Estimation of selected physicochemical properties for methylated naphthalene compounds

Liquid aqueous solubility (S(w,L)), octanol/water partition coefficients (K(ow)), liquid vapor pressure (P(v,L)), and Henry's law constants (H(c)) were estimated for 20 methylated naphthalenes ranging from monomethyl to tetramethylnaphthalenes. Chromatographic methods were used for the estimation. Chromatographic retention measurements were conducted for 11 reference compounds and regressions were fit between the retention indices and the physicochemical properties. HPLC octadecylsilyl column with acetonitrile/water eluent was used for the estimation of S(w,L) and K(ow). Two GC columns, HP5-MS and a more hydrophobic HP-1, were tested for the estimation of P(v,L). Measured retention indices for the methylated naphthalenes were entered to the regression equations to calculate the physicochemical properties for these compounds. Literature values, where available, were used to validate the calculated values. The method accurately estimated the physicochemical properties. Estimated S(w,L) and P(v,L) decreased with the number of methyl groups. K(ow) increased with the number of methyl groups. There was no obvious relation between H(c) and the number of methyl groups. Log S(w,L) ranged from 0.885 for 1,2,5,6-tetramethylnaphthalene to 2.269 for 1-methylnaphthalene (mmol/m(3)). Log K(ow) varied from 3.89 for 1-methylnaphthalene to 4.95 for 1,2,5,6-tetramethylnaphthalene. Log P(v,L) ranged from -0.983 for 1,2,5,6-tetramethylnaphthalene to 0.789 for 2-methylnaphthalene (Pa). Log H(c) varied from 1.03 for 1,4,5-trimethylnaphthalene to 1.73 for 2,6-dimethylnaphthalene (Pa m(3)/mol). There were no apparent effects of GC column hydrophobicity on the accuracy of the results. Estimation of S(w,L) and K(ow) based on GC retention indices was not as accurate as with HPLC. Comparison of the estimated values with values predicted by EPIWIN indicated that EPIWIN is useful in giving order-of-magnitude prediction of physicochemical properties.     

Correlation between bioassay-derived P4501A1 induction activity and chemical analysis of clam (Laternula elliptica) extracts from McMurdo Sound, Antarctica

Variable levels of halogenated aromatic hydrocarbons were measured in clams (Laternula elliptica) collected from McMurdo Sound, Antarctica. Clams collected in and near Winter Quarters Bay contained high levels of organochlorine compounds, particularly polychlorinated biphenyls (PCBs). A strong gradient has been documented in Winter Quarters Bay that been linked to human activities at McMurdo Station. The activity of clam extracts as inducers of P4501A1-dependent ethoxyresorufin O-deethylase (EROD) activity was determined using in vitro bioassays utilizing rat hepatoma H4IIE cells. The extracts which exhibited the highest induction activities were those derived from clams collected in contaminated areas. Additionally, there was an excellent linear correlation between induced EROD activity versus total PCB levels (r²=0.96). The complimentary nature of both the analytical and bioanalytical data confirms the utility of the latter assay and provides a method for estimating the 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) toxic equivalents in extracts from marine biota.     

Spatial and temporal variations of PM(2.5) concentration and composition throughout an urban area with high freeway density-the Greater Cincinnati study

The PM(2.5) concentration and its elemental composition were measured in the Cincinnati metropolitan area, which is characterized by intense highway traffic. The spatial and temporal variations were investigated for various chemical elements that contributed to the PM(2.5) fraction during a 1-year-long measurement campaign (December 2001-November 2002). The ambient aerosol monitoring was performed in 11 locations around the city during nine measurement cycles. During each cycle, four Harvard-type impactors were operating in parallel in specific locations to explore various factors affecting the PM(2.5) elemental concentrations. The sampling was performed during business days, thus assuring traffic uniformity. The 24-h PM(2.5) samples were collected on Teflon and quartz filters. Teflon filters were analyzed by X-ray fluorescence (XRF) analysis while quartz filters were analyzed by thermal-optical transmittance (TOT) analysis. In addition to PM(2.5) measurements, particle size-selective sampling was performed in two cycles using micro-orifice uniform deposit impactor; the collected fractionated deposits were analyzed by XRF. It was found that PM(2.5) concentration ranged from 6.70 to 48.3 mug m(-3) and had low spatial variation (median coefficient of variation, CV=11.3%). The elemental concentrations demonstrated high spatial variation, with the median CV ranged from 38.2% for Fe to 68.7% for Ni. For traffic-related trace metals, the highest concentration was detected in the city center site, which was close to a major highway. The particle size selective measurement revealed that mass concentration of the trace metals, such as Zn, Pb, Ni, as well as that of sulfur reach their peak values in the particle size range of 0.32-1.0 mum. Meteorological parameters and traffic intensity were not found to have a significant influence on the PM(2.5) elemental concentrations.     

