Efficacy of recent state implementation plans for 8-hour ozone

The development of state implementation plans (SIPs) for attainment of criteria pollutant standards is an integral component of air quality management in the United States. However, the content and efficacy of SIPs have rarely been examined systematically. Here, 20 SIPs developed in response to the 1997 8-hr ozone standard are reviewed as case studies of attainment efforts at the state level. Comparison of observed and model predicted ozone concentrations shows the US Environmental Protection Agency (EPA) recommended modeled attainment test to be a somewhat conservative predictor of attainment. Among 12 SIPs for regions that sought attainment by 2009, the test correctly predicted attainment and nonattainment in four and five regions, respectively; in the other three regions, attainment was observed despite predictions of nonattainment. However weight-of-evidence determinations and deviations from the recommended modeled attainment test methodology led five of these SIPs to predict attainment that was not in fact observed by 2009; three of those regions achieved attainment in 2010. Ozone and NO2 concentrations declined across much of the United States during the period covered by the SIPs, with rates of improvement strongly correlated with the initial pollution levels and hence greatest in nonattainment regions. However at monitors with mid-range levels of ozone initially, rates of reduction were largely independent of the initial attainment status of the region. This is consistent with thefact that apart from California, the majority of ozone precursor reductions documented by SIPs resulted from federal measures rather than from state or local controls specific to the nonattainment regions.     

Assessing Surface Water Quality and Its Relation with Urban Land Cover Changes in the Lake Calumet Area, Greater Chicago

Urban land use and land cover change significantly affect spatial and temporal patterns of runoff, which in turn impacts surface water quality. With the exponential growth in urban areas over the past three decades, changes in land use and land cover to cater for the growth of cities has been a conspicuous spectacle in urban spaces. The main goal of this study was to assess the impacts of land cover change on runoff and surface water quality using a partial area hydrology framework. The study employed ArcHydro GIS extension and a modified version of Long-Term Hydrologic and Nonpoint Source Pollution model (L-THIA-NPS) in estimating runoff and nonpoint source pollutant concentration around Lake Calumet between 1992 and 2001. Data employed include National Land Cover Data set, rainfall data, digital elevation model (DEM), Soil Survey Geographic (SSURGO) data, and The United States Environmental Protection Agency’s STORET (storage and retrieval) water quality data. The model was able to predict surface water quality reasonably well over the study period. Sensitivity analysis facilitated a manual calibration of the model. Model validation was executed by comparing simulated results following calibration and observed water quality data for the study area. The study demonstrates that the level of concentration of nonpoint source pollutants in surface water within an urban watershed heavily depends on the spatiotemporal variations in areas that contribute towards runoff compared to the spatial extent of change in major land use/land cover.     

Response of two terrestrial green microalgae (Chlorophyta, Trebouxiophyceae) isolated from Cu-rich and unpolluted soils to copper stress

Some algae inhabit Cu-polluted soils. Intracellular Cu-accumulation and production of non-protein thiols in response to copper stress were compared in Stichococcus minor and Geminella terricola isolated from Cu-polluted and unpolluted soils, respectively. Cu-exposed (0.5 μM) S. minor accumulated lower amounts of copper (0.38 mM) than G. terricola (4.20 mM) and maintained 8.5-fold higher level of glutathione (GSH) than G. terricola. The ratio GSH/0.5 GSSG in the Cu-treated S. minor (7.21) was 7-times higher than in G. terricola. Reduced and oxidized forms of phytochelatins were found in both algae. Under copper stress (5 μM) the ratio -SH_total/Cu_{intracellular} in S. minor ranged from 2.3 to 6.2, while it was lower than 1.0 in G. terricola. Low intracellular Cu-accumulation and maintenance of high GSH level concomitant with PCs production seem to be responsible for a higher Cu-resistance of S. minor than G. terricola.     

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.     

The Removal of Particulate Matter from Fluid Bed Catalytic Cracking Unit Stack Gases

The application of a high-efficiency centrifugal type of separator to fluid bed catalytic cracking units is described in which most of the catalyst particles often lost to the atmosphere are concentrated into a small part of the stack gas (2%). A further separation can then be made on this small stream by an auxiliary separator which further concentrates the catalyst particle into 0.1% of the initia stream. Performance of the main and auxiliary separators are such as to reduce the loss of catalyst particles in the stack gas from 800 ppm to less than 60 ppm in a typical unit. Large amounts of power can be recovered by application of expander turbines to catalytic cracking plants employing this system of separation.     

