Environmental photochemistry of PCDDs. Part I. Kinetics and quantum yields of the photodegration of 1,2,3,4,7-penta- and 1,2,3,4,7,8-hexachlorodibenzo-p-dixin in aqueous acetontrile

For the determination of the quantum yields of 1,2,3,4,7-pentachlorodibenzo-$\text{p}$-dioxin ($\text{1}$) and 1,2,3,4,7,8-hexachlorodibenzo-$\text{p}$-dioxin ($\text{2}$), ten Pyrex glass photochemical cells were constructed and their correction factors determined. Quantum yields at 313 nm for $\text{1}$ and $\text{2}$ in aqueous acetonitrile (4:6 v/v) were (9.781 ± 2.376) 10^?5 and (1.096 ± 0.020) × 10^?4, respectively. These quantum yields and the measured absorption spectra were used to estimate the environmental phototransformation first-order rate constants and photochemical half-lives of $\text{1}$ and $\text{2}$ in water under conditions of variable sunlight intensity during various seasons from solar intensity data available in the literature. In summer, typical half-lives for the phototransformation of $\text{1}$ and $\text{2}$, respectively, near the surface of water bodies at 40° north latitude would be 364 ± 88 and 151 ± 3 h; whilst such values in winter would be 1257 ± 309 and 518 ± 10 h.     

Uptake,depuration and biotransformation of anthracene by the scud Pontoporeia hoyi

Uptake, depuration and biotransformation rates of ¹⁴C-anthracene were determined for Pontoporeia hoyi, the dominant benthic invertebrate in the Great Lakes, at 4°, 7°, 10° and 15°C. The uptake rate constants for anthracene increased from 136±22 h^?1 (n=4, $\text{X}\text{?}\text{±1}\text{SD}$) to 215±45 h^?1 (n=4) over the temperature range studied and were seasonally dependent. The depuration rate constant at the apparent optimum temperature of 7°C was 0.015 h^?1 for anthracene. The biotransformation ability of P. hoyi is low, and degradation of anthracene was undetectable even after exposures of 48 h. The bioconcentration factor can be predicted from the uptake and depuration kinetics to be approximately 16,800 at 4°C. These experiments imply that P. hoyi may be very important in food chain biomagnification of some toxic organics.     

Biodegradation of Trifluralin in Harran Soil

Abstract

Degradation of trifluralin (α,α,α-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine) was investigated in soils taken from three different locations at Harran region of Turkey under laboratory conditions. Surface (0–10 cm) soils, which were taken from a pesticide untreated field Gürgelen, Harran-1 and Ikizce regions in the Harran Plain, were incubated in biometer flasks for 350 days at 25°C. Ring-UL-¹⁴C-trifluralin was applied at the rate of 2 µg g^?1 with 78.7 kBq radioactivity per 100 g soil flask. Evolved ¹⁴CO₂ was monitored in KOH traps throughout the experiment. Periodically, soil sub-samples were removed and extracted by supercritical fluid extraction (SFE). Unextractable soil-bound ¹⁴C residues were determined by combustion. During the 350 days incubation period 6.6, 5.4, and 3.3% of the applied radiocarbon was evolved as ¹⁴CO₂ from the Harran-1, Gürgelen, and Ikizce soil, respectively. At the end of 350 days the SFE-extractable and bound ¹⁴C-trifluralin residues were 39.0 and 29.2% of the initially applied herbicide in Gürgelen soil. The corresponding values for Harran-1 and Ikizce soils were 36.2, 28.4% and 41.6, 18.5% respectively.     

Photochemistry and environment. VII- The photohydrolysis of chlorobenzene: Studies of the excited state involved

Chlorobenzene excited in dilute aqueous solution is transformed quantitatively into phenol ($\text{ф= 0.10±0.02}$). This reaction involves a triplet state, since it is quenched by biacetyl and sensitized by ketones. Based on quenching experiments, the lifetime of the lowest triplet of chlorobenzene was measured as 30 ns. From the sensitized phosphorescence of biactyl, the quantum yield of intersystem crossing (S₁→T₁) was found to be 0.6 ±0.1. The photophysical characteristics of chlorobenzene are identical in acetonitrile (). Photosensitization of the photohydrolysis is observed with acetone and acetone D6 in aqueous solution. The quantum yield of the sensitized photohydrolysis is limited to 0.06±0.01. Hexadeuterated acetone appeared to be a more specific photosensitizer than acetone.     

