Geometric mean estimation from pooled samples

Biomonitoring for environmental chemicals presents various challenges due to the expense of measuring some compounds and the fact that in some samples the levels of many compounds may be below the limit of detection (LOD) of the measuring instrument. Even though various statistical methods have been developed to address issues associated with data being censored because results were below the LOD, the expense of measuring many compounds in large numbers of subjects remains a challenge. One solution to these challenges is to use pooled samples. There are many problems associated with the use of pooled samples as compared with individual samples, but using pooled samples can sometimes reduce the number of analytical measurements needed. Also, because pooled samples often have larger sample volumes, using pooled samples can result in lower LODs and thereby decrease the likelihood that results will be censored. However, many data sets obtained from environmental measurements have been shown to have a log-normal distribution, so using pooled samples presents a new problem: The measured value for a pooled sample is comparable to an arithmetic average of log-normal results and thus represents a biased estimate of the central tendency of the samples making up the pool. In this paper, we present a method for correcting the bias associated with using data from pooled samples with a log-normal distribution. We use simulation experiments to demonstrate how well the bias-correction method performs. We also present estimates for levels of PCB 153 and p,p'-DDE using data from pooled samples from the 2001 to 2002 National Health and Nutrition Examination Surveys.     

Conservation of Mammals in Eastern North American Wildlife Reserves: How Small Is Too Small?

Abstract: A common objective of methods of systematic reserve selection has been to maximize conservation benefits—frequently current species richness—while reducing the costs of acquiring and maintaining reserves. But the probability that a reserve will lose species in the future is frequently not known because the minimum area requirements for most species have not been estimated empirically. For reserves within the Alleghenian-Illinoian mammal province of eastern North America, we empirically estimated the minimum area requirement of terrestrial mammals such that reserves should not lose species because of insularization. We compared this estimate to the actual size of 2355 reserves and reserve assemblages within the mammal province. The estimated minimum area requirement was 5037 km² (95% CI: 2700–13,296 km²). Fourteen reserves and reserve assemblages were> 2700 km², 9 were> 5037 km², and 3 were> 13,296 km². These 14 reserves accounted for 73% of the total area of reserves and 10% of the total area of the mammal province. Few reserves appear large enough to avoid loss of some mammal species without the additional cost of active management of habitat or populations. Immigration corridors and buffer zones that combine small reserves into assemblages totaling at least 2700 km² may be the most efficient means of conserving mammals in these reserves.     

Measurement Error in Recreation Demand Models: The Joint Estimation of Participation, Site Choice, and Site Characteristics

In the demand for recreational fishing sites, an important explanatory variable differentiating sites is the unobserved expected catch rate. Since the observed catch rate is subject to sampling variability, using the average of a site's observed catch rates causes the parameter estimator on catch to be biased downward. We develop and demonstrate a solution to this errors-in-variables problem when there are repeated measurements on the catch rate. Consistent and efficient estimates of both the demand parameters and the expected catch rates are obtained by simultaneously estimating them by maximum likelihood. An empirical example demonstrates the importance of simultaneous estimation.     

The influence of suburban land use on habitat and biotic integrity of coastal Rhode Island streams

Watershed land use in suburban areas can affect stream biota through degradation of instream habitat, water quality, and riparian vegetation. By monitoring stream biotic communities in various geographic regions, we can better understand and conserve our watershed ecosystems. The objective of this study was to examine the relationship between watershed land use and the integrity of benthic invertebrate communities in eight streams that were assessed over a 3-year period (2001-2003). Sites were selected from coastal Rhode Island watersheds along a residential land-use gradient (4-59%). Using the rapid bioassessment protocol, we collected biological, physicochemical, habitat, and nutrient data from wadeable stream reaches and compared metrics of structure and integrity. Principal component analyses showed significant negative correlation of indicators for stream physicochemical, habitat, and instream biodiversity with increasing residential land use (RLU) in the watershed. The physicochemical variables that were most responsive to percent RLU were conductivity, instream habitat, nitrate, and dissolved inorganic nitrogen (DIN). The positive correlation of DIN with percent RLU indicated an anthropogenic source of pollution affecting the streams. The biotic composition of the streams shifted from sensitive to insensitive taxa as percent RLU increased; the most responsive biological variables were percent Ephemeroptera, percent Scrapers, percent Insects, and the Hilsenhoff biotic index. These data show the importance of land management and conservation at the watershed scale to sustaining the biotic integrity of coastal stream ecosystems.     

