Passive air sampling theory for semivolatile organic compounds

The mathematical modelling underlying passive air sampling theory can be based on mass transfer coefficients or rate constants. Generally, these models have not been inter-related. Starting with basic models, the exchange of chemicals between the gaseous phase and the sampler is developed using mass transfer coefficients and rate constants. Importantly, the inter-relationships between the approaches are demonstrated by relating uptake rate constants and loss rate constants to mass transfer coefficients when either sampler-side or air-side resistance is dominating chemical exchange. The influence of sampler area and sampler volume on chemical exchange is discussed in general terms and as they relate to frequently used parameters such as sampling rates and time to equilibrium. Where air-side or sampler-side resistance dominates, an increase in the surface area of the sampler will increase sampling rates. Sampling rates are not related to the sampler/air partition coefficient (K(SV)) when air-side resistance dominates and increase with K(SV) when sampler-side resistance dominates.     

Volatile nanoparticle formation and growth within a diluting diesel car exhaust

A major source of particle number emissions is road traffic. However, scientific knowledge concerning secondary particle formation and growth of ultrafine particles within vehicle exhaust plumes is still very limited. Volatile nanoparticle formation and subsequent growth conditions were analyzed here to gain a better understanding of "real-world" dilution conditions. Coupled computational fluid dynamics and aerosol microphysics models together with measured size distributions within the exhaust plume of a diesel car were used. The impact of soot particles on nucleation, acting as a condensational sink, and the possible role of low-volatile organic components in growth were assessed. A prescribed reduction of soot particle emissions by 2 orders of magnitude (to capture the effect of a diesel particle filter) resulted in concentrations of nucleation-mode particles within the exhaust plume that were approximately 1 order of magnitude larger. Simulations for simplified sulfuric acid-water vapor gas-oil containing nucleation-mode particles show that the largest particle growth is located in a recirculation zone in the wake of the car. Growth of particles within the vehicle exhaust plume up to detectable size depends crucially on the relationship between the mass rate of gaseous precursor emissions and rapid dilution. Chassis dynamometer measurements indicate that emissions of possible hydrocarbon precursors are significantly enhanced under high engine load conditions and high engine speed. On the basis of results obtained for a diesel passenger car, the contributions from light diesel vehicles to the observed abundance of measured nucleation-mode particles near busy roads might be attributable to the impact of two different time scales: (1) a short one within the plume, marked by sufficient precursor emissions and rapid dilution; and (2) a second and comparatively long time scale resulting from the mix of different precursor sources and the impact of atmospheric chemistry.     

Comparison of inclined plate sedimentation and dissolved air flotation for the minimisation of subsequent nitrogenous disinfection by-product formation

The formation of disinfection by-products (DBPs), including both nitrogenous disinfection by-products (N-DBPs) and carbonaceous disinfection by-products (C-DBPs), was investigated upon chlorination of water samples following two treatment processes: (i) coagulation-inclined plate sedimentation (IPS)-filtration and (ii) coagulation-dissolved air flotation (DAF)-filtration. The removal of algae, dissolved organic nitrogen (DON), dissolved organic carbon (DOC) and UV₂₅₄ by coagulation-DAF-filtration was superior to coagulation-IPS-filtration. On average, 53%, 53% and 31% of DOC, DON and UV₂₅₄ were removed by coagulation-DAF-filtration process, which were higher than 47%, 31% and 27% of that by coagulation-IPS-filtration process. Additionally, coagulation-IPS-filtration performed less well at removing the low molecular weight organics than coagulation-DAF-filtration process. The concentrations of chloroform, dichloroacetamide (DCAcAm) and dichloroacetonitrile (DCAN) formed during chlorination after coagulation-DAF-filtration reached their maximum values of 13, 1.5 and 4.7 μg L⁻¹, respectively, and were lower than those after coagulation-IPS-filtration with the maximum detected levels of 17, 2.9 and 6.3 μg L⁻¹. However, the trichloronitromethane (TCNM) concentration after the two processes was similar, suggesting that DON may have less of a contribution to TCNM formation than DCAcAm and DCAN.     