Precision and Accuracy in the Determination of Sulfur Oxides,Fluoride, and Spherical Aluminosilicate Fly Ash Particles in Project MOHAVE

The precision and accuracy of the determination of particu-late sulfate and fluoride, and gas phase SO₂ and HF are estimated from the results obtained from collocated replicate samples and from collocated comparison samples for high-and low-volume filter pack and annular diffusion denuder samplers. The results of replicate analysis of collocated samples and replicate analyses of a given sample for the determination of spherical aluminosilicate fly ash particles have also been compared. Each of these species is being used in the chemical mass balance source apportionment of sulfur oxides in the Grand Canyon region as part of Project MOHAVE, and the precision and accuracy analyses given in this paper provide input to that analysis. The precision of the various measurements reported here is ±1.8 nmol/m³ and ±2.5 nmol/m³ for the determination of SO₂ and sulfate, respectively, with an annular denuder. The precision is ±0.5 nmol/m³ and ±2.0 nmol/m³ for the determination of the same species with a high-volume or low-volume filter pack. The precision for the determination of the sum of HF(g) and fine particulate fluoride is ±0.3 nmol/m³. The precision for the determination of aluminosilicate fly ash particles is ±100 particles/m³. At high concentrations of the various species, reproducibility of the various measurements is ±10% to ±14% of the measured concentration. The concentrations of sulfate determined using filter pack samplers are frequently higher than those determined using diffusion denuder sampling systems. The magnitude of the difference (e.g., 2-10 nmol sulfate/m³) is small, but important relative to the precision of the data and the concentrations of particulate sul-fate present (typically 5-20 nmol sulfate/m³). The concentrations of SO₂(g) determined using a high-volume cascade impactor filter pack sampler are correspondingly lower than those obtained with diffusion denuder samplers. The concentrations of SO_x (SO₂(g) plus particulate sulfate) determined using the two samplers during Project MOHAVE at the Spirit Mountain, NV, and Hopi Point, AZ, sampling sites were in agreement. However, for samples collected at Painted Desert, AZ, and Meadview, AZ, the concentrations of SO_x and SO₂(g) determined with a high-volume cascade impactor filter pack sampler were frequently lower than those determined using a diffusion denuder sampling system. These two sites had very low ambient relative humidity, an average of 25%. Possible causes of observed differences in the SO₂(g) and sulfate results obtained from different types of samplers are given.     

Sources of submicron aerosol during fog-dominated wintertime at Kanpur

The main objective of this atmospheric study was to determine the major sources of PM₁ (particles having aerodynamic diameter <1.0 μm) within and near the city of Kanpur, in the Indo-Gangetic Plain. Day and night, 10 h long each, filter-based aerosol samples were collected for 4 months (November 2009 to February 2010) throughout the winter season. These samples were subjected to gravimetric and quantitative chemical analyses for determining water-soluble ions (NH₄ ⁺, F^?, Cl^?, NO₃ ^?, and SO₄ ^2?) using an ion chromatograph and trace elements using an inductively coupled plasma–optical emission spectrometer. The mean PM₁ mass concentrations were recorded as 114?±?71 μg/m³ (day) and 143?±?86 μg/m³ (night), respectively. A significantly higher diurnal contribution of ions (NH₄ ⁺, F^?, Cl^?, NO₃ ^?, and SO₄ ^2?) in PM₁ mass was observed during the fog-affected days and nights throughout the winter season, for which the average values were recorded as 38.09?±?13.39 % (day) and 34.98?±?12.59 % (night), respectively, of the total PM₁ mass. This chemical dataset was then used in a source-receptor model, UNMIX, and the model results are described in detail. UNMIX provided a maximum number of five source factors, including crustal material, composite vehicle, secondary aerosol, coal combustion, and iron/steel production and metallurgical industries, as the dominant air pollution sources for this study.     

Characterization of carbonaceous aerosols over Delhi in Ganga basin: seasonal variability and possible sources

The mass concentration of carbonaceous species, organic carbon (OC), and elemental carbon (EC) using a semicontinuous thermo-optical EC-OC analyzer, and black carbon (BC) using an Aethalometer were measured simultaneously at an urban mega city Delhi in Ganga basin from January 2011 to May 2012. The concentrations of OC, EC, and BC exhibit seasonal variability, and their concentrations were ～2 times higher during winter (OC 38.1?±?17.9 μg m^?3, EC 15.8?±?7.3 μg m^?3, and BC 10.1?±?5.3 μg m^?3) compared to those in summer (OC 14.1?±?4.3 μg m^?3, EC 7.5?±?1.5 μg m^?3, and BC 4.9?±?1.5 μg m^?3). A significant correlation between OC and EC (R?=?0.95, n?=?232) indicate their common emission sources with relatively lower OC/EC ratio (range 1.0–3.6, mean 2.2?±?0.5) suggests fossil fuel emission as a major source of carbonaceous aerosols over the station. On average, mass concentration of EC was found to be ～38 % higher than BC during the study period. The measured absorption coefficient (b_abs) was significantly correlated with EC, suggesting EC as a major absorbing species in ambient aerosols at Delhi. Furthermore, the estimated mass absorption efficiency (σ_abs) values are similar during winter (5.0?±?1.5 m² g^?1) and summer (4.8?±?2.8 m² g^?1). Significantly high aerosol loading of carbonaceous species emphasize an urgent need to focus on air quality management and proper impact assessment on health perspective in these regions.     

