two methodologies stand out over the others: using traffic count classification and using a land use map, both combined with a simplified road network. Both are top–down approaches that correlate well (0.9) with the reference emissions and capture emission peaks (within 30% relative error). Hence the proposed changes allow an improved balance between accuracy and costs (monetary, availability of data and time to obtain data).     

Degassing of H/He, CFCs and SF6 by denitrification: Measurements and two-phase transport simulations

The production of N₂ gas by denitrification may lead to the appearance of a gas phase below the water table prohibiting the conservative transport of tracer gases required for groundwater dating. We used a two-phase flow and transport model (STOMP) to study the reliability of ³H/³He, CFCs and SF₆ as groundwater age tracers under agricultural land where denitrification causes degassing. We were able to reproduce the amount of degassing (R² = 69%), as well as the ³H (R² = 79%) and ³He (R² = 76%) concentrations observed in a ³H/³He data set using simple 2D models. We found that the TDG correction of the ³H/³He age overestimated the control ³He/³He age by 2.1 years, due to the accumulation of ³He in the gas phase. The total uncertainty of degassed ³H/³He ages of 6 years (± 2 σ) is due to the correction of degassed ³He using the TDG method, but also due to the travel time in the unsaturated zone and the diffusion of bomb peak ³He. CFCs appear to be subject to significant degradation in anoxic groundwater and SF₆ is highly susceptible to degassing. We conclude that ³H/³He is the most reliable method to date degassed groundwater and that two-phase flow models such as STOMP are useful tools to assist in the interpretation of degassed groundwater age tracer data.     

Coupled infrared extinction spectra and size distribution measurements for several non-clay components of mineral dust aerosol (quartz, calcite, and dolomite)

Simultaneous size distributions and Fourier transform infrared (FTIR) extinction spectra have been measured for several representative components of mineral dust aerosol (quartz, calcite, and dolomite) in the fine particle size mode (D=0.1–1 μm). Optical constants drawn from the published literature have been used in combination with the experimentally determined size distributions to simulate the extinction spectra. In general, Mie theory does not accurately reproduce the peak position or band shape for the prominent IR resonance features in the 800–1600 cm⁻¹ spectral range. The resonance peaks in the Mie simulation are consistently blue shifted relative to the experimental spectra by 20–50 cm⁻¹. Spectral simulations, derived from a simple Rayleigh-based analytic theory for a “continuous distribution of ellipsoids” particle shape model, better reproduce the experimental spectra, despite the fact that the Rayleigh approximation is not strictly satisfied in these experiments. These results differ from our previous studies of particle shape effects in silicate clay mineral dust aerosols where a disk-shaped model for the particles was found to be more appropriate.     

Reduction of pharmaceutically active compounds by a lagoon wetland wastewater treatment system in Southeast Louisiana

A number of pharmaceutically active compounds (PhACs) have been detected in the aquatic environment as a result of discharges of municipal wastewater. In the state of Louisiana, USA, many municipalities treat wastewater using natural systems, such as lagoons and wetlands, rather than conventional wastewater treatment technologies. Nearly all research to date has focused on the fate of PhACs in conventional treatment plants, not constructed and natural wetlands. In the wastewater treatment plant (WWTP) for Mandeville, Louisiana, USA, wastewater flows of 7600 m³ d⁻¹ are treated in a series of aeration lagoons (basins), followed by a constructed wetland and UV disinfection, before being discharged into a natural forested wetland (i.e. Bayou Chinchuba) and eventually, Lake Pontchartrain. Thirteen out of the 15 PhACs investigated were detected in the wastewater inflow to the treatment plant. Only 9 of the 13 compounds were above the detection limits at the treatment plant effluent. The concentrations of most compounds were reduced by greater than 90% within the plant, while carbamazepine and sotalol were only reduced by 51% and 82%, respectively. The percent reductions observed in the Mandeville system were greater than reduction rates reported for conventional WWTPs; perhaps due to the longer treatment time (30 days). Most target PhACs were not completely removed before discharge into Lake Pontchartrain, although their collective annual loading was reduced to less than 1 kg and down to ppb with significant potential for dilution in the large lake.     

