Flux measurements of volatile organic compounds by the relaxed eddy accumulation method combined with a GC-FID system in urban Houston,Texas

A tall tower flux measurement setup was established in metropolitan Houston, Texas, to measure trace gas fluxes from emission sources in the urban surface layer. We describe a new relaxed eddy accumulation (REA) system combined with a dual-channel GC-FID used for VOC flux measurements, focusing on benzene, toluene, ethylbenzene and xylenes (BTEX) results. Ambient air sampled from 60 m above the ground next to a sonic anemometer was subsampled by a membrane pump and pushed into an REA valve system with two Teflon bag reservoirs, then transferred to two preconcentration units for thermal desorption. We discuss the performance of our system and the selected BTEX measurement results using approximately 8 weeks of data (May 22–July 22, 2008), presenting diurnal variations of concentrations and fluxes of these traffic tracers. The measured values exhibited diurnal cycles with dominant morning and midday peaks during weekdays related to rush hour traffic and additional weekday daytime toluene and xylenes emissions. Local evaporative emissions, likely from solvent usage, significantly contributed to the measured fluxes. We upscaled measured emissions to the county level using a high resolution land cover data set and compared the results with EPA’s National Emission Inventory (NEI).     

Chemical mass balance source apportionment for combined PM2.5 measurements from U.S. non-urban and urban long-term networks

The Minnesota Particulate Matter 2.5 (PM_2.5) Source Apportionment Study was undertaken to explore the utility of PM_2.5 mass, element, ion, and carbon measurements from long-term speciation networks for pollution source attribution. Ambient monitoring data at eight sites across the state were retrieved from the archives of the Interagency Monitoring of Protected Visual Environments (IMPROVE) and the Speciation Trends Network (STN; part of the Chemical Speciation Network [CSN]) and analyzed by an Effective Variance – Chemical Mass Balance (EV-CMB) receptor model with region-specific geological source profiles developed in this study. PM_2.5 was apportioned into contributions of fugitive soil dust, calcium-rich dust, taconite (low grade iron ore) dust, road salt, motor vehicle exhaust, biomass burning, coal-fired utility, and secondary aerosol. Secondary sulfate and nitrate contributed strongly (49–71% of PM_2.5) across all sites and was dominant (≥60%) at IMPROVE sites. Vehicle exhausts accounted for 20–70% of the primary PM_2.5 contribution, largely exceeding the proportion in the primary PM_2.5 emission inventory. The diesel exhaust contribution was separable from the gasoline engine exhaust contribution at the STN sites. Higher detection limits for several marker elements in the STN resulted in non-detectable coal-fired boiler contributions which were detected in the IMPROVE data. Despite the different measured variables, analytical methods, and detection limits, EV-CMB results from a nearby IMPROVE-STN non-urban/urban sites showed similar contributions from regional sources – including fugitive dust and secondary aerosol. Seasonal variations of source contributions were examined and extreme PM_2.5 episodes were explained by both local and regional pollution events.     

Plant availability of bound anilazine residues in a degraded loess soil

Abstract

The relative biological availability of [benzene ring‐U‐¹⁴C] and Ctriazine‐U‐¹⁴C] anilazine for maize plants was studied in a degraded loess soil in a standardized microecosystem. The total uptake of radiocarbon in the course of the 4‐week experiment was 3.1 and 4 % respectively of the radioactivity applied if anilazine was uniformly mixed into the soil immediately before beginning the experiment. However, if anilazine was subjected to a degradation at 65 % of the maximum water holding capacity of the soil and temperatures varying daily between 16 and 27°C for 100 days before the plant experiment then the uptake was reduced to 0.4 or 0.7 % respectively. The uptake from soil with non‐extractable (bound) anilazine residues was similarly low. The mineralization rate of aged and bound anilazine residues was below 0.1 % of the radioactivity applied. Up to 2/3 of the radioactivity present in the soil after the plant experiment remained in the humic fraction.     

Diflubenzuron residue and persistence on an oak forest after aerial application

Abstract

A twenty hectare forest block in central Pennsylvania was aerially sprayed with diflubenzuron (Dimilin 25W®) at the dose of 33.23g A.I./ha in 9.4 litres/ha. Leaf samples were collected from the upper and lower canopies of 27 oaks and understory within this block on the day of spray, May 29, 1991. Canopy leaves were also collected on May 31, June 10, July 29 and September 26, 1991.

