A Mixed-Order Model to Assess Contaminant Declines

We introduce a generalized form of the common first-order (exponential) decay model, that has potential utility for describing contaminant declines in environmental applications, particularly when declines are a mixture of many underlying processes. The exponent on contaminant concentration is left as a free parameter allowing the order of the reaction to be determined by the data. The mixed-order model is more flexible than models with the exponent determined a priori, facilitating an improved fit to observed behavior. We demonstrate the utility of this model, and compare it to two other models, by estimating PCB concentration declines in Lake Michigan fishes.     

Evaluations of combined zebrafish (Danio rerio) embryo and marine phytoplankton (Diacronema lutheri) toxicity of dissolved organic contaminants in the Ythan catchment,Scotland, UK

A wide variety of organic contaminants including pesticides, polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) have previously been detected in surface waters in the river Ythan catchment, North East Scotland UK. While the concentrations detected were below Water Framework Directive Environmental Quality Standards (WFD-EQSs) environmental exposures to the diverse mixtures of contaminants, known and unknown, may pose chronic and/or sublethal effects to non target organisms. The present study assessed the embryo and algal toxicity potential of freely dissolved organic contaminants from the Ythan catchment using silicone rubber passive sampling devices (SR-PSDs) and miniaturised bioassay techniques. Zebrafish (Danio rerio) embryos and marine phytoplankton species (Diacronema lutheri) were exposed to extracts from SR-PSDs deployed at different locations along the river Ythan and an undeployed procedural blank. Statistically significant developmental and algal toxicities were measured in all tests of extracts from deployed samples compared with the procedural blanks. This indicates environmental exposure to, and the combined toxicity potential of, freely dissolved organic contaminants in the catchment. The present and previous studies in the Ythan catchment, coupling SR-PSDs and bioassay techniques, have both helped to understand the interactions and combined effects of dissolved organic contaminants in the catchment. They have further revealed the need for improvement in the techniques currently used to assess environmental impact.     

Measurement of transferable chemical residue from nylon carpet using the California roller and a new mega-California roller

Human chemical exposures resulting from transfer of surface deposition on indoor nylon carpets may be estimated by measuring transferable residues (μ g chemical/cm² carpet). A weighted roller developed at California Department of Food and Agriculture (CDFA) has been extensively used to sample transferable residue for estimates of human exposure in risk characterization. A modified roller has been developed to evaluate the influence of pressure on transferable chemical residue since weight and force (or pressure, kg/m²) may vary person-to-person and activity-to-activity. A 30.5 cm diameter roller was used to apply 60 to 2100 kg/m² to bracket pressures exerted by humans on a flat nylon-carpeted surface. Measurements of transferable cyfluthrin residues were made after 1, 7, and 21 days. Total Soxhlet extractable cyfluthrin residues were relatively constant during the test period. Residue transferability decreased during the study period. Modest increases in the transferability of surface residues were observed over the broad range of pressures applied by the modified roller.     

Kinetics and Mechanism of the Reaction of Azide with Ozone in Aqueous Solution

ABSTRACT

The stoichiometry of the reaction of aqueous ozone with sodium azide was studied at pH 12 (mainly) where a yellow metastable intermediate is observed. We propose that this is hypoazidite (N₃O^- ), analogous to hypobromite, and that it plays a central role in the azide catalyzed decompostion of ozone. The yellow intermediate is unstable in acid, in which it rapidly decomposes, generating N₂ and NO₂ ^-.

The rate of reaction was studied at pH 2.0–3.5, with the ionic strength at 0.6 M and temperature at 3–15 ° C. The intrinsic second-order rate constants were found to be k _HN3 ≤ ≈ 400 M^-1sec^-1 and k _N3- = (8.7 ± 0.5) × 10⁵ M^-1sec^-1 (3 °C, 0.6 M), both in agreement with the only other previous study. The rate constant at 25 °C was estimated using the following experimentally determined parameters: ln k_N3- (M^-1sec^-1) = (5.73 ± 0.36) × 10³/T (K) + (28.34 ± 1.27). The value of k_N3- estimated in this way is (2.5 ± 0.1) × 10⁶ M^-1sec^-1 at 25 °C and 0.6 M. The enthalpy of reaction (A H) is -48 ± 3 kJ mol^-1.     

The Effect of Reformulated Gasoline on Ambient Carbon Monoxide Concentrations in Southeastern Wisconsin

Abstract

Reformulated gasoline (RFG) contains oxygen additives such as methyl tertiary butyl ether or ethanol. The additives enable vehicles to burn fuel with a higher air/fuel ratio, thereby lowering the emission of carbon monoxide (CO) and volatile organic compounds (VOCs). Because VOCs react with sunlight to form ozone (O₃), the Clean Air Act requires severe O₃ nonattainment areas such as southeastern Wisconsin to use RFG. On July 17, 2001, the U.S. Environmental Protection Agency (EPA) granted Milwaukee, WI, and Chicago, IL, a waiver from the VOC reduction requirement of Phase II RFG. The VOC reduction requirement was lowered from 27.4% of the 1990 baseline fuel to 25.4%. The assumption was that ethanol-blended RFG would lower summertime CO concentrations sufficiently to offset the increased VOC emissions. The waiver is estimated to increase VOC emissions by ～0.8%, or 0.4 t of VOC on a hot summer weekday. This study evaluates whether RFG has been effective in lowering southeastern Wisconsin ambient CO concentrations. Three years of ambient CO data before RFG was introduced were compared with the first three years of ambient CO data after RFG was introduced. This paper also evaluates how the meteorology, vehicle inspection/maintenance program, vehicle miles traveled, and stationary source emissions influence CO concentrations. The winter decrease in ambient CO concentrations was found to be statistically significant, while the summer data showed no statistically significant change, indicating that RFG is most effective lowering ambient CO concentrations in cold weather.     

