Laboratory study of the rates and products of the phototransformations of naphthalene adsorbed on samples of titanium dioxide,ferric oxide,muscovite, and fly ash

The photodegradation of naphthalene (NPH), chosen as a model of polynuclear aromatic pollutants, has been studied in the presence of a layer of four water-insoluble inorganic solids which can be found in the troposphere (TiO₂, Fe₂O₃, muscovite, and a fly ash sample). Direct photolysis of NPH is negligible at >340 nm. Dark adsorption of NPH on TiO₂ (mainly anatase, nonporous, 50 m² g^–1) at 293 K corresponds to a surface coverage ofca. 50% at equilibrium. Under these conditions (saturated surface), the stationary-state photocatalytic degradation reaches 0.4 molecule nm^–2 h^–1 (>340 nm, radiant fluxca. 22 mW cm^–2). Dioxygen is required and its partial pressure in air is such that the degradation is zero order in O₂. Water vapor markedly increases the rate. The other particulates have also an effect, less important than that of TiO₂, however quite noticeable with respect to surface area unit for the fly ash sample which contains 3.2% Fe₂O₃. Apart from 1,4-naphthoquinone, which is the main intermediate product in all cases, 2-naphthol, phthalide, phthaldialdehyde, phthalic acid, acetophenone, benzaldehyde, benzoic acid are also formed on dry TiO₂. Depending on their volatility, these compounds are transferred to the gas phase or remain principally adsorbed on the solid particles where they are further transformed. For instance, phthalic acid (or anhydride) and benzoic acid are generated from 1,4-naphthoquinone. Degradation mechanisms are briefly discussed.     

Wind-tunnel Modelling of Dispersion from a Scalar Area Source in Urban-Like Roughness

A wind-tunnel study was conducted to investigate ventilation of scalars from urban-like geometries at neighbourhood scale by exploring two different geometries a uniform height roughness and a non-uniform height roughness, both with an equal plan and frontal density of λ _p = λ _f = 25%. In both configurations a sub-unit of the idealized urban surface was coated with a thin layer of naphthalene to represent area sources. The naphthalene sublimation method was used to measure directly total area-averaged transport of scalars out of the complex geometries. At the same time, naphthalene vapour concentrations controlled by the turbulent fluxes were detected using a fast Flame Ionisation Detection (FID) technique. This paper describes the novel use of a naphthalene coated surface as an area source in dispersion studies. Particular emphasis was also given to testing whether the concentration measurements were independent of Reynolds number. For low wind speeds, transfer from the naphthalene surface is determined by a combination of forced and natural convection. Compared with a propane point source release, a 25% higher free stream velocity was needed for the naphthalene area source to yield Reynolds-number-independent concentration fields. Ventilation transfer coefficients w _T /U derived from the naphthalene sublimation method showed that, whilst there was enhanced vertical momentum exchange due to obstacle height variability, advection was reduced and dispersion from the source area was not enhanced. Thus, the height variability of a canopy is an important parameter when generalising urban dispersion. Fine resolution concentration measurements in the canopy showed the effect of height variability on dispersion at street scale. Rapid vertical transport in the wake of individual high-rise obstacles was found to generate elevated point-like sources. A Gaussian plume model was used to analyse differences in the downstream plumes. Intensified lateral and vertical plume spread and plume dilution with height was found for the non-uniform height roughness.     

A Wind Tunnel Model for Quantifying Fluxes in the Urban Boundary Layer

Transport of pollution and heatout of streets into the boundary layer above is not currently understood and so fluxes cannot be quantified. Scalar concentration within the street is determined by the flux out of it and so quantifying fluxes for turbulent flow over a rough urban surface is essential. We have developed a naphthalene sublimation technique to measure transfer from a two-dimensional street canyon in a wind tunnel for the case of flow perpendicular to the street. The street was coated with naphthalene, which sublimes at room temperature, so that the vapour represented the scalar source. The transfer velocity w_T relates the flux out of the canyon to the concentration within it and is shown to be linearly related to windspeed above the street. The dimensionless transfer coefficient w_T/U represents the ventilation efficiency of the canyon (here, w_T is a transfer velocity,U is the wind speed at the boundary-layer top). Observed values are between 1.5 and 2.7 ×10^-3 and, for the case where H/W0 (ratio of buildingheight to street width), values are in the same range as estimates of transfer from a flat plate, giving confidence that the technique yields accurate values for street canyon scalar transfer. w_T/U varies with aspect ratio (H/W), reaching a maximum in the wake interference regime (0.3 < H/W < 0.65). However, when upstream roughness is increased, the maximum in w_T/U reduces, suggesting that street ventilation is less sensitive to H/W when the flow is in equilibrium with the urban surface. The results suggest that using naphthalene sublimation with wind-tunnel models of urban surfaces can provide a direct measure of area-averaged scalar fluxes.     

