RP016 (CRA-1117-825974) Uae of Semipermeable Membrane Devices (SPMDs) in a Probabilistic Assessment of Virginia Rivers.
Start time: 8:00 AM
Cranor, W¹, Alvarez, D¹, Huckins, J¹, Perkins, S¹, Clark, R¹, Stewart, R², ¹ USGS, Columbia, MO, USA² Virginia Department of Environmental Quality, Richmond, VA, USA
The Virginia Department of Environmental Quality (VDEQ) has been charged with monitoring factors which may be indicators of water quality in free flowing freshwater streams and in estuarine waters. The VDEQ has adopted a strategy which incorporates a probabilistic monitoring program for free flowing freshwater streams, consisting of all non-tidal perennial streams and rivers within the Commonwealth of Virginia. As an integral part of this much larger study, lipid-containing semipermeable membrane devices (SPMDs) were used to sample ultra-trace (i.e., < ng/L) and trace (ng/L to mg/L) levels of hydrophobic organic contaminants in the water column of selected streams. The SPMDs were prepared by US Geological Survey (USGS) scientists and replicate samplers were deployed at 50 study sites by VDEQ personnel and recovered from 46 of the 50 sites. The SPMDs were processed and analyzed by USGS to determine concentrations of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), and selected current-use pesticides including trifluralin, diazinon, dacthal, chlorpyrifos, endosulfans, and permethrins in stream waters. A number of OCPs, PAHs, and current use pesticides were detected in SPMDs at most sites. However, only pentachloroanisole (PCA; a microbial methylation product of the wood-preservative pentachlorophenol) was found at quantifiable levels at every site analyzed. Elevated levels of PCBs were found only at two sites. The highest concentrations of individual PAHs at sample sites were phenanthrene, fluoranthene and pyrene. This observation is typical of PAH concentrations in environmental waters where these chemicals originate from pyrogenic sources. Previously developed models were employed to estimate aqueous concentrations of contaminants of concern in the water columns of the rivers studied.

RP017 (DOV-1117-815534) The ISOMET Sampler: A Simple, Clean Sampling Technique for Trace Metals in Water.
Start time: 8:00 AM
McCrea, R¹, Lawson, G¹, Madsen, N¹, Sardella, G¹, Dove, A¹, ¹ Environment Canada, Burlington, ON, Canada
The "ISOlation strategy for trace METal analysis" samplers have been designed by Environment Canada for the collection of reliable and uncontaminated mercury and trace metal samples from aquatic environments. These samplers have been used successfully at sites ranging from clean environments with ultra-low levels to contaminated sites. They are inexpensive and rugged, easy to use and require little training. The resulting data are comparable to those obtained by expert staff utilizing clean techniques with in-field clean room facilities.

RP018 (ALV-1117-051193) Protective deployment systems for sampling of airborne organic contaminants.
Start time: 8:00 AM
Alvarez, D¹, Cranor, W¹, Huckins, J¹, Cicenaite, A², Orazio, C¹, ¹ USGS - CERC, Columbia, MO, USA² Umea University, Umea, Sweden
Collecting a representative sample of airborne organic contaminants poses many challenges. One issue commonly overlooked is the potential photodegradation of chemicals after they are trapped by the sampling device. These chemicals can include polyaromatic hydrocarbons (PAHs) and polybrominated diphenyl ethers (PBDEs). Semipermeable membrane devices (SPMDs) have been used as airborne samplers of nonpolar organic contaminants for many years. The SPMDs are useful in that they provide a means of collecting a sample which can provide information on the time-weighted average concentration of targeted chemicals. A suite of deployment systems have been developed to protect SPMDs from potential chemical loss due to photodegradation during airborne exposure. Analysis of perdeuterated PAHs added to the SPMDs prior to use indicate that no photodegradation of PAHs occurred in SPMDs deployed in the new systems over a 28 day period. In comparison, SPMDs not fully protected from sunlight had no PAHs remaining after 28 days. Furthermore, the new system minimizes holding, exposure to light, and time required for deployment and retrieval of samplers. Considerations on the design and effects on sampling performance will be discussed.