Matrix-immobilized organoclay for the sorption of polycyclic aromatic hydrocarbons and pentachlorophenol from groundwater

Sorbent materials consisting of organoclay immobilized onto the surface of a solid support were evaluated for use in pentachlorophenol (PCP) and polycyclic aromatic hydrocarbon (PAH) remediation of groundwater at a creosote-contaminated Superfund site. Cetylpyridinium-exchanged low pH montmorillonite clay (CP-LPHM) was bonded to either sand (CP-LPHM/sand) or granular activated carbon (GAC) (CP-LPHM/GAC) using the free acid form of carboxymethylcellulose as an adhesive. Effluent from an oil-water separator was eluted through equal bed volumes of composite (4 g 3:2 CP-LPHM/GAC or 13 g CP-LPHM/sand), affinity-extracted, and quantitatively analyzed by GC/MS. PCP, naphthalene, fluorene, phenanthrene, pyrene, and total PAHs were initially reduced by both CP-LPHM/GAC (> or =99%, 61%, 99%, > or =99%, 97%, and 94%, respectively) and CP-LPHM/sand (90%, 70%, 94%, 95%, 93%, and 86%, respectively). Complete breakthrough of naphthalene occurred after approximately 15 h of elution through 3:2 CP-LPHM/GAC and 22 h through CP-LPHM/sand. PCP showed complete breakthrough following 18 h of elution through 3:2 CP-LPHM/GAC and 26 h through CP-LPHM/sand. However, 50% breakthrough was not attained for higher molecular weight PAHs, as fluoranthene, pyrene, benzo[a]anthracene, and chrysene continued to be greatly reduced with both 3:2 CP-LPHM/GAC (98%, 95%, 94%, and 95%, respectively) and CP-LPHM/sand (75%, 73%, 76%, and 78%, respectively) after 48 h of continuous elution. Results confirm prior studies, indicating that these organoclay-containing composites have a high capacity for contaminants found in wood preserving waste. Further, results suggest that the inclusion of CP-LPHM may be useful as part of an effective strategy for groundwater remediation of high concentrations of PCP and PAHs, in particular high molecular weight and carcinogenic PAHs.     

FIA/MS analysis of temporally ozonated benzo[a]pyrene and pyrene and their reaction products: inhibition of gap junction-mediated intercellular communication

In this study, the polycyclic aromatic hydrocarbons, benzo[a]pyrene (BaP) and pyrene, were subjected to temporal ozonation. The products from ozonation of 5 mg l(-1) BaP and 5 mg l(-1) pyrene, for varying time intervals (0, 1, 2, 3, 4, 5, 6, 8, 10, 20, and 30 min) were tested for their effects on gap junction-mediated intercellular communication (GJIC) in Clone 9 rat liver cells. Additionally, the ozonation products were also analyzed by flow injection analysis/mass spectrometry (FIA/MS) and the results were compared with the toxicity observed in the GJIC assay. Treatment of the Clone 9 cells with 5 mg l(-1) of ozonated BaP products resulted in a decrease in GJIC that was inversely proportional to the length of ozonation. The products from 1 min of ozonation resulted in a 92% decrease in the rate of GJIC, but with >5 min ozonation, the products did not suppress GJIC. In contrast, pyrene (0.5 mg l(-1)) required >10 min of ozonation to alleviate its effects on GJIC. FIA/MS, using atmospheric pressure chemical ionization (APCI), demonstrated products with higher molecular weights (MW) than their corresponding parent compounds, BaP (MW 252) and pyrene (MW 202). Ozonation of pyrene formed significantly fewer products than BaP. More importantly, pyrene ozonation products were constant from 1 to 10 min, while BaP ozonation products seemed to vary between time intervals. With the longer ozonation times (20 and 30 min), BaP and pyrene formed similar products (m/z peaks 157, 111, and 96). The suppression of GJIC by ozonated products seemed to correlate with oxidation of the aromatic ring framework. Further oxidation (longer ozonation times) to lower MW products correlated with restoration of normal GJIC.     