EMAP Design and River Reach File 3 (RF3) as a Sample Frame in the Central Valley, California

The Central Valley, California, R-EMAP project assessed the effects of highly modified, agriculturally dominated landuse on the aquatic resources of the lower portion of the Central Valley watersheds. The focus of this paper is to assess the utility of the EMAP design and the River Reach File version 3 (RF3) 1:100,000 scale Digital Line Graph (DLG) as a sampling frame. The study area is 34,099 mi²(88,316 km²) and comprises the lower reaches of the Sacramento River and San Joaquin River watersheds to the 1000 ft. (305 m) elevation. Sampling sites are selected using a tessellation stratified design to represent the two main populations of interest: natural streams and man-made waterways. Sites are selected to represent 13,226 miles of streams and sloughs, and 14,648 miles of irrigation canals, ditches and drains. To achieve an approximately equal sample size across stream orders and basins, the sample design was weighted by Strahler order categories to ensure sampling occurred in the higher order streams. Based on office and field reconnaissance, the study provided information on the quality of RF3 as a sampling frame. Site selection using RF3 had a success rate of approximately 44%. The RF3 database has an error rate of approximately 7%. When human influence factors were included, the error rate increased to 16%. There was an 11% error rate when selecting sites for natural streams, and approximately a 14% error rate for man-made waterways. The reconnaissance information indicated that presence or absence of irrigation ditches and return drains depends on changing agricultural uses. Some of the error in the RF3 for natural streams and man-made waterways can be attributed to rapid urban expansion, especially in the San Joaquin basin.     

Propanil in a Manitoba soil: an interactive spreadsheet model based on conventional chemical kinetics

An interactive spreadsheet model has been created for quantitative predictions of propanil sorption and reaction in a slurried Manitoba clay soil. Based on experimental values for the numbers of empty and filled sorption sites as reactants and products, the reaction mechanism has been described with conventional chemical kinetics. The on line HPLC μ extraction method revealed labile sorption, intraparticle diffusion, and a chemical reaction. Laidler's integral rate law for second order kinetics describes the labile sorption. Desorption, intraparticle diffusion, and the chemical reaction are all described by first order kinetics. The time dependent effects of initial concentration and amount of slurried soil can be predicted for sorption, intraparticle diffusion, and the amount of reaction product. Suggested applications include storm runoff and inputs for fate and transport hydrology models.     

Modeling to Evaluate Contribution of Oil and Gas Emissions to Air Pollution

Oil and gas production in the Western United States has increased considerably over the past 10 years. While many of the still limited oil and gas impact assessments have focused on potential human health impacts, the typically remote locations of production in the Intermountain West suggests that the impacts of oil and gas production on national parks and wilderness areas (Class I and II areas) could also be important. To evaluate this, we utilize the Comprehensive Air quality Model with Extensions (CAMx) with a year-long modeling episode representing the best available representation of 2011 meteorology and emissions for the Western United States. The model inputs for the 2011 episodes were generated as part of the Three State Air Quality Study (3SAQS). The study includes a detailed assessment of oil and gas (O&G) emissions in Western States. The year-long modeling episode was run both with and without emissions from O&G production. The difference between these two runs provides an estimate of the contribution of the O&G production to air quality. These data were used to assess the contribution of O&G to the 8 hour average ozone concentrations, daily and annual fine particulate concentrations, annual nitrogen deposition totals and visibility in the modeling domain. We present the results for the Class I and II areas in the Western United States. Modeling results suggest that emissions from O&G activity are having a negative impact on air quality and ecosystem health in our National Parks and Class I areas.

Implications: In this research, we use a modeling framework developed for oil and gas evaluation in the western United States to determine the modeled impacts of emissions associated with oil and gas production on air pollution metrics. We show that oil and gas production may have a significant negative impact on air quality and ecosystem health in some national parks and other Class I areas in the western United States. Our findings are of particular interest to federal land managers as well as regulators in states heavy in oil and gas production as they consider control strategies to reduce the impact of development.     

