Space-time analysis of the Air Quality Model Evaluation International Initiative (AQMEII) Phase 1 air quality simulations

This study presents an evaluation of summertime ozone concentrations over North America (NA) and Europe (EU) using the database generated from Phase 1 of the Air Quality Model Evaluation International Initiative (AQMEII). The analysis focuses on identifying temporal and spatial features that can be used to stratify operational model evaluation metrics and to test the extent to which the various modeling systems can replicate the features seen in the observations. Using a synoptic map typing approach, it is demonstrated that model performance varies with meteorological conditions associated with specific synoptic-scale flow patterns over both eastern NA and EU. For example, the root mean square error of simulated daily maximum 8-hr ozone was twice as high when cloud fractions were high compared with when cloud fractions were low over eastern NA. Furthermore, results show that over both NA and EU the regional models participating in AQMEII were able to better reproduce the observed variance in ambient ozone levels than the global model used to specify chemical boundary conditions, although the variance simulated by almost all regional models is still less that the observed variance on all spatiotemporal scales. In addition, all modeling systems showed poor correlations with observed fluctuations on the intraday time scale over both NA and EU. Furthermore, a methodology is introduced to distinguish between locally influenced and regionally representative sites for the purpose of model evaluation. Results reveal that all models have worse model performance at locally influenced sites. Overall, the analyses presented in this paper show how observed temporal and spatial information can be used to stratify operational model performance statistics and to test the modeling systems’ ability to replicate observed temporal and spatial features, especially at scales the modeling systems are designed to capture.

Implications: The analyses presented in this paper demonstrate how observed temporal and spatial information can be used to stratify operational model performance and to test the modeling systems’ ability to replicate observed temporal and spatial features. Decisions for the improvement of regional air quality models should be based on the information derived from only regionally representative sites.     

Effects of light and temperature fluctuations on the growth of Myriophyllum spicatum in toxicity tests—a model-based analysis

Laboratory toxicity tests are a key component of the aquatic risk assessments of chemicals. Toxicity tests with Myriophyllum spicatum are conducted based on working procedures that provide detailed instructions on how to set up the experiment, e.g., which experimental design is necessary to get reproducible and thus comparable results. Approved working procedures are established by analyzing numerous toxicity tests to find a compromise between practical reasons (e.g., acceptable ranges of ambient conditions as they cannot be kept completely constant) and the ability for detecting growth alterations. However, the benefit of each step of a working procedure, e.g., the random repositioning of test beakers, cannot be exactly quantified, although this information might be useful to evaluate working procedures. In this paper, a growth model of M. spicatum was developed and used to assess the impact of temperature and light fluctuations within the standardized setup. It was analyzed how important it is to randomly reassign the location of each plant during laboratory tests to keep differences between the relative growth rates of individual plants low. Moreover, two examples are presented on how modeling can give insight into toxicity testing. Results showed that randomly repositioning of individual plants during an experiment can compensate for fluctuations of light and temperature. A method is presented on how models can be used to improve experimental designs and to quantify their benefits by predicting growth responses.     

Rotary Kiln Incineration II. Laboratory-Scale Desorption and Kiln-Simulator Studies—Solids

With landfill costs increasing and regulations on landfilling becoming more stringent, alternatives to conventional hazardous waste treatment strategies are becoming more desirable. Incineration Is presently a permanent, proven solution for the disposal of most organic contaminants, but also a costly one, especially in the case of solids which require some auxiliary fuel. The goal of this research is to develop an understanding of the phenomena associated with the evolution of contaminants from solids In the primary combustor of an Incineration system. A four-fold approach is being used. First, a bench-scale particle characterization reactor was developed to study the transport phenomena on a particle basis, where the controlling processes are mainly intraparticle. Second, a bed-characterization reactor was built to examine the controlling transport phenomena within a bed of particles, where the processes are primarily interparticle. The results of these studies can be applied to any primary combustor. A pilot-scale rotary kiln was developed to study the evolution of contaminants from solids within a realistic temperature and rotation environment. Finally, in situ measurements are being obtained from a full-scale rotary-kiln.

