A Comprehensive Python Toolkit for Accessing High‐Throughput Computing to Support Large Hydrologic Modeling Tasks

The National Flood Interoperability Experiment (NFIE) was an undertaking that initiated a transformation in national hydrologic forecasting by providing streamflow forecasts at high spatial resolution over the whole country. This type of large‐scale, high‐resolution hydrologic modeling requires flexible and scalable tools to handle the resulting computational loads. While high‐throughput computing (HTC) and cloud computing provide an ideal resource for large‐scale modeling because they are cost‐effective and highly scalable, nevertheless, using these tools requires specialized training that is not always common for hydrologists and engineers. In an effort to facilitate the use of HTC resources the National Science Foundation (NSF) funded project, CI‐WATER, has developed a set of Python tools that can automate the tasks of provisioning and configuring an HTC environment in the cloud, and creating and submitting jobs to that environment. These tools are packaged into two Python libraries: CondorPy and TethysCluster. Together these libraries provide a comprehensive toolkit for accessing HTC to support hydrologic modeling. Two use cases are described to demonstrate the use of the toolkit, including a web app that was used to support the NFIE national‐scale modeling.     

Ultrafine particles near a major roadway in Raleigh,North Carolina: Downwind attenuation and correlation with traffic-related pollutants

Ultrafine particles (UFPs, diameter < 100 nm) and co-emitted pollutants from traffic are a potential health threat to nearby populations. During summertime in Raleigh, North Carolina, UFPs were simultaneously measured upwind and downwind of a major roadway using a spatial matrix of five portable industrial hygiene samplers (measuring total counts of 20–1000 nm particles). While the upper sampling range of the portable samplers extends past the defined “ultrafine” upper limit (100 nm), the 20–1000 nm number counts had high correlation (Pearson R = 0.7–0.9) with UFPs (10–70 nm) measured by a co-located research-grade analyzer and thus appear to be driven by the ultrafine range. Highest UFP concentrations were observed during weekday morning work commutes, with levels at 20 m downwind from the road nearly fivefold higher than at an upwind station. A strong downwind spatial gradient was observed, linearly approximated over the first 100 m as an 8% drop in UFP counts per 10 m distance. This result agreed well with UFP spatial gradients estimated from past studies (ranging 5–12% drop per 10 m). Linear regression of other vehicle-related air pollutants measured in near real-time (10-min averages) against UFPs yielded moderate to high correlation with benzene (R² = 0.76), toluene (R² = 0.49), carbon monoxide (R² = 0.74), nitric oxide (R² = 0.80), and black carbon (R² = 0.65). Overall, these results support the notion that near-road levels of UFPs are heavily influenced by traffic emissions and correlate with other vehicle-produced pollutants, including certain air toxics.     

Environmentally friendly production of thiobencarb (Bolero)

S-Alkyl thiocarbamates are commercially available and widely used for their herbicidal properties. Despite the numerous methods for synthesizing these compounds, most employ toxic reagents that are harmful to the environment. Within we report a novel efficient one-pot process for the formation of thiobencarb employing readily available reagents. This method makes use of a trichloroacetyl chloride adduct and requires no complex starting materials. Furthermore, this process is efficient, proceeds in high yields, and utilizes several recyclable reagents.     

Characterization of Emissions from Vehicles Using Methanol and Methanol-Gasoline Blended Fuels

Exhaust and evaporative emissions were examined from vehicles fueled with methanol or a gasoline-methanol blend. Regulated automobile pollutants, as well as detailed hydrocarbons, methanol, and aldehydes were measured, and exhaust emission trends were obtained for vehicle operation over five different driving cycles. Results indicated that use of the blended fuel does not generally have any significant effect on base-line exhaust emission rates of regulated pollutants; however, emission rates of aldehydes increased during the Federal Test Procedure. Aldehyde emissions from the methanol-fueled car were roughly an order of magnitude higher than those resulting from blended fuel usage. The hydrocarbon composition of evaporative emissions with the blended fuel was similar to that with the base-line fuel except when canister breakthrough occurred. Evaporative emissions during breakthrough were comprised chiefly of N-butane.     

Influence of air permeation of pheromone on response of male lesser peachtree borers1 and peachtree borers2

Abstract

Air permeation trials were conducted with Z,Z and E,Z isomers of 3,13‐octadecadien‐1‐ol acetate (ODDA) to determine response difference between males of the peachtree borer (PTB), Synanthedon exitiosa (Say), and lesser peachtree borer (LPTB), S. pictipes (Grote & Robinson), within and adjacent to permeated plots of a peach orchard. The pheromone was released from hollow fiber dispensers attached to the trees in the orchard.

In the pheromone‐treated plots, both E,Z and Z,Z‐ODDA significantly reduced trap captures of PTB relative to the untreated plot. The E,Z isomer also significantly reduced captures of LPTB males but captures in the Z,Z treatment were higher than in the untreated plots. The pheromone treatments also influenced trap capture of both PTB and LPTB male moths outside the permeated plots.     

