Weekday/Weekend Ozone Differences: What Can We Learn from Them?

Abstract

A national analysis of weekday/weekend ozone (O₃) differences demonstrates significant variation across the country. Weekend 1-hr or 8-hr maximum O₃ varies from 15% lower than weekday levels to 30% higher. The weekend O₃ increases are primarily found in and around large coastal cities in California and large cities in the Midwest and Northeast Corridor. Both the average and the 95th percentile of the daily 1-hr and 8-hr maxima exhibit the same general pattern. Many sites that have elevated O₃ also have higher O₃ on weekends even though traffic and O₃ precursor levels are substantially reduced on weekends. Detailed studies of this phenomenon indicate that the primary cause of the higher O₃ on weekends is the reduction in oxides of nitrogen (NO_x) emissions on weekends in a volatile organic compound (VOC)-limited chemical regime. In contrast, the lower O₃ on weekends in other locations is probably a result of NO_x reductions in a NO_x-limited regime. The NO_x reduction explanation is supported by a wide range of ambient analyses and several photochemical modeling studies. Changes in the timing and location of emissions and meteorological factors play smaller roles in weekend O₃ behavior. Weekday/weekend temperature differences do not explain the weekend effect but may modify it.     

Development of Emission Factors for Polycarbonate Processing

Abstract

Emission factors for selected volatile organic compounds (VOCs) and particulate emissions were developed while processing eight commercial grades of polycarbonate (PC) and one grade of a PC/acrylonitrile-butadiene-styrene (ABS) blend. A small commercial-type extruder was used, and the extrusion temperature was held constant at 304 °C. An emission factor was calculated for each substance measured and is reported as pounds released to the atmosphere/million pounds of polymer resin processed [ppm (wt/wt)]. Scaled to production volumes, these emission factors can be used by processors to estimate emission quantities from similar PC processing operations.     

Integrating local ecological knowledge and management practices of an isolated semi-arid papyrus swamp (Loboi, Kenya) into a wider conservation framework

The current study documented local utilization of Cyperus papyrus L. (papyrus), harvesting patterns, threats, and local management practices among the Endorois community living around Loboi swamp (Kenya). Papyrus is a highly productive freshwater macrophyte that is widely utilized throughout tropical Africa. However, increased human population and poverty, has led to over exploitation and conversion of papyrus wetlands to agricultural fields. Nonetheless, users of papyrus hold important local ecological knowledge (LEK) and practices. We show that Endorois practices on papyrus uses are compatible with the management priorities of the swamp and a wider conservation framework using data obtained from three focus group discussions (FGD), interviews of 34 households and 15 key informants. The study revealed that papyrus support local livelihood notably as a source of income (papyrus mats are sold), cattle fodder, roofing materials (shelter), and cooking fuel. The study further revealed important LEK relating to harvesting patterns, recovery after harvesting and traditional management practices. Correlation and principal component analyses showed that experienced old harvesters (EXPERT) avoided harvesting repeatedly at the same location (REVISIT), thereby allowing recovery of papyrus when compared to younger harvesters (r = 0.63, p < 0.01). However, over 70% of harvesters predicted a decrease in papyrus coverage in the future due to the current diversion of water from the swamp, and frequent droughts, despite the instituted traditional management strategies (e.g. rotational harvesting) to curb overharvesting. The study concluded that the documentation of site-scale papyrus users' profile, LEK, and traditional practices are vital for the conservation and management of Loboi swamp.     

Phytoremediation of an arsenic-contaminated site using Pteris vittata L. and Pityrogramma calomelanos var. austroamericana: a long-term study

This field study investigated the phytoremediation potential of two arsenic (As) hyperaccumulating fern species, Pityrogramma calomelanos var. austroamericana and Pteris vittata over 27-month duration at a disused As-contaminated cattle-dip site located at Wollongbar, NSW, Australia. Ferns planted in January 2009 were harvested following 10, 22 and 27 months of growth. A detailed soil sampling was undertaken in June 2009 (initial, n?=?42 per plot) and limited sampling in April 2011 (after 27 months, n?=?15 per plot) to measure total and phosphate-extractable As concentrations in soil at 0?-?20-, 20?-?40- and 40?-?60-cm depths. The choice of the limited number of samples was considered sufficient to estimate the changes in soil As concentration following phytoremediation based on a geostatistical model. The average frond dry biomass, As concentration and As uptake were significantly (P??0.05), respectively, by P. vittata. Our results show that phytoremediation time based on observed changes in soil As based on limited sampling is not reliable; hence, it is recommended that the frond As uptake should be considered in order to evaluate the phytoremediation efficiency of the two fern species at the experimental site. Using As uptake of the two fern species, we estimate that with P. calomelanos var. austroamericana it would take 55?-?125 years to decrease mean total As content below the ecological investigation level (20 mg kg(-1)) in the surface and subsurface soils, whereas with P. vittata 143?-?412 years would be required to achieve this target.     