Potential Impacts of Stormwater Runoff on Water Quality in Urban Sand Pits and Adjacent Groundwater1

Whittemore, Donald O., 2012. Potential Impacts of Stormwater Runoff on Water Quality in Urban Sand Pits and Adjacent Groundwater. Journal of the American Water Resources Association (JAWRA) 48(3): 584-602. DOI: 10.1111/j.1752-1688.2011.00637.x Abstract: Entrance of stormwater runoff into water-filled pits and adjacent aquifers is a contamination concern. The water and sediment quality in several sand pits and surrounding groundwater in Wichita, Kansas, were studied to comprehensively address stormwater runoff impact. The pits are used for residential development after sand and gravel mining. Water samples were analyzed for inorganic constituents, bacteria, and 252 organic compounds, and pit sediments for inorganic components and 32 organic chemicals. Although many pesticide and degradate compounds were found in the pit and well waters, none of these chemicals exceeded existing health levels. Other organic contaminants were detected in the waters, with those exceeding health levels at one site attributed to an undiscovered groundwater contamination plume and not to stormwater runoff. Persistent insecticides and polychlorinated biphenyls detected in sediment of two pits are related to the age of residential development. The concentration distributions of pesticides and other organics at most of the sites, as well as iron, manganese, and ammonia patterns in downgradient well waters relative to upgradient well and pit waters, indicate that groundwater quality at the sites is affected by contaminants entering the pit surface waters. Thus, although current stormwater runoff does not appear to have contaminated sand-pit water and adjacent groundwater above health levels, the data show that the potential exists if stormwater became polluted.     

Volatile organic compounds at two oil and natural gas production well pads in Colorado and Texas using passive samplers

A pilot study was conducted in application of the U.S. Environmental Protection Agency (EPA) Methods 325A/B variant for monitoring volatile organic compounds (VOCs) near two oil and natural gas (ONG) production well pads in the Texas Barnett Shale formation and Colorado Denver–Julesburg Basin (DJB), along with a traffic-dominated site in downtown Denver, CO. As indicated in the EPA method, VOC concentrations were measured for 14-day sampling periods using passive-diffusive tube samplers with Carbopack X sorbent at fenceline perimeter and other locations. VOCs were significantly higher at the DJB well pad versus the Barnett well pad and were likely due to higher production levels at the DJB well pad during the study. Benzene and toluene were significantly higher at the DJB well pad versus downtown Denver. Except for perchloroethylene, VOCs measured at passive sampler locations (PSs) along the perimeter of the Barnett well pad were significantly higher than PSs farther away. At the DJB well pad, most VOC concentrations, except perchloroethylene, were significantly higher prior to operational changes than after these changes were made. Though limited, the results suggest passive samplers are precise (duplicate precision usually ≤10%) and that they can be useful to assess spatial gradients and operational conditions at well pad locations over time-integrated periods.

Implications: Recently enacted EPA Methods 325A/B use passive-diffusive tube samplers to measure benzene at multiple fenceline locations at petrochemical refineries. This pilot study presents initial data demonstrating the utility of Methods 325A/B for monitoring at ONG facilities. Measurements revealed elevated concentrations reflective of production levels and spatial gradients of VOCs relative to source proximity at the Barnett well pad, as well as operational changes at the DJB well pad. Though limited, these findings indicate that Methods 325A/B can be useful in application to characterize VOCs at well pad boundaries.     

Spatial analysis of volatile organic compounds in South Philadelphia using passive samplers

Select volatile organic compounds (VOCs) were measured in the vicinity of a petroleum refinery and related operations in South Philadelphia, Pennsylvania, USA, using passive air sampling and laboratory analysis methods. Two-week, time-integrated samplers were deployed at 17 sites, which were aggregated into five site groups of varying distances from the refinery. Benzene, toluene, ethylbenzene, and xylene isomers (BTEX) and styrene concentrations were higher near the refinery’s fenceline than for groups at the refinery’s south edge, mid-distance, and farther removed locations. The near fenceline group was significantly higher than the refinery’s north edge group for benzene and toluene but not for ethylbenzene or xylene isomers; styrene was lower at the near fenceline group versus the north edge group. For BTEX and styrene, the magnitude of estimated differences generally increased when proceeding through groups ever farther away from the petroleum refining. Perchloroethylene results were not suggestive of an influence from refining. These results suggest that emissions from the refinery complex contribute to higher concentrations of BTEX species and styrene in the vicinity of the plant, with this influence declining as distance from the petroleum refining increases.

Implications: Passive sampling methodology for VOCs as discussed here is employed in recently enacted U.S. Environmental Protection Agency Methods 325A/B for determination of benzene concentrations at refinery fenceline locations. Spatial gradients of VOC concentration near the refinery fenceline were discerned in an area containing traffic and other VOC-related sources. Though limited, these findings can be useful in application of the method at such facilities to ascertain source influence.