Traffic and meteorological impacts on near-road air quality: summary of methods and trends from the Raleigh Near-Road Study

A growing number of epidemiological studies conducted worldwide suggest an increase in the occurrence of adverse health effects in populations living, working, or going to school near major roadways. A study was designed to assess traffic emissions impacts on air quality and particle toxicity near a heavily traveled highway. In an attempt to describe the complex mixture of pollutants and atmospheric transport mechanisms affecting pollutant dispersion in this near-highway environment, several real-time and time-integrated sampling devices measured air quality concentrations at multiple distances and heights from the road. Pollutants analyzed included U.S. Environmental Protection Agency (EPA)-regulated gases, particulate matter (coarse, fine, and ultrafine), and air toxics. Pollutant measurements were synchronized with real-time traffic and meteorological monitoring devices to provide continuous and integrated assessments of the variation of near-road air pollutant concentrations and particle toxicity with changing traffic and environmental conditions, as well as distance from the road. Measurement results demonstrated the temporal and spatial impact of traffic emissions on near-road air quality. The distribution of mobile source emitted gas and particulate pollutants under all wind and traffic conditions indicated a higher proportion of elevated concentrations near the road, suggesting elevated exposures for populations spending significant amounts of time in this microenvironment. Diurnal variations in pollutant concentrations also demonstrated the impact of traffic activity and meteorology on near-road air quality. Time-resolved measurements of multiple pollutants demonstrated that traffic emissions produced a complex mixture of criteria and air toxic pollutants in this microenvironment. These results provide a foundation for future assessments of these data to identify the relationship of traffic activity and meteorology on air quality concentrations and population exposures.     

Herbicide loading to shallow ground water beneath Nebraska's Management Systems Evaluation Area

Better management practices can counter deterioration of ground water quality. From 1991 through 1996 the influence of improved irrigation practices on ground water pesticide contamination was assessed at the Nebraska Management Systems Evaluation Area. Three 13.4-ha corn (Zea mays L.) fields were studied: a conventional furrow-irrigated field, a surge-irrigated field and a center pivot-irrigated field, and a center pivot-irrigated alfalfa (Medicago sativa L.) field. The corn fields received one identical banded application of Bicep (atrazine [6-chloro-N-ethyl-N'-(1-methylethyl)-1,3,5-triazine-2,4,-diamine] + metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl) acetamidel) annually; the alfalfa field was untreated. Ground water samples were collected three times annually from 16 depths of 31 multilevel samplers. Six years of sample data indicated that a greater than 50% reduction in irrigation water on the corn management fields lowered average atrazine concentrations in the upper 1.5 m of the aquifer downgradient of the corn fields from approximately 5.5 to <0.5 microg L(-1). Increases in deethylatrazine (DEA; 2-chloro-4-amino-6-isopropylamino-s-triazine) to atrazine molar ratios indicated that reducing water applications enhanced microbial degradation of atrazine in soil zones. The occurrence of peak herbicide loading in ground water was unpredictable but usually was associated with heavy precipitation within days of herbicide application. Focused recharge of storm runoff that ponded in the surge-irrigated field drainage ditch, in the upgradient road ditch, and at the downgradient end of the conventionally irrigated field was a major mechanism for vertical transport. Sprinkler irrigation technology limited areas for focused recharge and promoted significantly more soil microbial degradation of atrazine than furrow irrigation techniques and, thereby, improved ground water quality.     

Herbicides in ground water beneath Nebraska's Management Systems Evaluation Area

Profiles of ground water pesticide concentrations beneath the Nebraska Management Systems Evaluation Area (MSEA) describe the effect of 20 yr of pesticide usage on ground water in the central Platte Valley of Nebraska. During the 6-yr (1991-1996) study, 14 pesticides and their transformation products were detected in 7848 ground water samples from the unconfined water table aquifer. Triazine and acetamide herbicides applied on the site and their transformation products had the highest frequencies of detection. Atrazine [6-chloro-N-ethyl-N'-(1-methylethyl)-1,3,5-triazine-2,4,-diamine] concentrations decreased with depth and ground water age determined with 3H/3He dating techniques. Assuming equivalent atrazine input during the past 20 yr, the measured average changes in concentration with depth (age) suggest an estimated half-life of >10 yr. Hydrolysis of atrazine and deethylatrazine (DEA; 2-chloro-4-amino-6-isopropylamino-s-triazine) to hydroxyatrazine [6-hydroxy-N-ethyl-N'-(1-methylethyl)-1,3,5-triazine-2,4-diamine] appeared to be the major degradation route. Aqueous hydroxyatrazine concentrations are governed by sorption on the saturated sediments. Atrazine was detected in the confined Ogallala aquifer in ultra-trace concentrations (0.003 microg L(-1)); however, the possibility of introduction during reverse circulation drilling of these deep wells cannot be eliminated. In fall 1997 sampling, metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl) acetamide] was detected in 57% of the 230 samples. Metolachlor oxanilic acid [(2-ethyl-6-methylphenyl)(2-methoxy-1-methylethyl) amino]oxo-acetic acid] was detected in most samples. In ground water profiles, concentrations of metolachlor ethane sulfonic acid [2-[(ethyl-6-methylphenyl)(2-methoxy-1-methylethyl)amino]-2-oxo-ethanesulfonic acid] exceeded those of deethylatrazine. Alachlor [2-chloro-N-(2,6-diethylphenyl)-N-(methoxymethyl)acetamide] was detected in <1% of the samples; however, alachlor ethane sulfonic acid [2-[(2,6-diethylphenyl)(methoxymethyl)amino]-2-oxoethanesulfonic acid] was present in most samples (63%) and was an indicator of past alachlor use.     

