Revised algorithm for estimating light extinction from IMPROVE particle speciation data

The Interagency Monitoring of Protected Visual Environments (IMPROVE) particle monitoring network consists of approximately 160 sites at which fine particulate matter (PM2.5) mass and major species concentrations and course particulate matter (PM10) mass concentrations are determined by analysis of 24-hr duration sampling conducted on a 1-day-in-3 schedule A simple algorithm to estimate light extinction from the measured species concentrations was incorporated in the 1999 Regional Haze Rule as the basis for the haze metric used to track haze trends. A revised algorithm was developed that is more consistent with the recent atmospheric aerosol literature and reduces bias for high and low light extinction extremes. The revised algorithm differs from the original algorithm in having a term for estimating sea salt light scattering from Cl(-) ion data, using 1.8 instead of 1.4 for the mean ratio of organic mass to measured organic carbon, using site-specific Rayleigh scattering based on site elevation and mean temperature, employing a split component extinction efficiency associated with large and small size mode sulfate, nitrate and organic mass species, and adding a term for nitrogen dioxide (NO2) absorption for sites with NO2 concentration information. Light scattering estimates using the original and the revised algorithms are compared with nephelometer measurements at 21 IMPROVE monitoring sites. The revised algorithm reduces the underprediction of high haze periods and the overprediction of low haze periods compared with the performance of the original algorithm. This is most apparent at the hazier monitoring sites in the eastern United States. For each site, the PM10 composition for days selected as the best 20% and the worst 20% haze condition days are nearly identical regardless of whether the basis of selection was light scattering from the original or revised algorithms, or from nephelometer-measured light scattering.     

Electrochemical oxidation of benzene on boron-doped diamond electrodes

This work presents an electrochemical investigation of the benzene oxidation process in aqueous solution on boron-doped diamond (BDD) electrodes. Additionally, in order to determine the main products generated during the oxidation process, electrolysis and high performance liquid chromatography experiments were carried out. The complete degradation of this compound was performed aiming to a further application in waste water treatment. The cyclic voltammetry studies indicate that benzene is irreversibly oxidized in acid medium (H₂SO₄ 0.5 M) on the BDD electrode surface at 2.0 V versus Ag/AgCl in a diffusion controlled process. During the cycling, other products are generated, and a pair of peaks was observed that can be associated with the oxi-reduction of anyone of the following species: hydroquinone, benzoquinone, resorcinol or catechol. The electrolysis experiments were carried out at 2.4 and 2.5 V on the BDD electrode surface in a solution containing 1 × 10⁻² M of benzene (below the saturation concentration in aqueous solution), for 3 and 5 h, respectively. The main products measured were: hydroquinone, resorcinol, p-benzoquinone, catechol and phenol. The complete electrochemical benzene degradation was performed in the electrolysis experiments using a rotating BDD disc electrode (2.5 V for 5 h) and the main products detected were all measured at concentrations lower than 10⁻⁵ M in this condition. The boron-doped diamond electrode had proved to be a valuable tool for the electrochemical degradation of the benzene, a very stable chemical compound.     

Thermal volatilization properties of atmospheric nanoparticles

Thermal volatilization is explored as a means of inferring the chemical composition of atmospheric aerosol particles with diameters smaller than 10 nm (nanoparticles). Such particles contain too little mass for quantitative chemical determination by traditional analytical methods. Aerosols were subjected to increasing temperature in an oven and particle loss was measured as a function of temperature with the TSI model 3025 ultrafine condensation particle counter (UCPC), which is capable of counting particles with diameters as small as 3 nm. Particle nucleation was observed down stream of the oven when it was heated above about 400°C. To reduce this artifact, the sample air down stream of the oven was cooled to condense the hot gases and/or the freshly nucleated particles before they reached the UCPC. Controlled experiments were done with pure ammonium sulfate (NH₄)₂SO₄ particles. The experimental design was optimized based on the known concentration of pure (NH₄)₂SO₄ particles vaporized in the oven and the diffusion of this material to the walls of the sampling tube before the particle counter.     

