Heterogeneous conversion of nitric acid to nitrous acid on the surface of primary organic aerosol in an urban atmosphere

Nitrous acid (HONO), nitric acid (HNO₃), and organic aerosol were measured simultaneously atop an 18-story tower in Houston, TX during August and September of 2006. HONO and HNO₃ were measured using a mist chamber/ion chromatographic technique, and aerosol size and chemical composition were determined using an Aerodyne quadrupole aerosol mass spectrometer. Observations indicate the potential for a new HONO formation pathway: heterogeneous conversion of HNO₃ on the surface of primary organic aerosol (POA). Significant HONO production was observed, with an average of 0.97 ppbv event^?1 and a maximum increase of 2.2 ppb in 4 h. Nine identified events showed clear HNO₃ depletion and well-correlated increases in both HONO concentration and POA-dominated aerosol surface area (SA). Linear regression analysis results in correlation coefficients (r²) of 0.82 for HONO/SA and 0.92 for HONO/HNO₃. After correction for established HONO formation pathways, molar increases in excess HONO (HONO_excess) and decreases in HNO₃ were nearly balanced, with an average HONO_excess/HNO₃ value of 0.97. Deviations from this mole balance indicate that the residual HNO₃ formed aerosol-phase nitrate. Aerosol mass spectral analysis suggests that the composition of POA could influence HONO production. Several previously identified aerosol-phase PAH compounds were enriched during events, suggesting their potential importance for heterogeneous HONO formation.     

Estimating spatially-variable first-order rate constants in groundwater reactive transport systems

Numerical reactive transport models are often used as tools to assess aquifers contaminated with reactive groundwater solutes as well as investigating mitigation scenarios. The ability to accurately simulate the fate and transport of solutes, however, is often impeded by a lack of information regarding the parameters that define chemical reactions. In this study, we employ a steady-state Ensemble Kalman Filter (EnKF), a data assimilation algorithm, to provide improved estimates of a spatially-variable first-order rate constant λ through assimilation of solute concentration measurement data into reactive transport simulation results. The methodology is applied in a steady-state, synthetic aquifer system in which a contaminant is leached to the saturated zone and undergoes first-order decay. Multiple sources of uncertainty are investigated, including hydraulic conductivity of the aquifer and the statistical parameters that define the spatial structure of the parameter field. For the latter scenario, an iterative method is employed to identify the statistical mean of λ of the reference system. Results from all simulations show that the filter scheme is successful in conditioning the λ ensemble to the reference λ field. Sensitivity analyses demonstrate that the estimation of the λ values is dependent on the number of concentration measurements assimilated, the locations from which the measurement data are collected, the error assigned to the measurement values, and the correlation length of the λ fields.     

Interlaborafory Comparison of Formaldehyde Emissions from Particleboard Underlayment in Small-Scale Environmental Chambers

Formaldehyde (CH₂O) emissions from particleboard underlayment have been measured in 0.17 and 0.2 m³ chambers at separate laboratories to test the comparability of small scale environmental chamber measurements under different ventilation and product loading conditions. Absolute CH₂O calibration was established through intermethod comparison of different monitoring techniques against a CH₂O generation apparatus. Interlaboratory precision was enhanced via co-calibration of each laboratory’s CH₂O colorimetric analyzer against the same blank and bi-level generation source at the beginning and end of the study. The results show excellent intermethod and interlaboratory agreement in both the CH₂O calibration and particleboard emissions testing. The CH₂O emission rates of the test specimens demonstrate a Fick’s Law dependence on CH₂O vapor concentration. Measured CH₂O concentrations are described by a single-compartment, single emitter model, and are inversely proportional to the ratio [N/L (m/h)] of the air exchange rate [N(h^-1)] and product loading [L(m^-1)]. Comparison tests at varying N and L, but uniform N/L were performed; similar CH2O concentrations were measured for N and L levels selected from an indoor compartment model, and for fivefold larger N and L values, which are more convenient for small-scale chamber testing.     

Assessing President Obama’s climate change record

ABSTRACT

President Obama’s climate change record is assessed by looking at his success in translating policy goals into policy outputs (laws or regulatory action) during his time in office. Obama’s campaign speeches are examined to identify specific promises to take action on climate change before proceeding to examine whether, how and with what success he managed to act upon these pledges. Obama is shown to have set out a multi-pronged approach to deal with climate change in his campaign speeches and succeeded in translating many of his goals into policy outputs. This finding contributes to debates about Obama’s ‘green’ credentials.     

