Integrated Assessment Modeling of Atmospheric Pollutants in the Southern Appalachian Mountains. Part I: Hourly and Seasonal Ozone

Abstract

Recently, a comprehensive air quality modeling system was developed as part of the Southern Appalachians Mountains Initiative (SAMI) with the ability to simulate meteorology, emissions, ozone, size- and composition-resolved particulate matter, and pollutant deposition fluxes. As part of SAMI, the RAMS/EMS-95/URM-1ATM modeling system was used to evaluate potential emission control strategies to reduce atmospheric pollutant levels at Class I areas located in the Southern Appalachians Mountains. This article discusses the details of the ozone model performance and the methodology that was used to scale discrete episodic pollutant levels to seasonal and annual averages. The daily mean normalized bias and error for 1-hr and 8-hr ozone were within U.S. Environment Protection Agency guidance criteria for urban-scale modeling. The model typically showed a systematic overestimation for low ozone levels and an underestimation for high levels. Because SAMI was primarily interested in simulating the growing season ozone levels in Class I areas, daily and seasonal cumulative ozone exposure, as characterized by the W126 index, were also evaluated. The daily ozone W126 performance was not as good as the hourly ozone performance; however, the seasonal ozone W126 scaled up from daily values was within 17% of the observations at two typical Class I areas of the SAMI region. The overall ozone performance of the model was deemed acceptable for the purposes of SAMI’s assessment.     

Estrogenic and androgenic activities in total plasma measured with reporter-gene bioassays: relevant exposure measures for endocrine disruptors in epidemiologic studies?

Measurements of estrogenic and androgenic activities in total plasma with Chemically Activated LUciferase gene eXpression (CALUX?) bioassays could provide biologically relevant measures for exposure to endocrine disruptors in epidemiologic studies. The objective of this study was to explore the effects of a variety of sources of potential endocrine disruptors on estrogenic and androgenic activities in total plasma measured by CALUX?. Plasma samples and interview data on sources of potential endocrine disruptors were collected from 108 men with different exposures profiles. CALUX? measurements (BioDetection Services) involved human U2-OS cell lines controlled by the estrogen receptor alpha and the androgen receptor. Mean differences (beta) in 17β-estradiol equivalents (EEQs) and dihydrotestosterone equivalents (AEQs) between exposure groups were estimated using general linear models. Mean plasma AEQs and EEQs were 9.1×10(-1)ng/ml and 12.0pg/ml, respectively. Elevated AEQs were found in smokers (beta 1.9 (95%CI 0.1-3.6)×10(-1)ng/ml) and heavy drinkers (1.4 (0.2-3.1)×10(-1)ng/ml), and in men occupationally exposed to disinfectants (1.6 (0.3-3.5)×10(-1)ng/ml) or welding/soldering fumes (1.4 (-0.2-2.9)×10(-1)ng/ml). Occupational exposure to pesticides, disinfectants, and exhaust fumes seemed to be associated with increased plasma EEQs: 1.5 (-0.2-3.2)pg/ml, 2.1 (0.2-3.9)pg/ml, and 2.9 (0.6-5.2)pg/ml, respectively. Moderate to high plasma dioxin levels, measured in a subgroup by the dioxin-responsive CALUX?, were accompanied by a 20% increase in AEQs. This is the first study in which CALUX? was used to assess hormone activities in total plasma. Although the results are not yet readily interpretable, they indicate that these measurements can be valuable for epidemiologic studies on endocrine disruptors and give direction for further research.     