Variations in speciated emissions from spark-ignition and compression-ignition motor vehicles in California's south coast air basin

The U.S. Department of Energy Gasoline/Diesel PM Split Study examined the sources of uncertainties in using an organic compound-based chemical mass balance receptor model to quantify the contributions of spark-ignition (SI) and compression-ignition (CI) engine exhaust to ambient fine particulate matter (PM2.5). This paper presents the chemical composition profiles of SI and CI engine exhaust from the vehicle-testing portion of the study. Chemical analysis of source samples consisted of gravimetric mass, elements, ions, organic carbon (OC), and elemental carbon (EC) by the Interagency Monitoring of Protected Visual Environments (IMPROVE) and Speciation Trends Network (STN) thermal/optical methods, polycyclic aromatic hydrocarbons (PAHs), hopanes, steranes, alkanes, and polar organic compounds. More than half of the mass of carbonaceous particles emitted by heavy-duty diesel trucks was EC (IMPROVE) and emissions from SI vehicles contained predominantly OC. Although total carbon (TC) by the IMPROVE and STN protocols agreed well for all of the samples, the STN/IMPROVE ratios for EC from SI exhaust decreased with decreasing sample loading. SI vehicles, whether low or high emitters, emitted greater amounts of high-molecular-weight particulate PAHs (benzo[ghi]perylene, indeno[1,2,3-cd]pyrene, and coronene) than did CI vehicles. Diesel emissions contained higher abundances of two- to four-ring semivolatile PAHs. Diacids were emitted by CI vehicles but are also prevalent in secondary organic aerosols, so they cannot be considered unique tracers. Hopanes and steranes were present in lubricating oil with similar composition for both gasoline and diesel vehicles and were negligible in gasoline or diesel fuels. CI vehicles emitted greater total amounts of hopanes and steranes on a mass per mile basis, but abundances were comparable to SI exhaust normalized to TC emissions within measurement uncertainty. The combustion-produced high-molecular-weight PAHs were found in used gasoline motor oil but not in fresh oil and are negligible in used diesel engine oil. The contributions of lubrication oils to abundances of these PAHs in the exhaust were large in some cases and were variable with the age and consumption rate of the oil. These factors contributed to the observed variations in their abundances to total carbon or PM2.5 among the SI composition profiles.     

Remediating RDX-contaminated ground water with permanganate: laboratory investigations for the Pantex perched aquifer

Ground water beneath the U.S. Department of Energy Pantex Plant is contaminated with the high explosive RDX (hexahydro-1,3,5-trinitro-1,3,5 triazine). The USDOE Innovative Treatment and Remediation Demonstration (ITRD) program identified in situ oxidation by permanganate as a technology fit for further investigation. We evaluated the efficacy of KMnO(4) to transform and mineralize RDX by determining degradation kinetics and carbon mass balances using (14)C-RDX. Aqueous RDX solutions (2-5 mg L(-1)) and RDX-contaminated slurries (50% solids, w/v) were treated with KMnO(4) at 1000, 2000, 4000, and 20000 mg L(-1). Treating an aqueous RDX solution of 2.8 mg L(-1) with 20000 mg KMnO(4) L(-1) decreased RDX to 0.1 mg L(-1) within 11 d while cumulative mineralization proceeded for 14 d until 87% of the labeled carbon was trapped as (14)CO(2). Similar cumulative mineralization was obtained when Pantex aquifer material was included in the solution matrix. Other experiments using 4000 mg KMnO(4) L(-1) showed that initial RDX concentrations (1.3-10.4 mg L(-1)) or initial pH (4-11) had little effect on reaction rates. Attempts to identify RDX degradates and reaction products showed that N(2)O was a product of permanganate oxidation and constituted 20 to 30% of the N balance. Time-course measurements of a (14)C-RDX solution treated with KMnO(4) revealed few (14)C-labeled degradates but through liquid chromatography-mass spectrometry (LC-MS) analysis, we present evidence that 4-nitro-2,4-diaza-butanol is formed. Aquifer microcosm studies confirmed that the transformation products not mineralized by KMnO(4) were much more biodegradable than parent RDX. These results indicate permanganate can effectively transform and mineralize RDX in the presence of aquifer material and support its use as an in situ chemical oxidation treatment for the Pantex perched aquifer.