Improvements to standard methodologies for the analytical determination of metals in stationary-source emissions samples

Deficiencies with the current European reference method for the analysis using inductively couple plasma-mass spectrometry of metals in samples from stationary emissions sources are presented based on experimental data obtained from real samples. The effect of these deficiencies on the quality and accuracy of data is highlighted with biases of up to 40% being observed in real samples. Suggestions to improve the performance of the standard method are presented. In particular, the beneficial effect of using a drift correction procedure to account for the decrease in instrument sensitivity observed during an analytical measurement series is demonstrated. It is shown that this corrective procedure results in substantial improvements to the accuracy of data produced.     

Spatial trends of organochlorinated pesticides,polychlorinated biphenyls,and polybrominated diphenyl ethers in Atlantic Anguillid eels

The bioaccumulation of lipophilic contaminants such as polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), and polybrominated diphenyl ethers (PBDEs) can result in a reduction in fitness and spawner quality in eels and may be a factor in Anguillid sp. population declines. Contaminant concentrations in eels have been studied extensively in Europe, but data for American eels are severely lacking. Concentrations of PCBs, OCPs, and PBDEs were determined in American eel from eastern Canada and New York, USA, along with European eel from Belgium. Principal component analysis revealed that eels captured in the St. Lawrence estuary were a mixture of upstream migrants from the St. Lawrence River watershed, and fish captured in local tributaries. Contaminant concentrations were dependent on origin, related to the local environment, and were lower than historic values. In Canada, concentrations of OCPs and PCBs in eel tissues were below the Canadian human consumption guidelines for contaminants in fish, indicating that the current risk to consumers is low. However, concentrations of PCBs, total DDT, and mirex in eels from L. Ontario and the upper St. Lawrence R. were above Great Lakes guidelines for the protection of piscivorous predators. Concentrations of penta-BDE homologs exceeded the Canadian guideline for environmental quality in over half of the eels in this study, but concentrations of the other homolog groups were below the guideline.     

Correspondence of biological condition models of California streams at statewide and regional scales

We used boosted regression trees (BRT) to model stream biological condition as measured by benthic macroinvertebrate taxonomic completeness, the ratio of observed to expected (O/E) taxa. Models were developed with and without exclusion of rare taxa at a site. BRT models are robust, requiring few assumptions compared with traditional modeling techniques such as multiple linear regression. The BRT models were constructed to provide baseline support to stressor delineation by identifying natural physiographic and human land use gradients affecting stream biological condition statewide and for eight ecological regions within the state, as part of the development of numerical biological objectives for California’s wadeable streams. Regions were defined on the basis of ecological, hydrologic, and jurisdictional factors and roughly corresponded with ecoregions. Physiographic and land use variables were derived from geographic information system coverages. The model for the entire state (n?=?1,386) identified a composite measure of anthropogenic disturbance (the sum of urban, agricultural, and unmanaged roadside vegetation land cover) within the local watershed as the most important variable, explaining 56 % of the variance in O/E values. Models for individual regions explained between 51 and 84 % of the variance in O/E values. Measures of human disturbance were important in the three coastal regions. In the South Coast and Coastal Chaparral, local watershed measures of urbanization were the most important variables related to biological condition, while in the North Coast the composite measure of human disturbance at the watershed scale was most important. In the two mountain regions, natural gradients were most important, including slope, precipitation, and temperature. The remaining three regions had relatively small sample sizes (n?≤?75 sites) and had models that gave mixed results. Understanding the spatial scale at which land use and land cover affect taxonomic completeness is imperative for sound management. Our results suggest that invertebrate taxonomic completeness is affected by human disturbance at the statewide and regional levels, with some differences among regions in the importance of natural gradients and types of human disturbance. The construction and application of models similar to the ones presented here could be useful in the planning and prioritization of actions for protection and conservation of biodiversity in California streams.     