Degradation of acetic acid with sulfate radical generated by persulfate ions photolysis

The photolysis of was studied for the removal of acetic acid in aqueous solution and compared with the H₂O₂/UV system. The radicals generated from the UV irradiation of ions yield a greater mineralization of acetic acid than the OH radicals. Acetic acid is oxidized by radicals without significant formation of intermediate by-products. Increasing system pH results in the formation of OH radicals from radicals. Maximum acetic acid degradation occurred at pH 5. The results suggest that above this pH, competitive reactions with the carbon mineralized inhibit the reaction of the solute with and also OH radicals. Scavenging effects of two naturally occurring ions were tested; in contrast to ions, the presence of Cl⁻ ions enhances the efficiency of the /UV process towards the acetate removal. It is attributed to the formation of the Cl radical and its great reactivity towards acetate.     

Nature and prevalence of non-additive toxic effects in industrially relevant mixtures of organic chemicals

The concentration addition (CA) and the independent action (IA) models are widely used for predicting mixture toxicity based on its composition and individual component dose–response profiles. However, the prediction based on these models may be inaccurate due to interaction among mixture components. In this work, the nature and prevalence of non-additive effects were explored for binary, ternary and quaternary mixtures composed of hydrophobic organic compounds (HOCs). The toxicity of each individual component and mixture was determined using the Vibrio fischeri bioluminescence inhibition assay. For each combination of chemicals specified by the 2ⁿ factorial design, the percent deviation of the predicted toxic effect from the measured value was used to characterize mixtures as synergistic (positive deviation) and antagonistic (negative deviation). An arbitrary classification scheme was proposed based on the magnitude of deviation (d) as: additive (10%, class-I) and moderately (10 < d  30%, class-II), highly (30 < d  50%, class-III) and very highly (>50%, class-IV) antagonistic/synergistic. Naphthalene, n-butanol, o-xylene, catechol and p-cresol led to synergism in mixtures while 1, 2, 4-trimethylbenzene and 1, 3-dimethylnaphthalene contributed to antagonism. Most of the mixtures depicted additive or antagonistic effect. Synergism was prominent in some of the mixtures, such as, pulp and paper, textile dyes, and a mixture composed of polynuclear aromatic hydrocarbons. The organic chemical industry mixture depicted the highest abundance of antagonism and least synergism. Mixture toxicity was found to depend on partition coefficient, molecular connectivity index and relative concentration of the components.     

Impact of initial and boundary conditions on preferential flow

Preferential flow in soil is approached by a water-content wave, WCW, that proceeds downward from the ground surface. WCWs were obtained from sprinkler experiments with infiltration rates varying from 5 to 40 mm h^− 1. TDR-probes and tensiometers measured volumetric water contents θ(z,t) at seven depths, and capillary heads, h(z,t) at six depths in a column of an undisturbed soil. The wave is characterized by the velocity of the wetting front, c_W, the amplitude, w_S, and the final water content, θ. We tested with uni-variate and bi-variate linear regressions the impacts of initial volumetric water contents, θ_ini, and input rates, q_S, on c_W, w_S and θ.The test showed that θ_ini influenced θ and w_S and q_S effected c_W. The expected proportionality of w_S ≈ qs^1/3 was weak and c_W ≈ qs^2/3 was strong.     

pH dependence of persulfate activation by EDTA/Fe(III) for degradation of trichloroethylene

The ability of free ferrous ion activated persulfate (S₂O₈²⁻) to generate sulfate radicals (SO₄⁻) for the oxidation of trichloroethylene (TCE) is limited by the scavenging of SO₄⁻ with excess Fe²⁺ and a quick conversion of Fe²⁺ to Fe³⁺. This study investigated the applicability of ethylene-diamine-tetra-acetic acid (EDTA) chelated Fe³⁺ in activating persulfate for the destruction of TCE in aqueous phase under pH 3, 7 and 10. Fe³⁺ and EDTA alone did not appreciably degrade persulfate. The presence of TCE in the EDTA/Fe³⁺ activated persulfate system can induce faster persulfate and EDTA degradation due to iron recycling to activate persulfate under a higher pH condition. Increasing the pH leads to increases in pseudo-first-order-rate constants for TCE, S₂O₈²⁻ and EDTA degradations, and Cl generation. Accordingly, the experiments at pH 10 with different EDTA/Fe³⁺ molar ratios indicated that a 1/1 ratio resulted in a remarkably higher degradation rate at the early stage of reaction as compared to results by other ratios. Higher persulfate dosage under the EDTA/Fe³⁺ molar ratio of 1/1 resulted in greater TCE degradation rates. However, increases in persulfate concentration may also lead to an increase in the rate of persulfate consumption.     