Assessment of natural attenuation of aromatic hydrocarbons in groundwater near a former manufactured-gas plant, South Carolina, USA

 Shallow, anaerobic groundwater near a former manufactured-gas plant (MGP) in Charleston, South Carolina, USA, contains mono- and polycyclic aromatic hydrocarbons (MAHs and PAHs, respectively). Between 1994 and 1997, a combination of field, laboratory, and numerical-flow and transport-model investigations were made to assess natural attenuation processes affecting MAH and PAH distributions. This assessment included determination of adsorption coefficients (K _ad ) and first-order biodegradation rate constants (K _bio ) using aquifer material from the MGP site and adjacent properties. Naphthalene adsorption (K _ad =1.35×10^–7 m³/mg) to aquifer sediments was higher than toluene adsorption (K _ad =9.34×10^–10 m³/mg), suggesting preferential toluene transport relative to naphthalene. However, toluene and benzene distributions measured in January 1994 were smaller than the naphthalene distribution. This scenario can be explained, in part, by the differences between biodegradation rates of the compounds. Aerobic first-order rate constants of ¹⁴C-toluene, ¹⁴C-benzene, and ¹⁴C-naphthalene degradation were similar (–0.84, –0.03, and 0.88 day^–1, respectively), but anaerobic rate constants were higher for toluene and benzene (–0.002 and –0.00014 day^–1, respectively) than for naphthalene (–0.000046 day^–1). Both areal and cross-sectional numerical simulations were used to test the hypothesis suggested by these rate differences that MAH compounds will be contained relative to PAHs. Predictive simulations indicated that the distributions of toluene and benzene reach steady-state conditions before groundwater flow lines discharge to an adjacent surface-water body, but do discharge low concentrations of naphthalene. Numerical predictions were "audited" by measuring concentrations of naphthalene, toluene, and benzene at the site in early 1997. Measured naphthalene and toluene concentrations were substantially reduced and the areal extent of contamination smaller than was both observed in January 1994 and predicted for 1997. Measured 1997 benzene concentrations and distribution were shown to be relatively unchanged from those measured in 1994, and similar to predictions for 1997. Received: 26 June 1997 · Accepted: 25 August 1997     

High resolution spectral features of a series of aromatic hydrocarbons and BrO: Potential interferences in atmospheric OH-measurements

Naphthalene (C₁₀H₈), several other hydrocarbons, mostly derivates of naphthalene, and bromine oxide (BrO) were analyzed for narrow band (0.01 nm) absorption lines in the wavelength range between 307.7 and 308.3 nm to study their potential impact on OH radical measurements by differential absorption spectroscopy.Only naphthalene showed narrow band absorption lines in this wavelength region. From nine naphthalene lines the differential absorption cross-section was determined.The strongest naphthalene line at 308.002 nm is close to the Q ₁(2) OH line, but about a factor of 200 weaker (=(65.2±15.3)×10^-20 cm²/molec). The corresponding detection limit for naphthalene is about 15 ppt. We re-evaluated some spectra of our OH measurement campaign in July 1987 with respect to naphthalene and obtained an upper limit of 30 ppt for its concentration.BrO was recorded in the larger wavelength interval between 307.7 and 308.7 nm. Structured absorptions were only observed at wavelengths above 308.2 nm and no significant structures were found in the vicinity of the Q ₁(2) and Q ₁(3) OH lines.     

Scalar fluxes from urban street canyons. Part I: Laboratory simulation

Flow over urban surfaces depends on surface morphology and interaction with the boundary layer above. However, the effect of the flow on scalar fluxes is hard to quantify. The naphthalene sublimation technique was used to quantify scalar vertical fluxes out of a street canyon under neutral conditions. For an array of eight canyons with aspect ratio H/W=0.75 (here, H is building height and W is the street width), increased flux was observed in the first two or three canyons for moderate and low roughness upstream. This is consistent with predictions of the length scale for initial adjustment of flow to an urban canopy. The flux was constant after the initial adjustment region and thus dependent only on local geometry. For a street canyon in the equilibrium part of the array, each facet of the street canyon was coated with naphthalene to simulate scalar release from street, walls and roof, to evaluate the effect of street canyon geometry on fluxes for H/W=0.25, 0.6, 1 and 2. Fluxes from the roof and downstream wall were considerably larger than fluxes from the street and upstream wall, and only the flux from the downstream wall exhibited a simple decrease with H/W. For each H/W there was a monotonic decrease between downstream wall, street and upstream wall transfer. This suggests that flow decelerates around the recirculation region in the lee of the upstream building, i.e. a recirculating jet rather than a symmetrical vortex. The addition of a second source within the street canyon resulted in reduced fluxes from each facet for H/W>0.25, due to increased concentration of naphthalene in the canyon air.     