Recovery of diflubenzuron residues on fortified canopy‐leaf and litter‐leaf samples using analytical techniques employed in this study averaged 87.4% (SE = 7.5%) and 66.2% (SE = 8.2%), respectively.

On the day of spray, diflubenzuron residues on the upper canopy, lower canopy and understory averaged 81.18, 39.65 and 8.35 ng/cm², respectively. Diflubenzuron residues on canopy‐leaf samples collected 2, 12, 61 and 120 days post‐spray averaged 14.83 (SE = 10.19), 16.75 (SE = 9.95), 12.84 (SE = 8.25) and 11.20 (SE = 7.52) ng/cm², respectively. Diflubenzuron residues on litter‐leaf samples collected after leaf senescence ‐ 169 and 323 days post spray contained measurable amounts of diflubenzuron in 51 and 59% of the samples, respectively. Of the samples with measurable amounts of diflubenzuron, residues averaged 1.36 (SE = 2.44) and 0.65 ng/cm² (SE = 0.73) respectively.     

Evaluation of C18 solid‐phase extraction cartridges for the isolation of select pesticides and metabolites

Abstract

Nine different C₁₈ solid‐phase extraction (SPE) cartridges were evaluated for their efficiency at extracting nine pesticides and two s‐triazine metabolites from spiked deionized water samples. The SPE cartridges were found to contain nitrogen (N) and/or phosphorus (P) contaminants and varied in their extraction efficiency for certain pesticides and metabolites. Four of the nine SPE cartridges gave acceptable (70 to 120%) pesticide and metabolite recovery percentages, while five cartridges had marginal (50 to 70%) to poor (< 50%) recoveries. Statistical analyses showed that the poor to marginal recoveries found for three compounds could not be explained by considering several indigenous chemical and physical traits of the cartridge. It is suggested that proper SPE cartridge selection for pesticide recovery should be evaluated using several different cartridges.     

Toxicity of hydroquinone to different freshwater phototrophs is influenced by time of exposure and pH

The interaction of natural organic matter with phytoplankton communities in freshwater ecosystems is an intensively studied subject matter. Previous studies showed that apparently plant-derived phenols were able to inhibit algal and cyanobacterial growth. Furthermore, it was also assumed that humic substances (HS), which comprise the major part of dissolved organic carbon in freshwater ecosystems, directly interact with freshwater phototrophs. For example, quinoid building blocks of HS were thought to be algicidal. To identify key environmental variable for the toxic action of potential quinone algicides, we tested the toxicity of hydroquinone (HQ) to different eukaryotic and prokaryotic freshwater phototrophs in terms of growth performance and investigated also the effect of HQ oxidation at different pH values on its algicidal potential. It was shown that cyanobacterial species were much more susceptible to hydroquinone than coccal green algal species were, with Microcystis aeruginosa being the most sensitive species by far. In addition, it was obvious that the aging of hydroquinone-stock solution at pH 11 led to polymerization and, by this process, to a total loss of toxicity; whereas the algicidal potential sustained if the polyphenol was kept at pH 7. Since most lakes with heavy blooms of phototrophs possess pH values clearly above 7.0, it is questionable, if polyphenols in general and quinones in particular are the effective chemicals and if litter and straw leachates are applied as means to combat algal and cyanobacterial blooms.     

Photocatalytic degradation of contaminants of concern with composite NF-TiO2 films under visible and solar light

This study reports the synthesis and characterization of composite nitrogen and fluorine co-doped titanium dioxide (NF-TiO₂) for the removal of contaminants of concern in wastewater under visible and solar light. Monodisperse anatase TiO₂ nanoparticles of different sizes and Evonik P25 were assembled to immobilized NF-TiO₂ by direct incorporation into the sol–gel or by the layer-by-layer technique. The composite films were characterized with X-ray diffraction, high-resolution transmission electron microscopy, environmental scanning electron microscopy, and porosimetry analysis. The photocatalytic degradation of atrazine, carbamazepine, and caffeine was evaluated in a synthetic water solution and in an effluent from a hybrid biological concentrator reactor (BCR). Minor aggregation and improved distribution of monodisperse titania particles was obtained with NF-TiO₂-monodisperse (10 and 50 nm) from the layer-by-layer technique than with NF-TiO₂?+?monodisperse TiO₂ (300 nm) directly incorporated into the sol. The photocatalysts synthesized with the layer-by-layer method achieved significantly higher degradation rates in contrast with NF-TiO₂-monodisperse titania (300 nm) and slightly faster values when compared with NF-TiO₂-P25. Using NF-TiO₂ layer-by-layer with monodisperse TiO₂ (50 nm) under solar light irradiation, the respective degradation rates in synthetic water and BCR effluent were 14.6 and 9.5?×?10^?3?min^?1 for caffeine, 12.5 and 9.0?×?10^?3?min^?1 for carbamazepine, and 10.9 and 5.8?×?10^?3?min^?1 for atrazine. These results suggest that the layer-by-layer technique is a promising method for the synthesis of composite TiO₂-based films compared to the direct addition of nanoparticles into the sol.     

