Estimating the contribution of point sources to atmospheric metals using single-particle mass spectrometry

Single-particle mass spectra were collected using an Aerosol Time-of-Flight Mass Spectrometer (ATOFMS) during December of 2003 and February of 2004 at an industrially impacted location in East St. Louis, IL. Hourly integrated peak areas for twenty ions were evaluated for their suitability in representing metals/metalloids, particularly those reported in the US EPA Toxic Release Inventory (TRI). Of the initial twenty ions examined, six (Al, As, Cu, Hg, Ti, and V) were found to be unsuitable due to strong isobaric interferences with commonly observed organic fragments, and one (Be) was found to have no significant signal. The usability of three ions (Co, Cr, and Mn) was limited due to suspected isobaric interferences based on temporal comparisons with commonly observed organic fragments. The identity of the remaining ions (Sb, Ba, Cd, Ca, Fe, Ni, Pb, K, Se, and Zn) was substantiated by comparing their signals with the integrated hourly signals of one or more isotope ions. When compared with one-in-six day integrated elemental data as determined by X-ray fluorescence spectroscopy (XRF), the daily integrated ATOFMS signal for several metal ions revealed a semi-quantitative relationship between ATOFMS peak area and XRF concentrations, although in some cases comparison of these measurements were poor at low elemental concentrations/ion signals due to isobaric interferences. A method of estimating the impact of local point sources was developed using hourly integrated ATOFMS peak areas, and this method attributed as much as 85% of the concentration of individual metals observed at the study site to local point sources. Hourly surface wind data were used in conjunction with TRI facility emissions data to reveal likely point sources impacting metal concentrations at the study site and to illustrate the utility of using single-particle mass spectral data to characterize atmospheric metals and identify point sources.     

Genetic differentiation in Littorina saxatilis (Gastropoda)

Littorina saxatilis, an ovoviviparous gastropod, displays considerable morphological variability, perhaps due to limited dispersal abilities. Gene and genotype frequencies of 2 polymorphic enzymatic loci were determined electrophoretically for 7 populations of L. saxatilis, to estimate degree of population differentiation. Results show that significant population differentiation may occur over distances of as little as 2 km, while widely separated populations may be nearly identical. An index of probability of genotypic identity calculated for populations of L. saxatilis shows variable and heterogeneous values. Comparison of this index for L. saxatilis with an index for 12 populations of Nassarius obsoletus —which possesses strong dispersal abilities due to long-term veliger larva and high, homogeneous indices of probability of genotypic identity between populations — indicates a strong correlation between population differentiation and dispersal ability of the organism. Possible factors influencing population differentiation in L. saxatilis are discussed.     

A model for improving endangered species recovery programs

This paper discusses common organizational problems that cause inadequate planning and implementation processes of endangered species recovery across biologically dissimilar species. If these problems occur, even proven biological conservation techniques are jeopardized. We propose a solution that requires accountability in all phases of the restoration process and is based on cooperative input among government agencies, nongovernmental conservation organizations, and the academic community. The first step is formation of a task-oriented recovery team that integrates the best expertise into the planning process. This interdisciplinary team should be composed of people whose skills directly address issues critical for recovery. Once goals and procedures are established, the responsible agency (for example, in the United States, the US Fish and Wildlife Service) could divest some or all of its obligation for implementing the plan, yet still maintain oversight by holding implementing entities contractually accountable. Regular, periodic outside review and public documentation of the recovery team, lead agency, and the accomplishments of implementing bodies would permit evaluation necessary to improve performance. Increased cooperation among agency and nongovernmental organizations provided by this model promises a more efficient use of limited resources toward the conservation of biodiversity.     

Bioconcentration of nonylphenol in fathead minnows (Pimephales promelas)

Bioconcentration of p-nonylphenol (NP) by fathead minnows was determined under laboratory conditions. Fish were exposed continuously for 42 days to 0.33, 0.93 and 2.36 μgNP/l in a flow-through system. NP was Soxhlet extracted from whole fish homogenates with dichloromethane (DCM). The resulting extract was concentrated and bulk lipids removed by gel permeation and silica-gel chromatography. Compounds were identified and quantified by reverse-phase high-pressure liquid chromatography (RP-HPLC) with fluorescence detection. Mass spectrometry was used for verification of peak assignments. Bioconcentration factors (BCFs) ranged from 245 to 380.     

Determination of Baghouse Performance from Coal and Ash Properties: Part I

Baghouse performance at utility coal-fired power plants is determined by baghouse design, operating procedures, and the characteristics of the ash that is collected as a dustcake on the fabric filter. The Electric Power Research Institute has conducted laboratory research to identify the fundamental properties of dustcake ash that influence baghouse performance. A database was assembled including measured characteristics of dustcake ash and data describing operating parameters and performance of full-scale and pilot-scale baghouses. Semi-empirical models were developed that describe the effects of particle morphology, particle size, ash cohesivity and ash chemistry on filtering pressure drop and particulate emissions. Cohesivity was identified as the primary ash characteristic affecting baghouse performance. Predictions of performance can be based on physical or chemical characterizations of the ash to be filtered. Part II of this article will discuss the effects of ash and coal chemistry, and baghouse design and operation on performance.     