Sorption kinetics of naphthalene and phenanthrene in loess soils

A laboratory study was executed to investigate the effect of surfactants to enhance sorption of polycyclic aromatic hydrocarbon (PAH) contaminants in loess soil. Phenanthrene and naphthalene were chosen as organic contaminant indicators in loess soil modified by the cation surfactant hexadecyltrimethylammonium (HDTMA) bromide. The kinetic behavior of sorption during transport in natural and modified loess soil was studied. The results indicated that sorption rate in the cation surfactant modified loess soils was at least 3 times faster than that of the natural soil. A first-order kinetics model fitted the sorption data well for both soils. The sorption rates of the two organic compounds were related to their primary residual quantity on the soils. The experiments showed that sorption amounts approached constant values approximately within 30 and 90 min for naphthalene and phenanthrene at 298–318 K, respectively. The rate constants, however, displayed negative correlation with increasing temperature. With changing temperature, the activation energy was calculated at –6.196–1.172 kJ/mol for naphthalene and –28.86–15.70 kJ/mol for phenanthrene at 298–318 K. The results can be used to predict the sorption kinetics of phenanthrene and naphthalene in loess soils, and in a wider perspective, be used to better understand the transport of petroleum contaminants in the soil environment.     

Naphthalene Degradation Kinetics of Micrococcus sp., Isolated from Activated Sludge

Biodegradation of naphthalene by Micrococcus sp., isolated from the effluent of an activated sludge plant, was studied. The effects of pH (5–8), glucose concentration (100–1000 mg/L) and inoculum concentrations (1–5%) on the growth and naphthalene degradation potential of Micrococcus sp. were investigated. Maximum naphthalene degradation and subsequent high microbial growth were observed at optimum pH (pH 7), glucose concentration (500 mg/L) and inoculum concentration (3%). To investigate the maximum naphthalene tolerance potential of Micrococcus sp., very high concentrations of naphthalene (500–5000 mg/L) were used in the presence of non‐ionic surfactants. The examined surfactants (Triton X‐100 and Tween‐80) increased the bioavailability of naphthalene to the microbes and Complete naphthalene degradation by Micrococcus sp. was observed at an initial naphthalene concentration of 500 mg/L. However, the degradation potential decreases as the naphthalene concentration increases. Very high naphthalene concentrations also affected the growth of microbes and the corresponding substrate inhibition kinetics was described using four models (Haldane, Webb, Edward and Aiba). Based on correlation coefficient and percentage error values, all four substrate kinetic models were able to describe the dynamic behavior of naphthalene biodegradation by Micrococcus sp.     

海水中萘的光化学降解研究

系统研究了在高压汞灯或天然日光照射下萘在天然海水、人工海水和蒸馏水中的光降解情况。萘的光降解过程受到包括光源、溶液介质、溶解氧、重金属离子、光敏剂在内的各种因素的影响。实验证明，高压汞灯较天然日光更能有效地激发萘的光反应。开始的90min之内，萘的浓度慢慢下降，在照射90－120min后，萘的浓度迅速下降，这是整个萘光解过程中最有效的部分，一级反应速率常数为0.0075-0.0203min^-1。萘在天然海水中的光解速率大于在人工海水和蒸馏水中的光解速率，其主要原因是天然海水中存在天然光敏剂。同蒸馏水中的光反应相比，人工海水中的离子有助于提高萘的光解反应。然而，溶液中加入的重金属离子或光敏剂会改变萘的光解反应。此外，研究证明，溶解氧是必不可少的，它的存在大大加速了光反应。     

Hypoxia does not promote naphthalene bioaccumulation in the brown shrimp, Penaeus aztecus

Since increased ventilation is known to be a common strategy used by aquatic animals to cope with hypoxia, we tested in present study the hypothesis that hypoxia can promote the bioaccumulation of naphthalene, a representative polycyclic aromatic hydrocarbon (PAH), in Penaeus aztecus, a penaeid shrimp subject to hypoxia and PAH contamination in the northern Gulf of Mexico. For each of the two naphthalene concentrations, five groups of shrimps were, respectively, subjected to five different conditions, namely, clean seawater under normoxia, seawater containing acetone under normoxia and hypoxia, and seawater containing 10 or 250 μg/L naphthalene under normoxia and hypoxia. Our results suggest that hypoxia does not significantly alter naphthalene bioaccumulation in either the gills or the hepatopancreas of P. aztecus. The absence of a promoting effect of hypoxia on naphthalene bioaccumulation is attributed to the increased disposition of naphthalene when the shrimps are subjected to hypoxia.