Nematode species at risk--a metric to assess pollution in soft sediments of freshwaters

Soft sediments are often highly polluted as many of the toxic chemicals introduced into surface waters bind to settling particles. The resulting accumulation of pollutants in the sediments poses a risk for benthic communities. However, pollution induced changes in benthic communities have been difficult to determine when using macro-invertebrates as bioindicators, as these organisms are often absent in soft sediment. The present study therefore examined the ability of meiofaunal organisms, specifically, nematodes, to assess the ecological status of soft sediments. Over a 9-year period, nematode communities present in sediments collected from large rivers and lake Constance in Germany were studied. These sediments showed a large range of physico-chemical properties and anthropogenic contamination. After the degree of metal and organic contamination was translated into ecotoxicologically more relevant toxic units (TUs), multivariate methods were used to classify nematode taxa in species at risk (NemaSPEAR) or not at risk (NemaSPE(not)AR). This approach clearly distinguished the influence of sediment texture from that of the toxic potential of the samples and thus allowed classification of the nematode species according to their sensitivity to or tolerance of toxic stress. Two indices, expressing the proportion of species at risk within a sample (NemaSPEAR[%](metal), NemaSPEAR[%](organic)), were calculated from independent data sets obtained in field and experimental studies and showed good correlations with the toxic potential (field data) or chemical concentrations (microcosm data). NemaSPEAR[%] indices for metal and organic pollution were therefore judged to be suitable for assessing the impact of chemical contamination of freshwater soft sediments.     

A temporal trend study (1972-2008) of perfluorooctanesulfonate, perfluorohexanesulfonate, and perfluorooctanoate in pooled human milk samples from Stockholm, Sweden

The widespread presence of perfluorooctanesulfonate (PFOS), perfluorooctanoate (PFOA), and perfluorohexanesulfonate (PFHxS) in human general populations and their slow elimination profiles have led to renewed interest in understanding the potential human neonatal exposures of perfluoroalkyls (PFAs) from consumption of human milk. The objective of this study was to evaluate the concentrations of PFOS, PFHxS, and PFOA in pooled human milk samples obtained in Sweden between 1972 and 2008 (a period representing the most significant period of PFA production) and to see whether the time trend of these analytes parallels that indicated in human serum. Chemical analysis of PFOS, PFHxS, and PFOA was performed on pooled Swedish human milk samples from 1972 to 2008 after methodological refinements. The 20 samples which formed the 2007 pool were also analyzed individually to evaluate sample variations. Analyses were performed by HPLC-MS/MS. Due to the complexities of the human milk matrix and the requirement to accurately quantitate low pg/mL concentrations, meticulous attention must be paid to background contamination if accurate results are to be obtained. PFOS was the predominant analyte present in the pools and all three analytes showed statistically significant increasing trends from 1972 to 2000, with concentrations reaching a plateau in the 1990s. PFOA and PFOS showed statistically significant decreasing trends during 2001-2008. At the end of the study, in 2008, the measured concentrations of PFOS, PFHxS, and PFOA in pooled human milk were 75 pg/mL, 14 pg/mL, and 74 pg/mL, respectively. The temporal concentration trends of PFOS, PFHxS, and PFOA observed in human milk are parallel to those reported in the general population serum concentrations.     

Inhalation dose assessment of indoor radon progeny using biokinetic and dosimetric modeling and its application to Jordanian population

High indoor radon concentrations in Jordan result in internal exposures of the residents due to the inhalation of radon and its short-lived progeny. It is therefore important to quantify the annual effective dose and further the radiation risk to the radon exposure. This study describes the methodology and the biokinetic and dosimetric models used for calculation of the inhalation doses exposed to radon progeny. The regional depositions of aerosol particles in the human respiratory tract were firstly calculated. For the attached progeny, the activity median aerodynamic diameters of 50 nm, 230 nm and 2500 nm were chosen to represent the nucleation, accumulation and coarse modes of the aerosol particles, respectively. For the unattached progeny, the activity median thermodynamic diameter of 1 nm was chosen to represent the free progeny nuclide in the room air. The biokinetic models developed by the International Commission on Radiological Protection (ICRP) were used to calculate the nuclear transformations of radon progeny in the human body, and then the dosimetric model was applied to estimate the organ equivalent doses and the effective doses with the specific effective energies derived from the mathematical anthropomorphic phantoms. The dose conversion coefficient estimated in this study was 15 mSv WLM⁻¹ which was in the range of the values of 6-20 mSv WLM⁻¹ reported by other investigators. Implementing the average indoor radon concentration in Jordan, the annual effective doses were calculated to be 4.1 mSv y⁻¹ and 0.08 mSv y⁻¹ due to the inhalation of radon progeny and radon gas, respectively. The total annual effective dose estimated for Jordanian population was 4.2 mSv y⁻¹. This high annual effective dose calculated by the dosimetric approach using ICRP biokinetic and dosimetric models resulted in an increase of a factor of two in comparison to the value by epidemiological study. This phenomenon was presented by the ICRP in its new published statement on radon.     

