Chemical and Biological Characterization of Products of Incomplete Combustion from the Simulated Field Burning of Agricultural Plastic

Chemical and biological analyses were performed to characterize products of Incomplete combustion emitted during the simulated open field burning of agricultural plastic. A small utility shed equipped with an air delivery system was used to simulate pile burning and forced-air-curtain incineration of a nonhalogenated agricultural plastic that reportedly consisted of polyethylene and carbon black. Emissions were analyzed for combustion gases; volatile, semi-volatile, and particulate organics; and toxic and mutagenlc properties. Emission samples, as well as samples of the used (possibly pesticide-contaminated) plastic, were analyzed for the presence of several pesticides to which the plastic may have been exposed. Although a variety of alkanes, alkenes, and aromatic and polycyclic aromatic hydrocarbon (PAH) compounds were identified in the volatile, seml-volatlle, and particulate fractions of these emissions, a substantial fraction of higher molecular weight organic material was not identified. No pesticides were Identified in either combustion emission samples or dlchloromethane washes of the used plastic. When mutagenlcity was evaluated by exposing Salmonella bacteria (Ames assay) to whole vapor and vapor/partlculate emissions, no toxic or mutagenlc effects were observed. However, organic extracts of the particulate samples were moderately mutagenlc. This mutagenlcity compares approximately to that measured from residential wood heating on a revertant per unit heat release basis. Compared to pile burning, forced air slightly decreased the time necessary to burn a charge of plastic. There was not a substantial difference, however, in the variety or concentrations of organic compounds Identified In samples from these two burn conditions. This study highlights the benefits of a combined chemical/biological approach to the characterization of complex, multi-component combustion emissions. These results may not reflect those of other types of plastic that may be used for agricultural purposes, especially those containing halogens.     

The Validation of a Passive Sampler for Indoor and Outdoor Concentrations of Volatile Organic Compounds

Abstract

Volatile organlcs compounds (VOCs) are ubiquitous in the air we breathe. The use of passive samplers to measure these concentrations can be an effective technique. When exposed for long durations, a passive sampler may be a good tool for investigating chronic exposures to chemicals in the environment. A passive sampler that was designed for occupational exposures can be used as such a tool. Laboratory validation under as many conditions as possible needs to be accomplished so as to characterize the sampler with known parameters. This paper describes the methods and results of an investigation into the validity of using a passive monitor to sample VOCs for a three-week period. Two concentration levels, two relative humidities, and five VOCs were studied. Results indicate that the samplers work best under conditions of high concentration with low relative humidity and low concentration with high relative humidity. For the passive sampler, excluding chloroform, percent deviations from the predicted values varied between ?41 and +22 percent; while the values between the passive and the active samplers varied between ?27 and +24 percent. Benzene, heptane, and perchloroethylene were sampled with equal precision and accuracy.     

A Tracer Study of Headspace Ventilation in a Collector Sewer

ABSTRACT

A field-scale tracer test was conducted to evaluate in-situ ventilation rates in a major collector sewer. The sewer under study was ~11 km long and ranged from 0.61 to 2.1 m in diameter. For the purposes of the tracer testing, the collector was divided into four reaches, each of which was tested individually. The tracer test involved injecting a measured volume of CO gas into a manhole over a short time period. CO concentrations were then measured in the collector headspace at selected manholes along the length of the reach.

The technique employed successfully measured average headspace velocities over extended lengths of the collector. In a section that had a relatively stagnant headspace, ~1.1 km of sewer could be evaluated, with substantial tracer loss attributed to losses to manholes. In a section of the sewer with elevated headspace velocities, a section ~7.0 km long was successfully tested with one injection of tracer gas. The velocities observed in the collector varied substantially with time and location in the collector. The lowest velocities measured were in the upstream sections, with a minimum observed value of 3.8 m/min. The highest velocities were observed in the downstream sections, with a maximum value of 31.5 m/min. The presence of a substantial drop structure appeared to reduce the headspace velocity in the upstream reach. In general, there was an increasing trend in gas-phase flows with distance along the length of the collector. Flows at the discharge end of the collector were almost 2 orders of magnitude greater than those at the beginning.     

Issues Related to Solution Chemistry in Mercury Sampling Impingers

ABSTRACT

Analysis of Hg speciation in combustion flue gases is often accomplished in standardized sampling trains in which the sample is passed sequentially through a series of aqueous solutions to capture and separate oxidized Hg (Hg²⁺) and elemental Hg (Hg⁰). Such methods include the Ontario Hydro (OH) and the Alkaline Mercury Speciation (AMS) methods, which were investigated in the laboratory to determine whether the presence of Cl₂ and other common flue gas species can bias the partitioning of Hg⁰ to front impingers intended to isolate Hg²⁺ species. Using only a single impinger to represent the front three impingers for each method, it was found that as little as 1-ppm Cl₂ in a simulated flue gas mixture led to a bias of approximately 10-20% of Hg⁰ misreported as Hg²+ for both the OH and the AMS methods. Experiments using 100-ppm Cl₂ led to a similar bias in the OH method, but to a 30-60% bias in the AMS method. These false readings are shown to be due to liquid-phase chemistry in the impinger solutions, and not necessarily to the gas-phase reactions between Cl₂ and Hg as previously proposed. The pertinent solution chemistry causing the interference     

Windsor, Ontario exposure assessment study: design and methods validation of personal, indoor, and outdoor air pollution monitoring