Multivariate Bayesian analysis of atmosphere–ocean general circulation models

Numerical experiments based on atmosphere–ocean general circulation models (AOGCMs) are one of the primary tools in deriving projections for future climate change. Although each AOGCM has the same underlying partial differential equations modeling large scale effects, they have different small scale parameterizations and different discretizations to solve the equations, resulting in different climate projections. This motivates climate projections synthesized from results of several AOGCMs’ output. We combine present day observations, present day and future climate projections in a single highdimensional hierarchical Bayes model. The challenging aspect is the modeling of the spatial processes on the sphere, the number of parameters and the amount of data involved. We pursue a Bayesian hierarchical model that separates the spatial response into a large scale climate change signal and an isotropic process representing small scale variability among AOGCMs. Samples from the posterior distributions are obtained with computer-intensive MCMC simulations. The novelty of our approach is that we use gridded, high resolution data covering the entire sphere within a spatial hierarchical framework. The primary data source is provided by the Coupled Model Intercomparison Project (CMIP) and consists of 9 AOGCMs on a 2.8 by 2.8 degree grid under several different emission scenarios. In this article we consider mean seasonal surface temperature and precipitation as climate variables. Extensions to our model are also discussed.     

Variable predation risk and the dynamic nature of mosquito antipredator responses to chemical alarm cues

Summary. Predation is a pervasive selective agent highly variable in space and time. Due to the costs associated with antipredator responses, prey would be at a selective advantage if they respond to predation threats with an intensitfy matching the threat posed by the predator. Many aquatic organisms have been shown to use chemical alarm cues present in the water to assess the level of risk in their environment. This includes mosquito larvae which show antipredator responses to conspecific alarm cues. In this study, we investigated the nature of the responses of larval mosquitoes Culex restuans to those cues. In our initial observations, we showed pond/population differences in the response intensity of C. restuans to alarm cues. In experiment 1, we showed that the response intensity to alarm cues could be increased by increasing the background level of risk in the mosquitoes’ environment (by adding salamander predators) and once turned on, the response intensity to alarm cues was likely maintained for the remainder of the mosquitoes’ aquatic life. In experiments 2 and 3, we investigated if the increase in response intensity to alarm cues was directly correlated with the level of background risk in the mosquitoes’ environment. When given increasing levels of background risk, mosquito larvae subsequently showed a graded response to conspecific alarm cues. This series of experiments demonstrates that the response intensity of larval mosquitoes to a standard concentration of alarm cues is not fixed, but rather dependent on the background level of risk in the environment. An understanding of the background level of risk is particularly important for comparing antipredator responses of prey between habitats.     

Cobalt distribution and speciation: effect of aging, intermittent submergence, in situ rice roots

The speciation and distribution of Co in soils is poorly understood. This study was conducted using x-ray absorption spectroscopy (XAS) techniques to examine the influence of soluble cobalt in the +2 oxidation state (Co[II]) aging, submergence-dried cycling, and the presence of in vivo rice roots on the speciation and distribution of added Co(II) in soils. In the aging and submerged-dried cycling studies, Co was found to be associated with Mn oxide fraction (23 to 100% of total Co) and Fe oxide fractions (0 to 77% of total Co) of the soils as either Co(II) species or a mixed Co(II), and Co in the +3 oxidation state (Co[III]) species. The surface speciation of Co in the Mn oxide fraction suggests an innersphere complex was present and the speciation of Co in the Fe oxide fraction was an innersphere surface complex. The in vivo root box experiments showed similar Co speciation in the Mn oxide fraction (13 to 76% of total Co) as the aging and submerged-dried cycling studies. However, the Fe oxide fraction of the soil was unimportant in Co retention. A significant amount (24 to 87% of total Co) of the Co in root box treatments was identified as a Co precipitate. The importance of this finding is that in the presence of rice roots, the Co is redistributed to a Co precipitate. This work confirmed earlier macroscopic work that Mn oxides are important in the sequestration of Co in soils and the influence of roots needs to be taken into account when addressing Co speciation. The information gained from this study will be used to improve models to predict the lability and hence the availability of Co in terrestrial environments.     

Deforestation Projections for Carbon-Rich Peat Swamp Forests of Central Kalimantan,Indonesia

We evaluated three spatially explicit land use and cover change (LUCC) models to project deforestation from 2005–2020 in the carbon-rich peat swamp forests (PSF) of Central Kalimantan, Indonesia. Such models are increasingly used to evaluate the impact of deforestation on carbon fluxes between the biosphere and the atmosphere. We considered both business-as-usual (BAU) and a forest protection scenario to evaluate each model’s accuracy, sensitivity, and total projected deforestation and landscape-level fragmentation patterns. The three models, Dinamica EGO (DE), GEOMOD and the Land Change Modeler (LCM), projected similar total deforestation amounts by 2020 with a mean of 1.01 million ha (Mha) and standard deviation of 0.17 Mha. The inclusion of a 0.54 Mha strict protected area in the LCM simulations reduced projected loss to 0.77 Mha over 15 years. Calibrated parameterizations of the models using nearly identical input drivers produced very different landscape properties, as measured by the number of forest patches, mean patch area, contagion, and Euclidean nearest neighbor determined using Fragstats software. The average BAU outputs of the models suggests that Central Kalimantan may lose slightly less than half (45.1%) of its 2005 PSF by 2020 if measures are not taken to reduce deforestation there. The relatively small reduction of 0.24 Mha in deforestation found in the 0.54 Mha protection scenario suggests that these models can identify potential leakage effects in which deforestation is forced to occur elsewhere in response to a policy intervention.     