Interaction of higher marine fungi with the herbicide atrazine. III. Adsorption of atrazine to the marine fungus Dendryphiellasalina

The adsorption of the herbicide ¹⁴C-atrazine to the marine fungus $\text{Dendryphiella}$$\text{salina}$ was studied using sodium azide as an inhibitor of active uptake. Adsorption of atrazine (94 ppb) was found to reach equilibrium within six hours. Adsorption as a function of concentration (9.4 to 468 ppb) conformed to the empirically derived Freundlich equation giving a K value of 6.2. Atrazine on the fungal cell surface was easily desorbed by successive artificial seawater washes indicating a relatively loose binding. The ability of the marine fungus $\text{D.}$$\text{salina}$ to remove ¹⁴C-atrazine from an artificial seawater medium suggests an environmental role in the transport and redistribution of atrazine in estuaries.     

Characterization of emissions from portable household combustion devices: particle size distributions,emission rates and factors,and potential exposures

A series of source tests were conducted to characterize emissions of particulate matter (PM), carbon monoxide (CO), carbon dioxide (CO₂), methane (CH₄), and total hydrocarbon (THC ) from five types of portable combustion devices. Tested combustion devices included a kerosene lamp, an oil lamp, a kerosene space heater, a portable gas range, and four unscented candles. All tests were conducted either in a well-mixed chamber or a well-mixed room, which enables us to determine emission rates and emission factors using a single-compartment mass balance model. Particle mass concentrations and number concentrations were measured using a nephelometric particle monitor and an eight-channel optical particle counter, respectively. Real-time CO concentrations were measured with an electrochemical sensor CO monitor. CO₂, CH₄, and THC were measured using a GC-FID technique. The results indicate that all particles emitted during steady burning in each of the tested devices were smaller than 1.0 μm in diameter with the vast majority in the range between 0.1 and 0.3 μm. The PM mass emission rates and emission factors for the tested devices ranged from 5.6±0.1 to 142.3±40.8 mg h⁻¹ and from 0.35±0.06 to 9.04±4.0 mg g⁻¹, respectively. The CO emission rates and emission factors ranged from 4.7±3.0 to 226.7±100 mg h⁻¹ and from 0.25±0.12 to 1.56±0.7 mg g⁻¹, respectively. The CO₂ emission rates and emission factors ranged from 5500±700 to 210,000±90,000 mg h⁻¹ and from 387±45 to 1689±640 mg g⁻¹, respectively. The contributions of CH₄ and THC to emission inventories are expected to be insignificant due both to the small emission factors and to the relatively small quantity of fuel consumed by these portable devices. An exposure scenario analysis indicates that every-day use of the kerosene lamp in a village house can generate fine PM exposures easily exceeding the US promulgated NAAQS for PM_2.5.     

Environmental dynamics of phosphate esters. III. Comparison of the bioconcentration of four triaryl phosphates by fish

Uptake, clearance and extent of metabolism of ¹⁴C-labelled t-butylphenyldiphenyl phosphate (t-BPDP), tri-m-cresyl phosphate (mTCP), tri-p-cresyl phosphate (pTCP) and triphenyl phosphate (TPP) were studied in rainbow trout ($\text{Salmo}$$\text{gairdneri}$) and fathead minnows ($\text{Pimephales}$$\text{promelas}$) using short-term static exposures (50 and 5 μmg/L). Bioconcentration factors for pTCP, mTCP, TPP and tBPDP calculated by use of total radioactivity in whole fish were 1420, 784, 573 and 1096 respectively, for rainbow trout and 928, 596, 561 and 1010 respectively, for fathead minnows. Differences in rates of clearance and biotransformation among the four compounds were more closely related to their ease of hydrolysis than to hydrophobicity.     

Chemical characterization and source apportionment of fine and coarse particulate matter in Lahore,Pakistan