Removal of toxic ions (chromate, arsenate, and perchlorate) using reverse osmosis, nanofiltration, and ultrafiltration membranes

Rejection characteristics of chromate, arsenate, and perchlorate were examined for one reverse osmosis (RO, LFC-1), two nanofiltration (NF, ESNA, and MX07), and one ultrafiltration (UF and GM) membranes that are commercially available. A bench-scale cross-flow flat-sheet filtration system was employed to determine the toxic ion rejection and the membrane flux. Both model and natural waters were used to prepare chromate, arsenate, and perchlorate solutions (approximately 100 μg L⁻¹ for each anion) in mixtures in the presence of other salts (KCl, K₂SO₄, and CaCl₂); and at varying pH conditions (4, 6, 8, and 10) and solution conductivities (30, 60, and 115 mS m⁻¹). The rejection of target ions by the membranes increases with increasing solution pH due to the increasingly negative membrane charge with synthetic model waters. Cr(VI), As(V), and rejection follows the order LFC-1 (>90%) > MX07 (25–95%)  ESNA (30–90%) > GM (3–47%) at all pH conditions. In contrast, the rejection of target ions by the membranes decreases with increasing solution conductivity due to the decreasingly negative membrane charge. Cr(VI), As(V), and rejection follows the order CaCl₂ < KCl  K₂SO₄ at constant pH and conductivity conditions for the NF and UF membranes tested. For natural waters the LFC-1 RO membrane with a small pore size (0.34 nm) had a significantly greater rejection for those target anions (>90%) excluding (71–74%) than the ESNA NF membrane (11–56%) with a relatively large pore size (0.44 nm), indicating that size exclusion is at least partially responsible for the rejection. The ratio of solute radius (r_i,s) to effective membrane pore radius (r_p) was employed to compare ion rejection. For all of the ions, the rejection is higher than 70% when the r_i,s/r_p ratio is greater than 0.4 for the LFC-1 membrane, while for di-valent ions (, , and ) the rejection (38–56%) is fairly proportional to the r_i,s/r_p ratio (0.32–0.62) for the ESNA membrane.     

A new approach to quantify the degradation kinetics of linuron with UV, ozonation and UV/O3 processes

The degradation of linuron, one of phenylurea herbicides, was investigated for its reaction kinetics by different treatment processes including ultraviolet irradiation (UV), ozonation (O₃), and UV/O₃. The decay rate of linuron by UV/O₃ process was found to be around 3.5 times and 2.5 times faster than sole-UV and ozone-alone, respectively. Experimental results also indicate overall rate constants increased exponentially with pH above 9.0 while the increase of rate constants with pH below 9 is insignificant in O₃ system. All dominant parameters involved in the three processes were determined in the assistant of proposed linear models in this study. The approach was found useful in predicting the process performances through the quantification of quantum yield (rate constant for the formation of free radical HOO⁻ from ozone decomposition at high pH), rate constant of linuron with ozone (k_O3,LNR), rate constant of linuron with hydroxyl radical (k_OH,LNR), and α (the ratio of the production rate of OH and the decay rate of ozone in UV/O₃ system).     

Carbonaceous aerosol emissions from India

Budget estimate for carbonaceous aerosols including black carbon (BC) and organic carbon, emitted from the combustion of various fuels, is very important for regional climate studies. Emission factors for carbonaceous aerosols from bio-fuels and soft coke were determined in a controlled combustion study. The emission factors thus obtained along with those available for other fossil fuels consumed in different sectors have been applied to assess the budget for carbonaceous aerosols from India. Preliminary calculations give a range of 1.6–1.8 Tg of carbonaceous aerosols that include 0.4–1.4 Tg of BC. A major (80%) portion of carbonaceous aerosols emitted from India is found to originate from the use of biomass for energy as 70–80% of energy requirement in rural India is met by combustion of traditional bio-fuels.     