This paper describes results obtained in a study using a commercial sorbent contaminated with toluene. The data are from the particle-characterization reactor and the rotary-kiln simulator. The results show that the method of contamination and charge size do not have a large effect on desorption, while temperature and contaminant concentration are important parameters In the evolution of contaminants in a rotary kiln.     

Degradation of Phenolic Resin by Tremetes versicolor

A phenolic resin that is used as syntan in leather manufacturing was degraded using Tremetes versicolor. On degradation of this resin for eight days, the reduction in biochemical oxygen demand (BOD), chemical oxygen demand (COD) and total organic carbon (TOC) were 65.11, 76.66 and 72.94% respectively. It was found from the infra red (IR) spectra of the samples that up to seven days the aromaticity was not perturbed however there were reductions in BOD and COD. Addition of co-substrate starch, brought about reduction in BOD, COD and TOC by 85.36, 91.93 and 89.98% respectively. After eight days, there observed a disturbance in the aromatic ring. The enzyme was extracted and assayed for polyphenol oxidase and laccase. Polyphenol oxidase activity and laccase activity of the crude enzyme were found to be 31.4 and 1.67 U/mL. On ammonium sulfate precipitation and dialysis, the polyphenol oxidase activity and laccase activity were enhanced by 1.5- and 3.2-folds respectively.     

Why ozonolysis may not increase the hydrophilicity of particles

It is commonly assumed that atmospheric oxidation of hydrocarbon particles or hydrocarbon coatings on particles leads to polar products and increased water uptake, altering atmospheric visibility and increasing the likelihood they will act as cloud condensation nuclei (CCN). We show here through laboratory experiments that increased water uptake depends on the 3-dimensional structure of the particles. Laboratory studies of particles formed during ozonolysis of surface-bound alkenes, present as terminally unsaturated self-assembled monolayers (C8= SAM) on a silica substrate, were carried out at room temperature and 1 atm pressure. SAMs were exposed to ～10¹³ O₃ molecules cm^?3 for 40 min and resultant particles were analyzed using single particle Fourier transform infrared micro-spectroscopy (micro-FTIR) and secondary ion mass spectroscopy (SIMS). Spectroscopy results show that –COOH and other polar groups are formed but are buried inside a hydrophobic shell, consistent with earlier observations (McIntire et al., 2005, Moussa et al., 2009) that water uptake does not increase after reaction of the terminal alkene with O₃. These insights into the 3-D structure of particles formed on oxidation have important implications for the ability of secondary organic aerosols to act as CCN. In addition, the nature of the surface of the particles is expected to determine their uptake into biological systems such as the surface of the lungs.     

The application of profluorescent nitroxides to detect reactive oxygen species derived from combustion-generated particulate matter: Cigarette smoke – A case study

Reactive oxygen species (ROS) and related free radicals are considered to be key factors underpinning the various adverse health effects associated with exposure to ambient particulate matter. Therefore, measurement of ROS is a crucial factor for assessing the potential toxicity of particles. In this work, a novel profluorescent nitroxide, BPEAnit, was investigated as a probe for detecting particle-derived ROS. BPEAnit has a very low fluorescence emission due to inherent quenching by the nitroxide group, but upon radical trapping or redox activity, a strong fluorescence is observed. BPEAnit was tested for detection of ROS present in mainstream and sidestream cigarette smoke. In the case of mainstream cigarette smoke, there was a linear increase in fluorescence intensity with an increasing number of cigarette puffs, equivalent to an average of 101 nmol ROS per cigarette based on the number of moles of the probe reacted. Sidestream cigarette smoke sampled from an environmental chamber exposed BPEAnit to much lower concentrations of particles, but still resulted in a clearly detectible increase in fluorescence intensity with sampling time. It was calculated that the amount of ROS was equivalent to 50 ± 2 nmol per mg of particulate matter; however, this value decreased with ageing of the particles in the chamber. Overall, BPEAnit was shown to provide a sensitive response related to the oxidative capacity of the particulate matter. These findings present a good basis for employing the new BPEAnit probe for the investigation of particle-related ROS generated from cigarette smoke as well as from other combustion sources.     