Lahore, Pakistan is an emerging megacity that is heavily polluted with high levels of particle air pollution. In this study, respirable particulate matter (PM_2.5 and PM₁₀) were collected every sixth day in Lahore from 12 January 2007 to 19 January 2008. Ambient aerosol was characterized using well-established chemical methods for mass, organic carbon (OC), elemental carbon (EC), ionic species (sulfate, nitrate, chloride, ammonium, sodium, calcium, and potassium), and organic species. The annual average concentration (±one standard deviation) of PM_2.5 was 194 ± 94 μg m^?3 and PM₁₀ was 336 ± 135 μg m^?3. Coarse aerosol (PM_10?2.5) was dominated by crustal sources like dust (74 ± 16%, annual average ± one standard deviation), whereas fine particles were dominated by carbonaceous aerosol (organic matter and elemental carbon, 61 ± 17%). Organic tracer species were used to identify sources of PM_2.5 OC and chemical mass balance (CMB) modeling was used to estimate relative source contributions. On an annual basis, non-catalyzed motor vehicles accounted for more than half of primary OC (53 ± 19%). Lesser sources included biomass burning (10 ± 5%) and the combined source of diesel engines and residual fuel oil combustion (6 ± 2%). Secondary organic aerosol (SOA) was an important contributor to ambient OC, particularly during the winter when secondary processing of aerosol species during fog episodes was expected. Coal combustion alone contributed a small percentage of organic aerosol (1.9 ± 0.3%), but showed strong linear correlation with unidentified sources of OC that contributed more significantly (27 ± 16%). Brick kilns, where coal and other low quality fuels are burned together, are suggested as the most probable origins of unapportioned OC. The chemical profiling of emissions from brick kilns and other sources unique to Lahore would contribute to a better understanding of OC sources in this megacity.     

Organic and elemental carbon associated to PM10 and PM2.5 at urban sites of northern Greece

Organic carbon (OC) and elemental carbon (EC) concentrations, associated to PM₁₀ and PM_2.5 particle fractions, were concurrently determined during the warm and the cold months of the year (July–September 2011 and February–April 2012, respectively) at two urban sites in the city of Thessaloniki, northern Greece, an urban-traffic site (UT) and an urban-background site (UB). Concentrations at the UT site (11.3?±?5.0 and 8.44?±?4.08 14 μg m^?3 for OC₁₀ and OC_2.5 vs. 6.56?±?2.14 and 5.29?±?1.54 μg m^?3 for EC₁₀ and EC_2.5) were among the highest values reported for urban sites in European cities. Significantly lower concentrations were found at the UB site for both carbonaceous species, particularly for EC (6.62?±?4.59 and 5.72?±?4.36 μg m^?3 for OC₁₀ and OC_2.5 vs. 0.93?±?0.61 and 0.69?±?0.39 μg m^?3 for EC₁₀ and EC_2.5). Despite that, a negative UT-UB increment was frequently evidenced for OC_2.5 and PM_2.5 in the cold months possibly indicative of emissions from residential wood burning at the urban-background site. At both sites, cconcentrations of OC fractions were significantly higher in the cold months; on the contrary, EC fractions at the UT site were prominent in the warm season suggesting some influence from maritime emissions in the nearby harbor area. Secondary organic carbon, being estimated using the EC tracer method and seasonally minimum OC/EC ratios, was found to be an appreciable component of particle mass particularly in the cold season. The calculated secondary contributions to OC ranged between 35 and 59 % in the PM₁₀ fraction, with relatively higher values in the PM_2.5 fraction (39–61 %). The source origin of carbonaceous species was investigated by means of air parcel back trajectories, satellite fire maps, and concentration roses. A local origin was mainly concluded for OC and EC with limited possibility for long range transport of biomass (agricultural waste) burning aerosol.     

Gaseous and particulate water-soluble organic and inorganic nitrogen in rural air in southern Scotland

Simultaneous daily measurements of water-soluble organic nitrogen (WSON), ammonium and nitrate were made between July and November 2008 at a rural location in south-east Scotland, using a ‘Cofer’ nebulizing sampler for the gas phase and collection on an open-face PTFE membrane for the particle phase. Average concentrations of NH₃ were 82 ± 17 nmol N m^?3 (error is s.d. of triplicate samples), while oxidised N concentrations in the gas phase (from trapping NO₂ and HNO₃) were smaller, at 2.6 ± 2.2 nmol N m^?3, and gas-phase WSON concentrations were 18 ± 11 nmol N m^?3. The estimated collection efficiency of the nebulizing samplers for the gas phase was 88 (±8) % for NH₃, 37 (±16) % for NO₂ and 57 (±7) % for WSON; reported average concentrations have not been corrected for sampling efficiency. Concentrations in the particle phase were smaller, except for nitrate, at 21 ± 9, 10 ± 6 and 8 ± 9 nmol N m^?3, respectively. The absence of correlation in either phase between WSON and either (NH₃ + NH₄⁺) or NO₃^? concentrations suggests atmospheric WSON has diverse sources. During wet days, concentrations of gas and particle-phase inorganic N were lower than on dry days, whereas the converse was true for WSON. These data represent the first reports of simultaneous measurements of gas and particle phase water-soluble nitrogen compounds in rural air on a daily basis, and show that WSON occurs in both phases, contributing 20–25% of the total water-soluble nitrogen in air, in good agreement with earlier data on the contribution of WSON to total dissolved N in rainfall in the UK.