RP019 (HUC-1117-745606) Fundamentals of the use of performance reference compounds (PRCs) in passive samplers.
Start time: 8:00 AM
Huckins, J¹, Booij, K², Cranor, W¹, Alvarez, D¹, Gale, R¹, Bartkow, M³, Robertson, G⁴, Clark, R¹, Stewart, R⁵, ¹ USGS, Columbia, MO, USA² Royal Netherlands Institute for Sea Research, Texel, The Netherlands³ National Centre for Environmental Toxicology, Coopers Plains, Qeensland, Australia⁴ US EPA, Las Vegas, NV, USA⁵ Virginia Department of Environmental Quality, Richmond, VA, USA
PRCs are analytically non-interfering compounds with moderate- to relatively high-fugacities, which are added to passive samplers (e.g., the lipid of SPMDs) prior to deployment. The rate of PRC loss during an exposure can be used to estimate in situ sampling rates of the analytes (R_si) of interest. Estimates of R_si are possible because the PRC release rate constant (k_ep) is equal to the sampling rate of the PRC (R_sp; mLd^-1) divided by the sampler′s clearance capacity, where the clearance capacity is equal to the sampler′s equilibrium partition coefficient for the PRC (K_sp) times the sampler′s volume (V_s; mL). Although PRCs have been used for over a decade, there is very little information available about PRCs relative to: the appropriate numbers of chemicals and the K_ow range of candidate PRCs to employ, the applicability of the approach to field situations and different samplers, the effects of sampling media on the selection of PRCs, the analytical methods required for their quantification, the approaches for calculating sampling rates using PRCs, and the limitations of the technique. In this work, these issues are discussed in detail and general guidelines are recommended for using the PRC approach. Also, the types of calibration data (e.g., K_si) needed for the extrapolation of ambient concentrations of target compounds from their concentrations in a sampler are elucidated. Finally, a method is proposed to extend the PRC approach to integrative samplers such as the polar organic chemical integrative sampler, where uptake and release curves are likely anisotropic.

RP020 (KAW-1117-866414) Liquid phase microextraction with in situ derivatization and GC-MS for measurement bisphenol A in river water samples.
Start time: 8:00 AM
Kawaguchi, Migaku¹, Ito, Rie¹, Endo, Naoyuki¹, Saito, Koichi¹, Nakazawa, Hiroyuki¹, ¹ Department of Analytical Chemistry, Faculty of Pharmaceutical Sciences, Hoshi University, Tokyo, Japan
A novel method, based on liquid phase microextraction (LPME) with in situ derivatization and gas chromatography-mass spectrometry (GC-MS) is described for the determination of trace amounts of bisphenol A (BPA) in river water samples. Ten milliliters of river water sample was placed in a headspace vial containing surrogate standard. Then, 1 M potassium carbonate solution (1 ml) for pH adjustment, acetic acid anhydride (100 l) as the derivatization reagent, and a stir bar were added. The stirring was performed for 1 min. Then, the ultrasonication was performed for 3 min. A 10 l microsyringe was used for LPME. Before extraction, the syringe was rinsed with acetone followed by toluene 10 times to avoid carryover and air bubble formation. Four microliters of toluene was withdrawn into the syringe. The syringe needle tip was held 5 mm below the surface of a sample solution. LPME was performed at room temperature for 90 min while stirring at 1000 rpm. After the extraction, 2 l of extract was carefully withdrawn into the syringe. The extract was then injected into the GC-MS system. The detection limit and quantitation limit of BPA in river water samples is 2 and 10 ng l^-1 (ppt), respectively. Calibration for BPA was shown to be linear with a correlation coefficient of >0.999. The average recoveries of BPA in river water samples are higher than 95 % (RSD: < 10 %) with correction using an added surrogate standard, bisphenol A-¹³C₁₂. This simple analytical method may be applicable to the high sensitive determination of trace amounts of BPA in various liquid samples.

RP021 (DEM-1117-825858) PCBs in Paint – Where to look and how to test.
Start time: 8:00 AM
McTigue, J.¹, Demers, G.¹, Lynch, J.², Dow, K.², ¹ ERM, Boston, MA, USA² Yankee Atomic Electric Company, Rowe, MA, USA
Historically, polychlorinated biphenyls (PCBs) have been used in specialized paint formulations, which have been found at power plants, on military installations, and on military ships. Due to the uncommon nature of PCBs in paint, there is limited information available regarding environmental assessments focused on the nature of how paint chips containing PCBs migrate in the environment and how best to detect them. Detailed environmental assessments have been performed to address a release of paint chips containing PCBs at a former nuclear power plant in western Massachusetts. Stormwater and wind-blown deposition provided migration pathways for the paint chips. Sampling of soil, groundwater, catchbasins, sediments, , surface water, and fish tissues was performed to evaluate the migration pathways of the PCB-containing paint chips. Field screening was conducted using a magnetic particle immunoassay technique. Laboratory analyses of soil and sediment samples were performed by EPA Method 8082 using both soxhlet and ultrasonic extraction. Fish tissue samples were analyzed by Method 8082 and for congeners. The various analytical methods generally had a good correlation, but with some discrepancies that were attributed to the variability associated with the nature of paint chip particulates. Comparison of the two extraction methods for sediment determined that, on average, results were 35 percent higher using ultrasonic extraction. Comparison of Method 8082 and congener analytical results showed similar results, with the congener method being on average 35 percent higher than the total using Method 8082, with lower detection limits obtained using the congener method. The results of these investigations provide a framework for where to look for PCBs in paint and how to analyze various media to determine the extent of impact.