Hydrolysis of chlorpyrifos in natural waters of the Chesapeake Bay

Chlorpyrifos is the most widely used insecticide in the Chesapeake Bay region. Recent studies show that this organophospate chemical is consistently present in the air, rain and surface waters of the Chesapeake Bay region, suggesting a long environmental half-life. Hydrolytic degradation of chlorpyrifos is likely a dominant removal process, but existing hydrolysis data do not reflect conditions in the Chesapeake Bay. In this project, hydrolysis rates of chlorpyrifos were measured in sterilized, ambient water from the mouth of four Chesapeake Bay tributaries ranging in salinity from 0 to 17 ppt. The measured hydrolysis half-lives varied from 24 d in the Patuxent River to 126 d in the Susquehanna River. These results indicate that pH alone cannot be used as a single parameter to predict hydrolysis under field conditions. The influence of copper concentration, and other water constituents, need to be further evaluated as they may emerge as independent predictors to assess the fate of pesticides in natural systems.     

Costs, emissions reductions, and vehicle repair: evidence from Arizona

The Arizona inspection and maintenance (I/M) program provides one of the first opportunities to examine the costs and effectiveness of vehicle emission repair. This paper examines various aspects of emission reductions, fuel economy improvements, and repair costs, drawing data from over 80,000 vehicles that failed the I/M test in Arizona between 1995 and the first half of 1996. We summarize the wealth of data on repair from the Arizona program and highlight its limitations. Because missing or incomplete cost information has been a serious shortcoming for the evaluation of I/M programs, we develop a method for estimating repair costs when they are not reported. We find surprising evidence that almost one quarter of all vehicles that take the I/M test are never observed to pass the test. Using a statistical analysis, we provide some information about the differences between the vehicles that pass and those that do not. Older, more polluting vehicles are much more likely never to pass the I/M test, and their expected repair costs are much higher than those for newer cars. This paper summarizes the evidence on costs and emission reductions in the Arizona program, comparing costs and emissions reductions between cars and trucks. Finally, we examine the potential for more cost-effective repair, first through an analysis of tightening I/M cut points and then by calculating the cost savings of achieving different emission reduction goals when the most cost-effective repairs are made first.     

Propylene glycol vapor contamination in controlled environment growth chambers: toxicity to corn and soybean plants

A major, often unrecognized variable regulating plant growth in semi-closed environment is air contaminant. The vapor of propylene glycol (PG), which was used as coolant in growth chambers, has been found to be toxic to corn (Zea mays L.) and soybean (Glycine max L.) plants. PG solution leaked from a valve packing system and volatilized to vapor, which was trapped in a semi-closed growth chamber. Symptoms of leaf edge chlorosis, later developing into necrosis, were observed on the third day of emergence or on the third day after moving healthy plants into the chamber. For young soybean plants, symptoms were slightly different from those observed in corn plants; the chlorosis symptoms were not uniformly distributed on all leaves. Some soybean leaves curled up and others had white spots. This problem was identified by using a portable photoionization detector to obtain instantaneous readings of total volatile organic compound concentrations inside the chambers. The presence of PG in selected chambers was verified using sample collection with solid phase microextraction (SPME) followed by analysis with multi-dimensional gas chromatography mass spectrometry (MD-GC-MS). This information is pertinent to researchers who use controlled environment to grow plants.     

Determination of vapor pressure-temperature relationships of current–use pesticides and transformation products

Sub-cooled liquid vapor pressures (P_L ⁰) of current–use organochlorine and organophosphate pesticides (chlorothalonil, chlorpyrifos methyl, diazinon, fipronil) and selected transformation products (chlorpyrifos oxon, heptachlor epoxide, oxychlordane, 3,5,6-trichloro-2-pyridinol) were determined at multiple temperatures using the gas chromatography retention time technique. Results were utilized to determine vapor pressure-temperature relationships and to calculate enthalpies of vaporization (ΔH_vap). While results for chlorothalonil and diazinon were comparable with published values, the measured value for fipronil (1.82 × 10^{? 6} Pa) is almost an order of magnitude higher than the reported literature value (3.7 × 10^{? 7} Pa). The availability of vapor pressure temperature relationships for these chemicals will aid in pesticide risk assessment development and improve the effectiveness of mitigation and remediation efforts.     

Concentrations of particulate matter emitted from large cattle feedlots in Kansas

Particulate matter (PM) emitted from cattle feedlots are thought to affect air quality in rural communities, yet little is known about factors controlling their emissions. The concentrations of PM (i.e., PM2.5, PM10, and total suspended particulates or TSP) upwind and downwind at two large cattle feedlots (KS1, KS2) in Kansas were measured with gravimetric samplers from May 2006 to October 2009 (at KS1) and from September 2007 to April 2008 (at KS2). The mean downwind and net (i.e., downwind - upwind) mass concentrations of PM2.5, PM10, and TSP varied seasonally, indicating the need for multiple-day, seasonal sampling. The downwind and net concentrations were closely related to the moisture content of the pen surface. The PM2.5/PM10 and PM2.5/TSP ratios at the downwind sampling location were also related to the moisture content of the pen surface, humidity, and temperature. Measurement of the particle size distribution downwind of the feedlot with a cascade impactor showed geometric mean diameter ranging from 7 to 18 microm, indicating that particles that were emitted from the feedlots were generally large in size.     

Measured concentrations of herbicides and model predictions of atrazine fate in the Patuxent River estuary

The environmental fate of herbicides in estuaries is poorly understood. Estuarine physical transport processes and the episodic nature of herbicide release into surface waters complicate interpretation of water concentration measurements and allocation of sources. Water concentrations of herbicides and two triazine degradation products (CIAT [6-amino-2-chloro-4-isopropylamino-s-triazine] and CEAT [6-amino-2-chloro-4-ethylamino-s-triazine]) were measured in surface water from four sites on 40 d from 4 Apr. through 29 July 19% in the Patuxent River estuary, part of the Chesapeake Bay system. Atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine) was most persistent and present in the highest concentrations (maximum = 1.29 microg/L). Metolachlor [2-chloro-6'-ethyl-N-(2-methoxy-1-methylethyl)-o-acetoluidide], CIAT, CEAT, and simazine (1-chloro-3,5-bisethylamino-2,4,6-triazine) were frequently detected with maximum concentration values of 0.61, 1.1, 0.76, and 0.49 microg/L, respectively. A physical transport model was used to interpret atrazine concentrations in the context of estuarine water transport, giving estimates of in situ degradation rates and total transport. The estimated half-life of atrazine in the turbid, shallow upper estuary was t(1/2) = 20 d, but was much longer (t(1/2) = 100 d) in the deeper lower estuary. Although most (93%) atrazine entered the estuary upstream via the river, simulations suggested additional inputs directly to the lower estuary. The total atrazine load to the estuary from 5 April to 15 July was 71 kg with 48% loss by degradation and 31% exported to the Chesapeake Bay. Atrazine persistence in the estuary is directly related to river flows into the estuary. Low flows will increase atrazine residence time in the upper estuary and increase degradation losses.