Assessment of pumped mercury vapour adsorption tubes as passive samplers using a micro-exposure chamber

Mercury vapour adsorption tubes manufactured for pumped sampling and analysis have been evaluated for their performance as passive samplers. This has been done by exposing these tubes in a novel micro-exposure chamber. The uptake rates of these tubes have been found to be low (approximately 0.215 ml min(-1)) as compared to bespoke passive samplers for mercury vapour (typically in excess of 50 ml min(-1)). The measured uptake rates were shown to vary significantly between tubes and this was attributed to the variability in the air-sorbent interface and the proportion of the cross sectional area removed by the crimp in the quartz tubes used to secure the sorbent material. As a result of this variability the uptake rate of each tube must be determined using the micro-exposure chamber prior to deployment. Results have shown that the uptake rate determined in the micro-exposure chamber is invariant of concentration, and therefore these uptakes rates may be determined at a high mercury vapour concentration for many tubes at once in less than one hour. The uptake rate of the adsorption tubes under these conditions may be determined with a precision of 5%. Measurements made on a limited field trial in indoor and outdoor ambient air have shown that these tubes give results in acceptable agreement with more traditional pumped sampling methods, although longer sampling periods are required in order to reduce the uncertainty of the measurement, which is currently approximately 30%.     

Assessing soil lead contamination in Dallas Texas

During the summer of 1982, the U.S. Environmental Protection Agency conducted a comprehensive multimedia environmental monitoring program in the vicinity of two secondary lead smelters and at one reference site in Dallas, Texas. This monitoring program included a major soils investigation with the collection and analysis of over 2700 soil samples. In addition, approximately 1000 blood and 840 house dust samples were collected and analyzed for their lead content.Utilizing geostatistics and the data obtained from a portion of the soil samples, isopleths of constant soil lead concentrations within each of the three monitoring sites were identified. Presented are the soil monitoring strategy and the geostatistical techniques selected for identifying the distributions of soil lead patterns at each of the three monitoring sites. In addition, the soil sampling and analytical methods used, the sample handling and preparation procedures, and the geostatistical results obtained are identified.     

Ambient site, home outdoor and home indoor particulate concentrations as proxies of personal exposures

Despite strong longitudinal associations between particle personal exposures and ambient concentrations, previous studies have found considerable inter-personal variability in these associations. Factors contributing to this inter-personal variability are important to identify in order to improve our ability to assess particulate exposures for individuals. This paper examines whether ambient, home outdoor and home indoor particle concentrations can be used as proxies of corresponding personal exposures. We explore the strength of the associations between personal, home indoor, home outdoor and central outdoor monitoring site ("ambient site") concentrations of sulfate, fine particle mass (PM(2.5)) and elemental carbon (EC) by season and subject for 25 individuals living in the Boston, MA, USA area. Ambient sulfate concentrations accounted for approximately 70 to 80% of the variability in personal and indoor sulfate levels. Correlations between ambient and personal sulfate, however, varied by subject (0.1-1.0), with associations between personal and outdoor sulfate concentrations generally mirroring personal-ambient associations (median subject-specific correlations of 0.8 to 0.9). Ambient sulfate concentrations are good indicators of personal exposures for individuals living in the Boston area, even though their levels may differ from actual personal exposures. The strong associations for sulfate indicate that ambient concentrations and housing characteristics are the driving factors determining personal sulfate exposures. Ambient PM(2.5) and EC concentrations were more weakly associated with corresponding personal and indoor levels, as compared to sulfate. For EC and PM(2.5), local traffic, indoor sources and/or personal activities can significantly weaken associations with ambient concentrations. Infiltration was shown to impact the ability of ambient concentrations to reflect exposures with higher exposures to particles from ambient sources during summer. In contrast in the winter, lower infiltration can result in a greater contribution of indoor sources to PM(2.5) and EC exposures. Placing EC monitors closer to participants' homes may reduce exposure error in epidemiological studies of traffic-related particles, but this reduction in exposure error may be greater in winter than summer. It should be noted that approximately 20% of the EC data were below the field limit of detection, making it difficult to determine if the weaker associations with the central site for EC were merely a result of methodological limitations.     

The US National Cancer Institute's natural products repository; origins and utility

The US National Cancer Institute's natural products collection program has been running since 1986 and over the years the materials collected and processed have been stored in a repository that as a result of initial planning, has permitted the establishment of a national resource that is now being utilized as a drug discovery tool for any disease of interest to the NIH by researchers world-wide. This paper describes the history of the program.