The Effect of Fuel Composition on Atmospheric Aerosol Due to Auto Exhaust

Aerosols attributable to automobile exhaust can be classified as two types—primary aerosol (initially present in the exhaust) and secondary aerosol (generated photochemically from hydrocarbons and nitrogen oxides in the exhaust). In this study, investigation was made of possible effects of motor-fuel composition on the formation of these aerosols. Secondary aerosol, of principal interest in this work, was produced by irradiating auto exhaust in Battelle-Columbus’ 610 ft³ environmental chamber. A limited number of determinations of primary aerosol in diluted auto exhaust was made at the exit of a 36 ft dilution runnel. Determination of both primary and secondary aerosol was based on light-scattering measurements.

Exhaust was generated with seven full-boiling motor gasolines, both leaded and nonleaded, in a 1967 Chevrolet which was not equipped with exhaust-emission control devices. Changes in fuel composition produced a maximum factor of three difference in light scattering due to primary aerosol. Aerosol yields, for consecutive driving cycles on the same fuel, vary considerably; as a result, ranking the fuels on the basis of average primary aerosol yield was not very meaningful. In addition to fuel composition, the more important independent variables are initial SO₂ concentration, relative humidity and initial hydrocarbon concentration. Statistical analysis of the data indicates that the seven test fuels can be divided into two arbitrary groups with regard to secondary aerosol-forming potential. The fuels in the lower light-scattering group had aromatic contents of 15 and 21%, while those in the higher light-scattering group had aromatic contents of 25, 48, and 55%. Although the fuels can be grouped on the basis of a compositional factor, the grouping of fuels with aromatic content ranging from 25 to 55% indicates that this compositional factor cannot be equated simply with aromatic content. In an associated study of the aerosol-forming potential of individual hydrocarbons prominent in auto exhaust, it was observed that aromatics produce substantially more photochemical aerosol than olefins and paraffins. However, experiments with binar/hydrocarbon mixtures containing aromatjcs, as well as in these exhaust experiments, a strong dependence of aerosol yield on the aromatic components is is not observed. Thus, the data indicate that the dependence of secondary aerosol formation on fuel factors is a complex one and cannot be predicted solely on the basis of a sirigle hydrocarbon component reactivity scale.

The two types of automobile aerosol did not have the same dependence on fuel, composition. The variation in total light scattering attributable to primary plus secondary aerosol was less than that due to either component alone. It therefore was concluded that the light scattering due to automobile exhaust emissions in these experiments was not significantly affected by changing fuel composition.     

Correction methods for organic carbon artifacts when using quartz-fiber filters in large particulate matter monitoring networks: the regression method and other options

Sampling and handling artifacts can bias filter-based measurements of particulate organic carbon (OC). Several measurement-based methods for OC artifact reduction and/or estimation are currently used in research-grade field studies. OC frequently is not artifact-corrected in large routine sampling networks (e.g., U.S. Environmental Protection Agency (EPA)'s Chemical Speciation Network). In some cases, the OC artifact has been corrected using a regression method (RM) for artifact estimation. In this method, the gamma-intercept of the regression of the OC concentration on the fine particle (PM2.5) mass concentration is taken to be an estimate of the average OC sampling artifact (net of positive and negative artifacts). This paper discusses options for artifact correction in large routine sampling networks. Specifically, the goals are to (1) articulate the assumptions and limitations inherent to the RM, (2) describe other artifact correction approaches, and (3) suggest a cost-effective method for artifact correction in large monitoring networks. The RM assumes a linear relationship between measured OC and PM mass: a constant slope (OC mass fraction) and a constant intercept (RM artifact estimate). These assumptions are not always valid. Additionally, outliers and other individual data points can have a large influence on the RM artifact estimates. The RM yields results within the range of measurement-based methods for some datasets and not for others. Given that the adsorption of organic gases increases with atmospheric concentrations of organics, subtraction of an average artifact from all samples (e.g., across multiple sites) will underestimate OC for lower-concentration samples (e.g., clean sites) and overestimate OC for higher-concentration samples (e.g., polluted sites). For relatively accurate, simple, and cost-effective artifact OC estimation in large networks, the authors suggest backup filter sampling on at least 10% of sampling days at all sites with artifact correction on a sample-by-sample basis as described herein.     