Highly dynamic fission–fusion species can exhibit leadership when traveling

Leadership by specific individuals is thought to enhance the fitness of followers by allowing them to take advantage of the knowledge or skills of key individuals. In general, consistent leadership is expected to occur primarily in stable groups of related individuals where the benefits enhance the inclusive fitness of a leader. Societies with less stability in group composition (i.e., fission–fusion groups) are less likely to feature unshared decision making. However, in situations where frequent interactions among individuals occur (e.g., small population size and small range of movement) and/or the complexity of the environment requires substantial experience and knowledge, consistent leadership might be expected. We tested if a highly dynamic fission–fusion population of bottlenose dolphins (Tursiops truncatus), inhabiting a complex environment, exhibited leadership when traveling. A small number of specific individuals led group travel more often than expected by chance, and were more likely to initiate successful direction changes of groups than following individuals. The number of leaders in a group remained relatively constant across a wide range of group sizes and was not affected by the number of potential leaders (i.e., those that had led previously) present in the group. Together, these results suggest that leadership can occur in species with high rates of group fission and fusion. Therefore, the loss of key individuals could have disproportionate effects on population dynamics.     

Brevetoxins in sharks and rays (Chondrichthyes, Elasmobranchii) from Florida coastal waters

In October 2000, a mass mortality of blacktip sharks (Carcharhinus limbatus) and Atlantic sharpnose sharks (Rhizoprionodon terraenovae) in northwest Florida occurred in conjunction with a Karenia brevis red tide bloom. Before this incident, no information existed on red tide-induced shark mortalities or baseline brevetoxin levels in sharks and rays from red tide-endemic areas. We report here that brevetoxin accumulation in live and red tide-killed elasmobranchs is common during K. brevis blooms and non-bloom periods. Strong relationships were found between the frequency of red tide blooms and the average brevetoxin concentrations in elasmobranch tissues. The presence of brevetoxins in Atlantic coast sharks in the absence of documented K. brevis blooms may suggest that blooms are occurring in areas that are not well monitored. Although red tide-related shark mortalities are rarely observed, the presence of brevetoxins in shark embryos raises questions about the effects these toxins may have on the reproductive success of sharks.     

Evaluation of filter-based aerosol measurements during the 1987 Southern California Air Quality Study

The Southern California Air Quality Study (SCAQS) was conducted during the summer and fall of 1987 to assess the causes of elevated ozone and suspended particulate matter concentrations in California's South Coast Air Basin (SoCAB). Extensive gaseous (i.e. nitric acid, ammonia, sulfur dioxide) and particle (i.e. PM_2.5 and PM₁₀ mass, elements, ions, carbon) measurements were acquired for 11 days during the summer at nine locations, and six days during the fall at six locations. Outliers were identified so that they could be excluded from further statistical analyses. Carbon and elemental measurements were found to be negatively biased by 20% owing to inhomogenous aerosol deposits on the SCAQS filters and analysis methods which were applied to a portion of the filters. These biases seem relatively consistent, however, and should not affect conclusions drawn from data analysis efforts if they are appropriately considered. Significant fractions (30–60%) of ammonium nitrate volatilized during the summer when temperatures were higher. Less than 10% typically volatilized during the fall when temperatures were lower. Anion/cation balances support the accuracy and precision estimates of the nitrate, sulfate, and ammonium measurements. Coarse particle sulfate was generally low, while coarse particle nitrate was most pronounced at the coastal sites.This paper documents SCAQS filter-based aerosol measurement methods, and evaluates the accuracy, precision, and validity of the data set. Various comparisons were made for: (1) PM_2.5/PM₁₀ ratios for mass and major chemical species; (2) sum of chemical species versus measured mass; (3) sulfate versus sulfur ratios; (4) PM_2.5 particulate nitrate versus nitric acid-denuded nitrate; and (5) anion/cation balances. The measurement and evaluation techniques presented in this paper serve as a guideline for other data analysis and modeling studies.