Numerical simulation of an array of fences in Saemangeum reclaimed land

This paper discusses about the quantitative effect of windbreak fences on wind velocity in the reclaimed land at Saemangeum in South Korea. Windbreak fences were constructed in the reclaimed land to reduce the wind velocity to prevent the generation and diffusion of dust. However, up to this time, no in-depth studies were conducted to quantitatively measure the effect of the windbreak fences on wind velocity thus an optimum windbreak structure is not yet determined. Using CFD simulations, the effects of fence porosity, fence height, and the distance between the adjacent fences were investigated. A wind tunnel experiment was initially conducted and data gathered were used to develop the CFD models. From the experiments and CFD simulations, the overall percentage difference of the measured velocities was 7.20% which is generally acceptable to establishing the reliability of the CFD models. The reduction effect on wind velocity was measured in between the adjacent fences up to a height of 0.6 m from the ground surface. In terms of porosity ( = 0, 0.2, 0.4, 0.6), 0.2 was found to be the optimum value. Conversely, the effect of fence height (0.6, 0.8 and 1.0 m) showed no significant difference; therefore, 0.6 m height is recommended. In addition, the reduction effect of distance between the adjacent fences (2, 4 and 6 m) on wind velocity having a 0.2 porosity has decreased to about 75% regardless of the distance. In the case of the reclaimed land in Saemangeum, a decrease of 75% can prevent the generation and diffusion of dusts. However, the source of dusts is very large. Therefore, constructing an array of windbreak with 6 m distance between them is deemed necessary.     

Impact of the Saharan dust outbreaks on the ambient levels of total suspended particles (TSP) in the marine boundary layer (MBL) of the Subtropical Eastern North Atlantic Ocean

Six years (1998–2003) of measurements of ambient air concentrations of total suspended particulate (TSP) measured at a rural background monitoring station in Tenerife (Canary Islands), the El Río station (ER, 28°08′35″N, 16°39′20″W, 500 m a.s.l.) were studied. African dust outbreaks were objectively identified using a new quantitative tool, called the African Index. This index indicates the percentage of time that an air mass remained over an African region at one of three possible height intervals of the lower troposphere. After identifying these episodes, a study of the background TSP levels at the ER station and of direct and indirect (those which cause vertical deposition of dust) African air mass intrusion impacts was performed. Taking into account both direct and indirect episodes, a total of 322 days of African dust intrusion were objectively identified (a mean of 54 episodes per year) in the period 1998–2003, some of them caused by “transition episodes” or “return African air masses”. A subjective method confirmed that 256 of these days were caused by direct impacts of African dust on the ER station. A mean TSP value of 21.6 μg m⁻³ was found at the station during this period. All the episodes occurred when the TSP concentration was >28.5 μg m⁻³. The TSP background (14 μg m⁻³) can be assumed to be representative of the MBL of the Eastern North Atlantic subtropical region. The highest number of dust gravitational settlement (or indirect) episodes occurs in summer, but the highest contribution of these episodes to the TSP levels is in March with a monthly mean TSP contribution of up to 30.5 μg m⁻³.     

Simulation of aerosol radiative properties with the ORISAM-RAD model during a pollution event (ESCOMPTE 2001)

The aim of this study is to present the organic and inorganic spectral aerosol module-radiative (ORISAM-RAD) module, allowing the 3D distribution of aerosol radiative properties (aerosol optical depth, single scattering albedo and asymmetry parameter) from the ORISAM module. In this work, we test ORISAM-RAD for one selected day (24th June) during the ESCOMPTE (expérience sur site pour contraindre les modèles de pollution atmosphérique et de transport d’emissions) experiment for an urban/industrial aerosol type. The particle radiative properties obtained from in situ and AERONET observations are used to validate our simulations. In a first time, simulations obtained from ORISAM-RAD indicate high aerosol optical depth (AOD)0.50–0.70±0.02 (at 440 nm) in the aerosol pollution plume, slightly lower (10–20%) than AERONET retrievals. In a second time, simulations of the single scattering albedo (ω_o) have been found to well reproduce the high spatial heterogeneities observed over this domain. Concerning the asymmetry parameter (g), ORISAM-RAD simulations reveal quite uniform values over the whole ESCOMPTE domain, comprised between 0.61±0.01 and 0.65±0.01 (at 440 nm), in excellent agreement with ground based in situ measurements and AERONET retrievals. Finally, the outputs of ORISAM-RAD have been used in a radiative transfer model in order to simulate the diurnal direct radiative forcing at different locations (urban, industrial and rural). We show that anthropogenic aerosols strongly decrease surface solar radiation, with diurnal mean surface forcings comprised between −29.0±2.9 and −38.6±3.9 W m⁻², depending on the sites. This decrease is due to the reflection of solar radiations back to space (−7.3±0.8<ΔF_TOA<−12.3±1.2 W m⁻²) and to its absorption into the aerosol layer (21.1±2.1<ΔF_ATM<26.3±2.6 W m⁻²). These values are found to be consistent with those measured at local scale.