Optimum conditions for microbial carbonate precipitation

The type of bacteria, bacterial cell concentration, initial urea concentration, reaction temperature, the initial Ca(2+) concentration, ionic strength, and the pH of the media are some factors that control the activity of the urease enzyme, and may have a significant impact on microbial carbonate precipitation (MCP). Factorial experiments were designed based on these factors to determine the optimum conditions that take into consideration economic advantage while at the same time giving quality results. Sporosarcina pasteurii strain ATCC 11859 was used at constant temperature (25°C) and ionic strength with varying amounts of urea, Ca(2+), and bacterial cell concentration. The results indicate that the rate of ureolysis (k(urea)) increases with bacterial cell concentration, and the bacterial cell concentration had a greater influence on k(urea) than initial urea concentration. At 25 mM Ca(2+) concentration, increasing bacterial cell concentration from 10(6) to 10(8)cells mL?1 increased the CaCO(3) precipitated and CO(2) sequestrated by over 30%. However, when the Ca(2+) concentration was increased 10-fold to 250 mM Ca(2+), the amount of CaCO(3) precipitated and CO(2) sequestrated increased by over 100% irrespective of initial urea concentration. Consequently, the optimum conditions for MCP under our experimental conditions were 666 mM urea and 250 mM Ca(2+) at 2.3×10? cells mL?1 bacterial cell concentration. However, a greater CaCO(3) deposition is achievable with higher concentrations of urea, Ca(2+), and bacterial cells so long as the respective quantities are within their economic advantage. X-ray Diffraction, Scanning Electron Microscopy and Energy Dispersive X-ray analyzes confirmed that the precipitate formed was CaCO(3) and composed of predominantly calcite crystals with little vaterite crystals.     

Analysis of a Farquhar-von Caemmerer-Berry leaf-level photosynthetic rate model for Populus tremuloides in the context of modeling and measurement limitations

The balance of mechanistic detail with mathematical simplicity contributes to the broad use of the Farquhar, von Caemmerer and Berry (FvCB) photosynthetic rate model. Here the FvCB model was coupled with a stomatal conductance model to form an [A,g_s] model, and parameterized for mature Populus tremuloides leaves under varying CO₂ and temperature levels. Data were selected to be within typical forest light, CO₂ and temperature ranges, reducing artifacts associated with data collected at extreme values. The error between model-predicted photosynthetic rate (A) and A data was measured in three ways and found to be up to three times greater for each of two independent data sets than for a base-line evaluation using parameterization data. The evaluation methods used here apply to comparisons of model validation results among data sets varying in number and distribution of data, as well as to performance comparisons of [A,g_s] models differing in internal-process components.     

Kinetics of the tropospheric formaldehyde loss onto mineral dust and urban surfaces

The kinetics of the heterogeneous reaction between gaseous HCHO and TiO₂/SiO₂ mineral coatings were investigated using a coated-wall flow tube to mimic HCHO loss on mineral aerosol and TiO₂ coated depolluting urban surfaces. The measured uptake kinetics were strongly enhanced when the flow tube was irradiated with 340–420 nm UV light with an irradiance of 1.45 mW cm^?2. The associated BET uptake coefficients ranged from (3.00 ± 0.45) × 10^?9 to (2.26 ± 0.34) × 10^?6 and were strongly dependent on HCHO initial concentration, relative humidity, temperature, and TiO₂ content in the mineral coating, which ranged from 3.5 to 32.5 ppbv, 6–70%, 278–303 K, and 1–100 %wt, respectively. The measured kinetics were well described using a Langmuir–Hinshelwood type formalism. The estimated uptake coefficients were used to discuss the importance of heterogeneous HCHO surface loss, in terms of deposition lifetimes, as compared to major homogeneous gas-phase losses such as OH reaction and photolysis. It is found that deposition may compete with gas-phase removal of HCHO in a dense urban environment if more than 10% of the urban surface is covered with TiO₂ treated material.     

Use of CALPUFF for exposure assessment in a near-field,complex terrain setting

CALPUFF is an atmospheric source-receptor model recommended by the U.S. Environmental Protection Agency for use on a case-by-case basis in complex terrain and wind conditions. The ability of the model to provide useful information for exposure assessments in areas with those topographical and meteorological conditions has received little attention. This is an important knowledge gap for use of CALPUFF outside of regulatory applications, such as exposure analyses conducted in support of risk assessments and health studies. We compared deposition of cadmium (Cd), lead (Pb), and zinc (Zn) calculated with CALPUFF as a result of emissions from a zinc smelter with corresponding concentrations of the metals measured in attic dust and soil samples obtained from the surrounding area. On a point-by-point analysis, predictions from CALPUFF explained 11% (lead) to 53% (zinc) of the variability in concentrations measured in attic dust. Levels of heavy metals in soil interpolated to 100 residential addresses from the distribution of concentrations measured in soil samples also agreed well with deposition predicted with CALPUFF: R² of 0.46, 0.76, and 079 for Pb, Cd, and Zn, respectively. Community-average concentrations of Cd, Pb, and Zn measured in soil were significantly (p < 0.0001) and strongly correlated (R² ranged from 0.77 to 0.98) with predicted deposition rates. These findings demonstrate that CALPUFF can provide reasonably accurate predictions of the patterns of long-term air pollutant deposition in the near-field associated with emissions from a discrete source in complex terrain. Because deposition estimates are calculated as a linear function of air concentrations, CALPUFF is expected to be reliable model for prediction of long-term average, near-field ambient air concentrations in complex terrain as well.