The influence of EDDS and EDTA on the uptake of heavy metals of Cd and Cu from soil with tobacco Nicotiana tabacum

Phytoextraction, the use of plants to extract contaminants from soils and groundwater, is a promising approach for cleaning up soils contaminated with heavy metals. In order to enhance phytoextraction the use of chelating agents has been proposed. This study aims to assess whether ethylene diamine disuccinate (EDDS), a biodegradable chelator, can be used for enhanced phytoextraction purposed, as an alternative to ethylene diamine tetraacetate (EDTA). EDDS revealed a higher toxicity to tobacco (Nicotiana tabacum) in comparison to EDTA, but no toxicity to microorganisms. The uptake of Cu was increased by the addition of EDTA and EDDS, while no increase was observed in the uptake of Cd. Both chelating agents showed a very low root to shoot translocation capability and the translocation factor was lower than the one of the control. Heavy metals where significantly more phytoavailable than in the control, even after harvesting, resulting in a high heavy metal leaching possibility, probably owing to a low biodegradation rate of EDDS. New seedlings which were transplanted into the EDDS treated pots 7d after the phytoextraction experiment, showed signs of necrosis and chlorosis, which resulted in a significantly lower biomass in comparison to the control. The seedlings on the EDTA treated pots showed no toxicity signs. Contrary to previous opinions the results of this study revealed the chelating agents EDTA and EDDS as unsuitable for enhanced phytoextraction using tobacco.     

Impacts of atmospheric pollution on the plant communities of British acid grasslands

Air pollutants are recognised as important agents of ecosystem change but few studies consider the effects of multiple pollutants and their interactions. Here we use ordination, constrained cluster analysis and indicator value analyses to identify potential environmental controls on species composition, ecological groupings and indicator species in a gradient study of UK acid grasslands. The community composition of these grasslands is related to climate, grazing, ozone exposure and nitrogen deposition, with evidence for an interaction between the ecological impacts of base cation and nitrogen deposition. Ozone is a key agent in species compositional change but is not associated with a reduction in species richness or diversity indices, showing the subtly different drivers on these two aspects of ecosystem degradation. Our results demonstrate the effects of multiple interacting pollutants, which may collectively have a greater impact than any individual agent.     

Bacterial diversity in paclobutrazol applied agricultural soils

The aim of this study was to investigate the bacterial communities on paclobutrazol [(2RS, 3RS)-1-(4-Chlorophenyl)-4, 4-dimethyl-2-(1H-1,2,4-triazol-1-yl) pentan-3-ol]–applied agricultural soils by denaturing gradient gel electrophoresis (DGGE) of polymerase chain reaction (PCR) amplified 16S rDNA gene fragments. Three different agricultural soil samples were collected from paclobutrazol applied mango and waxapple orchards, peanut fields and untreated rice fields as a control for DGGE analysis. The DGGE pattern of PCR- generated 16S rDNA gene fragments indicated that the bacterial populations from four paclobutrazol–applied soils of peanut fields were closely related to each other and two paclobutrazol–applied soils of mango and waxapple orchards harbored closely related bacterial communities. But, paclobutrazol–free agricultural soils comprised relatively a different bacterial group. However, the bacterial populations of mango and waxapple orchard are completely different from the bacterial communities of peanut field. Further purification and sequence analysis of 40 DGGE bands followed by phylogenetic tree assay showed similar results that soil bacteria from paclobutrazol applied mango and waxapple orchard are phylogenetically related. Based on the phylogenetic analysis, the clone M-4 was clad 100 % (bootstrap value) with Mycobacterium sp. The Mycobacterium sp. has been proved to degrade the phenolic compounds such as phenol, 4-chlorphenol, 2,4-dichlorophenol and paclobutrazol molecule containing chlorobenzene ring.     