Epidemic Disease and the Catastrophic Decline of Australian Rain Forest Frogs

In the montane rain forests of eastern Australia at least 14 species of endemic, stream-dwelling frogs have disappeared or declined sharply (by more than 90%) during the past 15 years. We review available information on these declines and present eight lines of evidence that collectively suggest that a rapidly spreading, epidemic disease is the most likely responsible agent. The extreme virulence of the putative frog patbogen suggests it is likely exotic to Australian rain forests. We propose that exotic pathogens may be responsible for some recent declines of amphibian populations on other continents and that the intercontinental spread of such pathogens is greatly facilitated by human activities such as the thriving international trade in aquarium fish. Our hypothesis may help explain why some amphibian populations in seemingly pristine environments have mysteriously declined.     

Assessing Retrospective National Water Model Streamflow with Respect to Droughts and Low Flows in the Colorado River Basin

Streamflow monitoring in the Colorado River Basin (CRB) is essential to ensure diverse needs are met, especially during periods of drought or low flow. Existing stream gage networks, however, provide a limited record of past and current streamflow. Modeled streamflow products with more complete spatial and temporal coverage (including the National Water Model [NWM]), have primarily focused on flooding, rather than sustained drought or low flow conditions. Objectives of this study are to (1) evaluate historical performance of the NWM streamflow estimates (particularly with respect to droughts and seasonal low flows) and (2) identify characteristics relevant to model inputs and suitability for future applications. Comparisons of retrospective flows from the NWM to observed flows from the United States Geological Survey stream gage network over 22 years in the CRB reveal a tendency for underestimating low flow frequency, locations with low flows, and the number of years with low flows. We found model performance to be more accurate for the Upper CRB and at sites with higher precipitation, snow percent, baseflow index, and elevations. Underestimation of low flows and variable model performance has important implications for future applications: inaccurate evaluations of historical low flows and droughts, and less reliable performance outside of specific watershed/stream conditions. This highlights characteristics on which to focus future model development efforts.     

Assessment of the Commercial Potential for the High Intensity Ionizer in the Electric Utility Industry

The high intensity ionizer (HII) has reached a level of development where projections can be made of its potential for enhancing electrostatic precipitator (ESP) performance within the electric utility industry. Future ESP performance requirements are forecast based on a scenario of possible changes in regulations for mass emissions, fine particulate, and opacity. An assessment is made of the alternative means of upgrading ESP performance over the next 15 years. It is concluded that of 570 ESP estimated to require upgrading by 1995 to meet possibly more stringent regulations, approximately 20%—or 117 units—may employ HII.     

Metrics of progress in the understanding and management of threats to Australian birds

Although evidence-based approaches have become commonplace for determining the success of conservation measures for the management of threatened taxa, there are no standard metrics for assessing progress in research or management. We developed 5 metrics to meet this need for threatened taxa and to quantify the need for further action and effective alleviation of threats. These metrics (research need, research achievement, management need, management achievement, and percent threat reduction) can be aggregated to examine trends for an individual taxon or for threats across multiple taxa. We tested the utility of these metrics by applying them to Australian threatened birds, which appears to be the first time that progress in research and management of threats has been assessed for all threatened taxa in a faunal group at a continental scale. Some research has been conducted on nearly three-quarters of known threats to taxa, and there is a clear understanding of how to alleviate nearly half of the threats with the highest impact. Some management has been attempted on nearly half the threats. Management outcomes ranged from successful trials to complete mitigation of the threat, including for one-third of high-impact threats. Progress in both research and management tended to be greater for taxa that were monitored or occurred on oceanic islands. Predation by cats had the highest potential threat score. However, there has been some success reducing the impact of cat predation, so climate change (particularly drought), now poses the greatest threat to Australian threatened birds. Our results demonstrate the potential for the proposed metrics to encapsulate the major trends in research and management of both threats and threatened taxa and provide a basis for international comparisons of evidence-based conservation science.