A national probabilistic study of polybrominated diphenyl ethers in fish from US lakes and reservoirs

Polybrominated diphenyl ethers (PBDEs) are persistent, bioaccumulative, and toxic chemicals that are present in air, water, soil, sediment, and biota (including fish). Most previous studies of PBDEs in fish were spatially focused on targeted waterbodies. National estimates were developed for PBDEs in fish from lakes and reservoirs of the conterminous US (excluding the Laurentian Great Lakes) using an unequal probability design. Predator (fillet) and bottom-dweller (whole-body) composites were collected during 2003 from 166 lakes selected randomly from the target population of 147,343 lakes. Both composite types comprised nationally representative samples that were extrapolated to the sampled population of 76,559 and 46,190 lakes for predators and bottom dwellers, respectively. Fish were analyzed for 34 individual PBDE congeners and six co-eluting congener pairs representing a total of 46 PBDEs. All samples contained detectable levels of PBDEs, and BDE-47 predominated. The maximum aggregated sums of congeners ranged from 38.3 ng/g (predators) to 125 ng/g (bottom dwellers). Maximum concentrations in fish from this national probabilistic study exceeded those reported from recent targeted studies of US inland lakes, but were lower than those from Great Lakes studies. The probabilistic design allowed the development of cumulative distribution functions to quantify PBDE concentrations versus the cumulative number of US lakes from the sampled population.     

Dissipation,half-lives,and mass spectrometric identification of chlorpyrifos and its two metabolites on field-grown collard and kale

The persistence and fate of chlorpyrifos and its two metabolites, chlorpyrifos-oxon and the 3, 5, 6-trichloro-2-pyridinol (TCP) break-down product were investigated on kale and collard leaves under field conditions. A simultaneous extraction and quantification procedure was developed for chrorpyrifos and its two main metabolites. Residues of chlorpyrifos, chlorpyrifos oxon, and TCP were determined using a gas chromatograph (GC) equipped with an electron capture detector (GC/ECD). Chlorpyrifos metabolites were detectable up to 23 days following application. Residues were confirmed using a GC equipped with a mass selective detector (GC/MSD) in total ion mode. Initial residues of chlorpyrifos were greater on collard (14.5 µg g^?1) than kale (8.2 µg g^?1) corresponding to half-lives (T_1/2) values of 7.4 and 2.2 days, respectively. TCP, the hydrolysis product, was more persistent on collards with an estimated T_1/2 of 6.5 days compared to kale (T_1/2 of 1.9 days).     

Repellency and oviposition deterrence of wild tomato leaf extracts to spider mites,Tetranychus urticae Koch

Glandular trichomes on the leaves of wild tomato, Lycopersicon hirsutum f. hirsutum Mull, also known as Solanum habrochaites (Solanaceae) synthesize and accumulate high levels of methyl ketones (MKs). The potential of using MKs as alternatives to synthetic acaricides for controlling the twospotted spider mite, Tetranychus urticae Koch, is explored in this study. Plants of L. hirsutum accession LA 407 having high concentrations of MKs were grown from seeds under greenhouse conditions. The main objective of this investigation was to conduct bioassays that are quick and easy to implement, consistent over time (repeatable) with the ability to utilize small amounts of test material for testing repellency and fecundity (number of eggs laid by a female mite) of MKs in pure forms and in LA 407 crude extracts. Four MKs (2-tridecanone, 2-undecanone, 2-dodecanone, 2-pentadecanone) and their mixture were screened for their repellency and ability to alter fecundity of spider mites. All MKs repelled spider mites at the two periods tested. Following spraying of tomato leaf extracts prepared in ethanol (ethanol extracts), average number of eggs laid per female mite on bean leaf discs dropped from 0.8 to 0.3 and from 0.9 to 0.3 at 4 and 24 h after exposure representing 65 and 68% reduction, respectively. However, spraying of tomato leaf extracts prepared in water (water extracts) reduced number of eggs laid per female mite from 1.7 to 0.7 and from 2.6 to 0.9 at 4 and 24 h after exposure representing 60 and 67% reduction, respectively. We concluded that all MKs have repellent and egg laying deterrence activities against spider mites. This investigation suggests that ethanol and water extracts of LA 407 have a potential for repelling female spider mites and reducing their laid eggs which might be explored under field conditions for managing populations of spider mites, which could reduce reliance on synthetic acaricides.     

Synthetic SO2 Sorbents for Fluidized-Bed Coal Combustors

The information presented in this paper is directed to engineers who are involved with environmental emissions from coal conversion plants. Synthetic sorbents were investigated as an alternative to natural sorbents (limestone) for the removal of SO₂ from the combustion gas in a fluidized-bed coal combustor. The sulfation rate of a synthetic sorbent, CaO in α-AI₂O₃, was determined as a function of gas composition, temperature, and calcium concentration in the sorbent. The reaction was found to be diffusion-controlled above 850°C and kinetically controlled at lower temperatures. The physical characteristics of the support material have a major effect oh the sulfation kinetics. Porosity measurements indicated that supports containing large pores (>0.2 µm) produced sorbents having high sulfation rates and that pores with diameters less than 0.2 µm did not contribute significantly to the capture of SO₂. The sorbents SrO in α-AI₂O₃ and BaO in α-AI₂O₃ had lower SO₂ capture rates than did CaO in α-AI₂O₃. The alkali metal oxide sorbents K₂O and Na₂O in α-AI₂O₃ captured SO₂ much faster than did the alkaline earth metal oxides.