Estimation and characterization of children’s ambient generated exposure to PM2.5 using sulphate and elemental carbon as tracers

Children’s exposures to ambient and non-ambient fine particulate matter (PM_2.5) were determined using the sulphate and elemental carbon components of the PM_2.5 mixture as tracers of the ambient contribution during a 6-week winter period in Prince George, British Columbia, Canada. Personal exposures to PM_2.5 were measured in children at 5 elementary schools located throughout the city and ambient samples were collected on school rooftops. Average ambient levels and personal exposures during this time period were 13.8 μg m^?3 and 16.4 μg m^?3 respectively. From the data pooled across individuals, use of the two different tracers indicated identical estimates of median exposure to ambient PM_2.5 (7.5 μg m^?3) and similar estimates of non-ambient generated exposure (6.4 and 5.0 μg m^?3) and infiltration (0.49 and 0.52) for the sulphate and elemental carbon approach, respectively. The median fraction of the ambient concentration resulting in exposure or exposure factors were 0.54 and 0.55 respectively, however lower values of 0.46 and 0.42 were determined from regression analysis. A strong association was found between exposure to ambient PM_2.5 and measured ambient concentrations at both the closest school monitor (median r = 0.92) and a central site (median r = 0.88) demonstrating that the central site monitor was suitable for assessing longitudinal ambient generated exposure throughout the city. These results support the use of elemental carbon as a tracer of ambient generated exposure and the use of ambient data as estimates of longitudinal changes in children’s exposure in this setting. The importance of both ambient and non-ambient sources of PM_2.5 is emphasized by their almost equal contribution to total personal exposures. Comparison with other studies suggests a limited influence of climate and the cold season in Prince George on exposure levels and found similar mean non-ambient generated exposures despite large variability across and within subjects in any given location.     

Using variance components to estimate power in a hierarchically nested sampling design

We used variance components to assess allocation of sampling effort in a hierarchically nested sampling design for ongoing monitoring of early life history stages of the federally endangered Devils Hole pupfish (DHP) (Cyprinodon diabolis). Sampling design for larval DHP included surveys (5 days each spring 2007–2009), events, and plots. Each survey was comprised of three counting events, where DHP larvae on nine plots were counted plot by plot. Statistical analysis of larval abundance included three components: (1) evaluation of power from various sample size combinations, (2) comparison of power in fixed and random plot designs, and (3) assessment of yearly differences in the power of the survey. Results indicated that increasing the sample size at the lowest level of sampling represented the most realistic option to increase the survey’s power, fixed plot designs had greater power than random plot designs, and the power of the larval survey varied by year. This study provides an example of how monitoring efforts may benefit from coupling variance components estimation with power analysis to assess sampling design.     

Degradation of PVC Containing Mixtures in the Presence of HCl Fixators

Degradation of a model polymer mixture (PVC/PS/PE) and a waste polymer mixture in the presence of HCl fixators (Red Mud, precipitated CaCO₃ and dolamite) was studied using thermal gravimetric analysis (TGA) and a cycled-spheres-reactor. The experiments in cycled-spheres reactor model were performed by stepwise pyrolysis. Liquid products and HCl from each step were collected separately. For the model polymer mixture, the precipitated CaCO₃ showed the best effect on the fixation of evolved HCl and the reduction of chlorine content in the liquid products whereas RM yielded the best result for the waste polymer mixture. In addition, using HCl fixator also affected the degradation of both types of polymer mixture, leading to the formation of more gaseous and less residue.     

Predicting Satisfaction with Smart Irrigation Controllers and Their Long‐Term Use among Homeowners in Central Florida

Studies throughout Florida have shown smart controllers can substantially reduce irrigation under residential high‐water use conditions. However, successful promotion requires understanding the link between controller performance and the mechanisms by which they are adopted. This article compares irrigation water‐use and survey data collected from households installed with soil moisture sensor and evapotranspiration controllers. The study investigated whether the relative change in irrigation use between two years preceding and two years following installation was a reliable predictor of a homeowner's satisfaction with the device and likelihood of continuing to use it. Results indicated relative changes in irrigation use were only significantly associated with the quality of controller programming. Satisfaction with the controller was largely attributable to satisfaction with the appearance of the landscape and the perceived water‐saving effectiveness of the controller whereas the likelihood of its continued use was only significantly predicted by the level of technical knowledge regarding its functioning and whether or not challenges were experienced with it. Targeting homeowners with supplemental user‐friendly information may best support their long‐term adoption of smart controllers while providing irrigation contractors with training in implementation techniques would represent an integrated strategy for added reductions in residential outdoor water use.