Is shrimp farming a successful adaptation to salinity intrusion? A geospatial associative analysis of poverty in the populous Ganges–Brahmaputra–Meghna Delta of Bangladesh

The Ganges–Brahmaputra–Meghna delta of Bangladesh is one of the most populous deltas in the world, supporting as many as 140 million people. The delta is threatened by diverse environmental stressors including salinity intrusion, with adverse consequences for livelihood and health. Shrimp farming is recognised as one of the few economic adaptations to the impacts of the rapidly salinizing delta. Although salinity intrusion and shrimp farming are geographically co-located in the delta, there has been no systematic study to examine their geospatial associations with poverty. In this study, we use multiple data sources including Census, Landsat Satellite Imagery and soil salinity survey data to examine the extent of geospatial clustering of poverty within the delta and their associative relationships with salinity intensity and shrimp farming. The analysis was conducted at the union level, which is the lowest local government administrative unit in Bangladesh. The findings show a strong clustering of poverty in the delta, and whilst different intensities of salinization are significantly associated with increasing poverty, neither saline nor freshwater shrimp farming has a significant association with poverty. These findings suggest that whilst shrimp farming may produce economic growth, in its present form it has not been an effective adaptation for the poor and marginalised areas of the delta. The study demonstrates that there are a series of drivers of poverty in the delta, including salinization, water logging, wetland/mudflats, employment, education and access to roads, amongst others that are discernible spatially, indicating that poverty alleviation programmes in the delta require strengthening with area-specific targeted interventions.     

Rapid and Sensitive LC/MS/MS Direct Injection Method for the Determination of Trace Level Corexit EC9500A Oil Dispersant in Seawater

A rapid and sensitive liquid chromatography tandem mass spectrometry (LC/MS/MS) method for the determination of trace dioctyl sulfosuccinate (DOSS) concentrations in seawater samples has been established. The method is well suited to aquatic environment impact monitoring following application of the dispersant Corexit EC9500A. Linearity of the method was demonstrated down to 0.05 ng/mL^?1 (0.05 µgL^?1) DOSS in seawater, with a 2.4% relative standard deviation precision for preparation replicates. A US EPA method limit of detection of <0.02 ng/mL^?1 (<0.02 µgL^?1) was calculated and specificity was confirmed by monitoring of two qualifier ions at 291.1 m/z and 227.1 m/z. These transitions were confirmed by QToF analysis to be associated with the DOSS precursor ion at 421.2 m/z. For application to seawater samples and samples containing oil particulates, a practical and repeatable calibration range of 0.5 ng/mL^?1 (0.5 µgL^?1) to 25.0 ng/mL^?1 (25.0 µgL^?1) DOSS is reported. The method was shown to have excellent precision and accuracy, with a consistent ≤1.6% relative standard deviation for system suitability standards at 0.5 ng/mL^?1 (0.5 µgL^?1) and linear weighted (1/x) regression coefficients of determination ≥0.995. The surfactant nature of the analyte is discussed in relation to detection limit and loss of analyte. Speculation of a relationship between DOSS in association or aggregation with divalent cations, such as Ca²⁺ present in salt water and hard water, is suggested. The consequent effects on cell ionic balance and membrane function are discussed.     

COVID-19: how a self-monitoring checklist can empower early intervention and slow disease progression

The SARS-CoV-2 novel coronavirus pandemic has revealed many scientific, social, and institutional challenges required to improve the health and wellbeing of individuals stricken by this disease. While organizations and governing institutions have risen to the task to concurrently prepare for and respond to this pandemic under conditions of high uncertainty and extreme pressure, another important aspect of this viral infection deserves attention and is not being fully considered, that is early intervention strategies and structured tools for individuals who test positive for the virus and begin developing symptoms. For those whose infection is progressing, we describe the potential benefits of a self-monitoring tool for use in combination with physician directed early medical interventions to slow COVID-19 progression.

     

Spatial and temporal changes in group dynamics and range use enable anti-predator responses in African buffalo

The reintroduction of large predators provides a framework to investigate responses by prey species to predators. Considerable research has been directed at the impact that reintroduced wolves (Canis lupus) have on cervids, and to a lesser degree, bovids, in northern temperate regions. Generally, these impacts alter feeding, activity, and ranging behavior, or combinations of these. However, there are few studies on the response of African bovids to reintroduced predators, and thus, there is limited data to compare responses by tropical and temperate ungulates to predator reintroductions. Using the reintroduction of lion (Panthera leo) into the Addo Elephant National Park (AENP) Main Camp Section, South Africa, we show that Cape buffalo (Syncerus caffer) responses differ from northern temperate ungulates. Following lion reintroduction, buffalo herds amalgamated into larger, more defendable units; this corresponded with an increase in the survival of juvenile buffalo. Current habitat preference of buffalo breeding herds is for open habitats, especially during the night and morning, when lion are active. The increase in group size and habitat preference countered initial high levels of predation on juvenile buffalo, resulting in a return in the proportion of juveniles in breeding herds to pre-lion levels. Our results show that buffalo responses to reintroduced large predators in southern Africa differ to those of northern temperate bovids or cervids in the face of wolf predation. We predict that the nature of the prey response to predator reintroduction is likely to reflect the trade-off between the predator selection and hunting strategy of predators against the life history and foraging strategies of each prey species.