A calibrated auction-conjoint valuation method: Valuing pork and eggs produced under differing animal welfare conditions

This paper develops a valuation method which generates consistent and systematic estimates of people's preferences for complex multi-attribute goods by inextricably linking auction bids with conjoint ratings. The advantage of the valuation approach is that it permits the estimation of people's values for many potential goods, allows one to decompose people's values for a good into its sub-components, and permits the study of preference heterogeneity without distributional assumptions. We apply the method to an important and increasingly controversial topic: animal welfare. The method is used to determine people's preferences for eggs and pork produced from different production systems. Data from experiments conducted in three diverse U.S. locations (Chicago, IL; Dallas, TX; and Wilmington, NC) indicates that people are, on average, willing to pay $0.95 more for a dozen eggs raised in an aviary, pasture system vs. a cage system, and are willing to pay $2.02 more for two-pounds of pork chops raised in a pasture system as opposed to a crate system.     

Injectors for capillary gas chromatography and their application to environmental analysis

The application of different injectors in capillary gas chromatography (GC) analysis of semi-volatile organic contaminants in environmental samples prepared in organic solvents is reviewed. The injectors examined include a split/splitless injector in splitless mode (SS), cold on-column (COC), and programmable temperature vaporizer (PTV) and adaptations of these injector designs. Key issues when selecting an injector include properties of the analyte, such as potential for thermal degradation or discrimination of high boiling point compounds within the injector, and the ability of the GC systems to handle large volume injections (LVI) primarily to lower detection limits and allow direct coupling with sample preparation techniques such as at-line or on-line solid phase extraction (SPE). LVI also require consideration of matrix interference issues. This review examines only injector chamber modifications that are feasible with a standard GC configuration, however some modifications to the chromatographic system to extend the range of applicability of gas chromatography analysis for environmental samples are also noted.     

Female encounter rate and the calling behavior and mating propensity of male Requena verticalis (Orthoptera: Tettigoniidae)

Mating effort, the energy exerted in finding and persuading a member of the opposite sex to mate, may be influenced by how frequently potential mates are encountered. Specifically, males that frequently encounter females may reduce calling effort and be less eager to mate than males that infrequently encounter females. An experiment was set up to test this hypothesis, using the tettigoniid Requena verticalis. We examined the song structure, calling activity and mating propensity of individual males exposed to one of five different encounter rates with virgin females. Song structure and calling effort were significantly altered by an encounter with a female. After an encounter, males significantly increased chirp rate and decreased variability in interchirp interval. Encounters also stimulated a male to call and to continue to call for up to two hours. The elapsed time since mating affected mating propensity but not calling activity. Mating propensity asymptotically increased to reach a maximum by day 17 since last mating. However, neither the frequency of encounters, nor the number of previous encounters experienced by a male, influenced calling activity or the propensity of a male to mate. The significance of changes in song structure and calling activity following an encounter, and of increasing male mating propensity over time, are discussed. Correspondence to: G.R. Allen     

Biologically directed environmental monitoring, fate, and transport of estrogenic endocrine disrupting compounds in water: A review

Endocrine disrupting compounds (EDCs) are contaminants that may be hormonally active at low concentrations and are emerging as a major concern for water quality. Estrogenic EDCs (e-EDCs) are a subclass of EDCs that, when organisms are exposed to them, function as estrogens. Given that there are numerous e-EDCs that can negatively affect humans and wildlife, general screening techniques like biologically based assays (BBAs) may provide major advantages by estimating the total estrogenic effects of many e-EDCs in the environment. These techniques may potentially be adapted for field portable biologically directed sampling and analyses. This article summarizes available BBAs used to measure estrogenic e-EDCs in the environmental samples and also presents results relating to fate and transport of e-EDCs. Estrogenic EDCs appear to be almost ubiquitous in the environment, despite low solubility and high affinity of organic matter. Potential transport mechanisms may include: (1) transport of more soluble precursors, (2) colloid facilitated transport, (3) enhanced solubility through elevated pH, and (4) the formation of micelles by longer-chain ethoxylates. Due to their persistent and ubiquitous nature, source control strategies for e-EDCs may reduce influent concentration to wastewater treatment plants so that the post treatment effluent will decrease concentrations to estrogenically inactive levels. Alternatively if source reduction is not possible, then more testing is needed on tertiary treatment technologies and treatment efficiencies for e-EDCs. There is still a need for research on remediation and restoration approaches for habitats disturbed by elevated e-EDC concentrations.     

Experimental manipulation of mate choice by male katydids: the effect of female encounter rate

Summary This study tests the general prediction that discrimination among potential mates increases with the availability of potential mates. Specifically, we conducted two experiments that examined mate choice by male zaprochiline katydids in relation to their prior encounter rate with females. The probability of mate acceptance or rejection was measured for males given either frequent or no contact with females in the laboratory (experiment 1) and males taken directly from natural areas of either high or low female abundance (experiment 2). In both experiments, males with low female encounter rates were more likely to mate than males with high female encounter rates. In both cases, the decreased mating probability of males in the high encounter treatment resulted from their tendency to reject lighter (and less fecund) females. Despite the presumed advantage to males of selecting heavier females, field data indicate that, unlike females, males do not aggregate in rich food patches. Possible explanations for this finding are discussed. Offprint requests to: T.E. Shelly at the present address