Arsenic stabilization by zero-valent iron,bauxite residue,and zeolite at a contaminated site planting Panax notoginseng

Panax notoginseng (Burk.) F.H. Chen, a rare traditional Chinese medicinal herb, is a widely used phytomedicine used all over the world. In recent years, the arsenic contamination of the herb and its relative products becomes a serious problem due to elevated soil As concentration. This study aimed to evaluate the effects of different types and dosages of amendments on As stabilization in soil and its uptake by P. notoginseng. Results showed that comparing to control treatment, the As concentrations of P. notoginseng declined by 49–63%, 43–61% and 52–66% in 0.25% zero-valent iron (Fe(0)), 0.5% bauxite residue, and 1% zeolite treatment, respectively; whereas the biomasses were elevated by 62–116%, 45–152% and 114–265%, respectively. The As(III) proportions of P. notoginseng increased by 8%, 9%, and 8%, and the transfer factors of As from root to shoot increased by 37%, 42% and 84% in the optimal treatments of Fe(0), bauxite residue, and zeolite. For soil As, all the three amendments could transform the non-specifically adsorbed As fraction to hydrous oxides Fe/Al fractions (by Fe(0) and red mud) or specifically adsorbed As fraction (by zeolite), therefore reduced the bioavailability of soil As. With a comprehensive consideration of stabilization efficiency, plant growth, environmental influence, and cost, Fe(0) appeared to be the best amendment, and zeolite could also be a good choice. In conclusion, this study was of significance in developing As contamination control in P. notoginseng planting areas, and even other areas for medicinal herb growing.     

Evaluation of food chain transfer of the antibiotic oxytetracycline and human risk assessment

There has been recent concern regarding the possibility of antibiotics entering the aquatic food chain and impacting human consumers. This work reports experimental results of the bioconcentration of the antibiotic oxytetracycline (OTC) by the Asian watermeal plant (Wolffia globosa Hartog & Plas) and bioaccumulation of OTC in watermeal and water by the seven-striped carp (Probarbus jullieni). They show, for the first time, the extent to which OTC is able to transfer from water to plant to fish and enter the food chain. The mean bioconcentration factor (dry weight basis) with watermeal was 1.28 × 10³ L kg⁻¹. Separate experiments were undertaken to characterize accumulation of OTC by carp from water and watermeal. These showed the latter pathway to be dominant under the conditions employed. The bioconcentration and biomagnification factors for these processes were 1.75 L kg⁻¹ and 2 × 10⁻⁴ kg g⁻¹ respectively. Using an aqueous concentration range of 0.34–3.0 μg L⁻¹, hazard quotients for human consumption of contaminated fish of 1.3 × 10⁻² to 1.15 × 10⁻¹ were derived.     

Glutamine synthetase and protease enzyme activities and growth response of ruminal bacterium Prevotella ruminicola strain B14 to nitrogen source and concentration

Abstract

The objective of this study was to determine the effects of varying nitrogen sources and concentrations upon glutamine synthetase and protease activities in Prevotella ruminicola strain B₁4. Based on growth response it appears that ammonium chloride or pepticase limited P. ruminicola becomes nitrogen limited when nitrogen concentration is at 0.5 mM. However, when casein was provided as the sole source of nitrogen P. ruminicola becomes nitrogen limited at 2.5 mM. Glutamine synthetase activity was measured from mid‐log phase cells grown in either nitrogen‐limited or non‐limited conditions. No activity was detectable in the non‐limited treatments. However, in the N‐ limited treatments, pepticase had the highest activity (20.76 units), followed by ammonium chloride (18.72 units) and casein (14.42 units). Protease activity assays indicated that nitrogen‐limited cultures had higher proteolytic activity than non‐limited cultures. Moreover, these activities appeared to follow the same response pattern as the previously observed glutamine synthetase activities. The results of this study indicate that P. ruminicola strain B, 4 protease activity may be influenced by nitrogen concentration such that activity increases when nitrogen availability decreases.