The Windsor, Ontario Exposure Assessment Study evaluated the contribution of ambient air pollutants to personal and indoor exposures of adults and asthmatic children living in Windsor, Ontario, Canada. In addition, the role of personal, indoor, and outdoor air pollution exposures upon asthmatic children's respiratory health was assessed. Several active and passive sampling methods were applied, or adapted, for personal, indoor, and outdoor residential monitoring of nitrogen dioxide, volatile organic compounds, particulate matter (PM; PM-2.5 pm [PM2.5] and < or =10 microm [PM10] in aerodynamic diameter), elemental carbon, ultrafine particles, ozone, air exchange rates, allergens in settled dust, and particulate-associated metals. Participants completed five consecutive days of monitoring during the winter and summer of 2005 and 2006. During 2006, in addition to undertaking the air pollution measurements, asthmatic children completed respiratory health measurements (including peak flow meter tests and exhaled breath condensate) and tracked respiratory symptoms in a diary. Extensive quality assurance and quality control steps were implemented, including the collocation of instruments at the National Air Pollution Surveillance site operated by Environment Canada and at the Michigan Department of Environmental Quality site in Allen Park, Detroit, MI. During field sampling, duplicate and blank samples were also completed and these data are reported. In total, 50 adults and 51 asthmatic children were recruited to participate, resulting in 922 participant days of data. When comparing the methods used in the study with standard reference methods, field blanks were low and bias was acceptable, with most methods being within 20% of reference methods. Duplicates were typically within less than 10% of each other, indicating that study results can be used with confidence. This paper covers study design, recruitment, methodology, time activity diary, surveys, and quality assurance and control results for the different methods used.     

Differential toxicity of silver and titanium dioxide nanoparticles on Drosophila melanogaster development, reproductive effort, and viability: size, coatings and antioxidants matter

Silver and titanium dioxide nanoparticles are known to induce oxidative stress in vitro and in vivo. Here we test if they impact development, mating success, and survivorship in Drosophila melanogaster, and if so, if these effects are reversible by antioxidants. Ingestion of nanotitanium dioxide during the larval stage of the life cycle showed no effects on development or survivorship, up to doses of 200 μg mL⁻¹. Conversely, ingestion of nanosilver had major dose, size, and coating-dependent effects on each of these aspects of life history. Each of these effects was partially or fully reversible by vitamin C. Larvae growing on nanosilver supplemented with vitamin C showed a greater than twofold increase in survivorship compared to flies reared on nanosilver alone, and a threefold increase in mating success. Vitamin C also rescued cuticular and pigmentation defects in nanosilver fed flies. Biochemical assays of superoxide dismutase and glutathione show these markers respond to nanotitanium dioxide and nanosilver induced oxidative stress, and this response is reduced by vitamin C. These results indicate that life history effects of nanosilver ingestion result from oxidative stress, and suggest antioxidants as a potential remediation for nanosilver toxicity. Conversely, the lack of nanotitanium dioxide life history toxicity shows that oxidative stress does not necessarily result in whole organism effects, and argues that nanoparticle toxicity needs to be examined at different levels of biological organization.     

Region-wide retreats from lower elevations of range-restricted birds across the Northern Andes

Local studies show upslope shifts in the distribution of tropical birds in response to warming temperatures. Unanswered is whether these upward shifts occur regionally across many species. We considered a nearly 2000-km length of the Northern Andes, where deforestation, temperature, and extreme weather events have increased during the past decades. Range-restricted bird species are particularly vulnerable to such events and occur in exceptionally high numbers in this region. Using abundant crowd-sourced data from the Cornell Lab of Ornithology database, eBird, and the Global Biodiversity Information Facility, we documented distributions of nearly 200 such species. We examined whether species shifted their elevational ranges over time by comparing observed versus expected occurrences below a low elevational threshold and above a high elevational threshold for 2 periods: before and after 2005. We predicted fewer observations at lower elevations (those below the threshold) and more at upper elevations (those above the threshold) after 2005. We also tested for deforestation effects at lower elevations within each species’ distribution ranges. We compared relative forest loss with the differences between observed and expected occurrences across the elevational range. Species’ retreats from lower elevations were ubiquitous and involved a 23–40% decline in prevalence at the lowest elevations. Increases at higher elevations were not consistent. The retreats occurred across a broad spectrum of species, from predominantly lowland to predominantly highland. Because deforestation showed no relationship with species retreats, we contend that a warming climate is the most parsimonious explanation for such shifts.     

Random forest models to estimate bankfull and low flow channel widths and depths across the conterminous United States

Channel dimensions (width and depth) at varying flows influence a host of instream ecological processes, as well as habitat and biotic features; they are a major consideration in stream habitat restoration and instream flow assessments. Models of widths and depths are often used to assess climate change vulnerability, develop endangered species recovery plans, and model water quality. However, development and application of such models require specific skillsets and resources. To facilitate acquisition of such estimates, we created a dataset of modeled channel dimensions for perennial stream segments across the conterminous United States. We used random forest models to predict wetted width, thalweg depth, bankfull width, and bankfull depth from several thousand field measurements of the National Rivers and Streams Assessment. Observed channel widths varied from <5 to >2000 m and depths varied from <2 to >125 m. Metrics of watershed area, runoff, slope, land use, and more were used as model predictors. The models had high pseudo R² values (0.70–0.91) and median absolute errors within ±6% to ±21% of the interquartile range of measured values across 10 stream orders. Predicted channel dimensions can be joined to 1.1 million stream segments of the 1:100 K resolution National Hydrography Dataset Plus (version 2.1). These predictions, combined with a rapidly growing body of nationally available data, will further enhance our ability to study and protect aquatic resources.