Second generation anticoagulant rodenticides in predatory birds: Probabilistic characterisation of toxic liver concentrations and implications for predatory bird populations in Canada

Second-generation anticoagulant rodenticides (SGARs) are widely used to control rodent pests but exposure and poisonings occur in non-target species, such as birds of prey. Liver residues are often analysed to detect exposure in birds found dead but their use to assess toxicity of SGARs is problematic. We analysed published data on hepatic rodenticide residues and associated symptoms of anticoagulant poisoning from 270 birds of prey using logistic regression to estimate the probability of toxicosis associated with different liver SGAR residues. We also evaluated exposure to SGARs on a national level in Canada by analysing 196 livers from great horned owls (Bubo virginianus) and red-tailed hawks (Buteo jamaicensis) found dead at locations across the country. Analysis of a broader sample of raptor species from Quebec also helped define the taxonomic breadth of contamination. Calculated probability curves suggest significant species differences in sensitivity to SGARs and significant likelihood of toxicosis below previously suggested concentrations of concern (<0.1mg/kg). Analysis of birds from Quebec showed that a broad range of raptor species are exposed to SGARs, indicating that generalised terrestrial food chains could be contaminated in the vicinity of the sampled areas. Of the two species for which we had samples from across Canada, great horned owls are exposed to SGARs to a greater extent than red-tailed hawks and the liver residue levels were also higher. Using our probability estimates of effect, we estimate that a minimum of 11% of the sampled great horned owl population is at risk of being directly killed by SGARs. This is the first time the potential mortality impact of SGARs on a raptor population has been estimated.     

Perfluoroalkyl carboxylates and sulfonates and precursors in relation to dietary source tracers in the eggs of four species of gulls (Larids) from breeding sites spanning Atlantic to Pacific Canada

In the present study, we identified and examined the spatial trends, sources and dietary relationships of bioaccumulative perfluorinated sulfonate (PFSA; C(6), C(8), and C(10) chain lengths) and carboxylate (PFCA; C(6) to C(15) chain lengths) contaminants, as well as precursor compounds including several perfluorinated sulfonamides, and fluorotelomer acids and alcohols, in individual eggs (collected in 2008) from four gull species [glaucous-winged (Larus glaucescens), California (Larus californicus), ring-billed (Larus delawarensis) and herring (Larus argentatus) gulls] from 15 marine and freshwater colony sites in provinces across Canada. The pattern of PFSAs was dominated by perfluorooctane sulfonate (PFOS; >89% of ΣPFSA concentration) regardless of egg collection location. The highest ΣPFSA concentrations were found in the eggs collected in the urbanized areas in the Great Lakes and the St. Lawrence River area [Big Chicken Island 308 ng/g ww, Toronto Harbour 486 ng/g ww, and Ile Deslauriers (HG) 299 ng/g ww]. Also, eggs from all freshwater colony sites had higher ΣPFSA concentrations, which were significant (p<0.05) in many cases, compared to the marine sites with the exception of the Sable Island colony in Atlantic Canada off the coast of Nova Scotia. C(6) to C(15) chain length PFCAs were detected in the eggs, although the pattern was variable among the 15 sites, where PFUnA and PFTrA dominated the pattern for most colonies. Like the ΣPFSA, the highest concentrations of ΣPFCA were found in the eggs from Big Chicken Island, Toronto Harbour, Ile Deslauriers (HG), and Sable Island, although not all freshwater sites had higher concentrations compared to marine sites. Dietary tracers [δ(15)N and δ(13)C stable isotopes (SIs)] revealed that PFSA and PFCA exposure is colony dependent. SI signatures suggested that gulls from most marine colony sites were exposed to PFCs via marine prey. The exception was the Mandarte Island colony in Pacific British Columbia, where PFSA and PFCA exposure appeared to be via terrestrial and/or freshwater prey consumption. The same was true for the freshwater sites where egg SIs suggested both aquatic and terrestrial prey consumption as the source for PFC exposure depending on the colony. Both aquatic (marine and freshwater) and terrestrial prey are likely sources of PFC exposure to gulls but exposure scenarios are colony-specific.