Phenotypic variation and adaptive reaction to the presence of predator in two Daphnia species (Daphniiformes, <Emphasis Type="Italic">Daphnia</Emphasis>) in Lake Baikal

The effect of invertebrate predation pressure by the cladoceran Leptodora kindti on the population structure of Daphnia galeata and D. hyalina has been estimated by analyzing the occurrence frequency of the normal and spined morphotypes in Lake Baikal. It is shown that the growth of L. kindti population density leads to an increase in the proportion of the spined morphotype, while that of that of the normal morphotype decreases.     

Effects of agricultural pesticides on the health of Rana pipiens frogs sampled from the field

There is evidence that over the last 30 years, there have been mass declines in diverse geographic locations among amphibian populations due to disease outbreaks. Multiple causes have been suggested to explain this increase in disease incidence. Among these, climate changes, environmental pollution and reduced water quality are gaining attention. Indeed, some chemicals of environmental concerns are known to alter the immune system. It is possible that exposure to these pollutants could alter the immune system of anurans and render them more susceptible to different pathogens. In this study, we sampled Rana pipiens in five different sites near St. Lawrence River (Quebec, Canada) during the months of July and September in 2001. Two of these sites were protected areas, in which low levels of pesticides were detected, while the remaining three sites were located in areas with intensive corn and soybeans cultivations. Our results demonstrated that frogs living in agricultural regions are smaller in size and weight than frogs living in areas with lower levels of pesticides at both sampling times. Moreover, we have observed a significant decrease in the number of splenocytes (cellularity) and the phagocytic activity in frogs sampled in impacted sites. Taken together, these results suggest that frogs living in agricultural regions might be more vulnerable to infections and diseases through their smaller size and alteration of their immune system. Our results also contribute to the overall discussion on factors involved in amphibian declines.     

PAH air pollution at a Portuguese urban area: carcinogenic risks and sources identification

This study aimed to characterize air pollution and the associated carcinogenic risks of polycyclic aromatic hydrocarbon (PAHs) at an urban site, to identify possible emission sources of PAHs using several statistical methodologies, and to analyze the influence of other air pollutants and meteorological variables on PAH concentrations.The air quality and meteorological data were collected in Oporto, the second largest city of Portugal. Eighteen PAHs (the 16 PAHs considered by United States Environment Protection Agency (USEPA) as priority pollutants, dibenzo[a,l]pyrene, and benzo[j]fluoranthene) were collected daily for 24 h in air (gas phase and in particles) during 40 consecutive days in November and December 2008 by constant low-flow samplers and using polytetrafluoroethylene (PTFE) membrane filters for particulate (PM₁₀ and PM_2.5 bound) PAHs and pre-cleaned polyurethane foam plugs for gaseous compounds. The other monitored air pollutants were SO₂, PM₁₀, NO₂, CO, and O₃; the meteorological variables were temperature, relative humidity, wind speed, total precipitation, and solar radiation. Benzo[a]pyrene reached a mean concentration of 2.02 ng?m^?3, surpassing the EU annual limit value. The target carcinogenic risks were equal than the health-based guideline level set by USEPA (10^?6) at the studied site, with the cancer risks of eight PAHs reaching senior levels of 9.98?×?10^?7 in PM₁₀ and 1.06?×?10^?6 in air. The applied statistical methods, correlation matrix, cluster analysis, and principal component analysis, were in agreement in the grouping of the PAHs. The groups were formed according to their chemical structure (number of rings), phase distribution, and emission sources. PAH diagnostic ratios were also calculated to evaluate the main emission sources. Diesel vehicular emissions were the major source of PAHs at the studied site. Besides that source, emissions from residential heating and oil refinery were identified to contribute to PAH levels at the respective area. Additionally, principal component regression indicated that SO₂, NO₂, PM₁₀, CO, and solar radiation had positive correlation with PAHs concentrations, while O₃, temperature, relative humidity, and wind speed were negatively correlated.