Fukushima fallout in Northwest German environmental media

Traces of short- and long-lived fallout isotopes (¹³¹I, ¹³⁴Cs and ¹³⁷Cs) were found in environmental samples collected in Northwest Germany (rain water, river sediment, soil, grass and cow milk) from March to May 2011, following the radioactivity releases after the nuclear accident in Fukushima, Japan. The measured concentrations are consistent with reported concentrations in air, amount of rainfall and expected values applying simple radioecological models. The [¹³⁴Cs]/[¹³⁷Cs] ratio reported for air (about 1) allows for discrimination between “recent” and “old” ¹³⁷Cs. Expected ¹³⁶Cs values fell below the detection limits of the instrumentation, despite large sample masses and long counting times.     

Awareness and convenience are important in increasing conference sustainability

Conference organizers are increasingly making efforts to reduce resource use at conferences, yet few responsibilities are placed on attendees. We hosted an ecology conference and offered attendees a discount if they took a sustainability pledge agreeing to reduce their resource use at the conference. In a post-conference survey, 83% of respondents reported fulfilling the pledge, but 62% indicated that convenience was the biggest obstacle impeding their ability to continue the pledge during and after the conference. We found great willingness by attendees to reduce resource use at and beyond our conference, and facilitating their participation was an important part of our success.     

Role of black carbon in the distribution of polychlorinated dibenzo-p-dioxins/dibenzofurans in aged field-contaminated soils

Floodplain soils containing elevated levels of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) were collected from several locations along the Tittabawassee River (Michigan, USA). The PCDD/F profiles of these soils exhibited distinct congener patterns consistent with byproducts from either chloralkali manufacturing or chlorophenols productions. Black carbon (BC) particles were isolated for the first time from floodplain soil impacted by PCDD/Fs. Petrographic analysis showed that BC particles, including coal, oxidized coal, metallurgical coke, depositional carbon, coal tar/pitch, cenosphere, and charcoal, comprised approximately 30% by volume of the organic fraction with size range of 250 μm-2000 μm from a typical floodplain soil. The BC particles with anthropogenic origin such as pitch and coke associated with the chloralkali production process served as both the source and subsequent transporter for the highly hydrophobic PCDD/Fs. These anthropogenic BC particles were enriched with high levels of PCDFs, containing approximately 1000-fold the concentration found in the bulk soil. The strong association of PCDD/Fs with anthropogenic BC directly impacts the physicochemical and biological availability thus the risk associated with these hydrophobic organochlorines in soils and sediments.     

Responses of a soil bacterium, Pseudomonas chlororaphis O6 to commercial metal oxide nanoparticles compared with responses to metal ions

The toxicity of commercially-available CuO and ZnO nanoparticles (NPs) to pathogenic bacteria was compared for a beneficial rhizosphere isolate, Pseudomonas chlororaphis O6. The NPs aggregated, released ions to different extents under the conditions used for bacterial exposure, and associated with bacterial cell surface. Bacterial surface charge was neutralized by NPs, dependent on pH. The CuO NPs were more toxic than the ZnO NPs. The negative surface charge on colloids of extracellular polymeric substances (EPS) was reduced by Cu ions but not by CuO NPs; the EPS protected cells from CuO NPs-toxicity. CuO NPs-toxicity was eliminated by a Cu ion chelator, suggesting that ion release was involved. Neither NPs released alkaline phosphatase from the cells’ periplasm, indicating minimal outer membrane damage. Accumulation of intracellular reactive oxygen species was correlated with CuO NPs lethality. Environmental deposition of NPs could create niches for ion release, with impacts on susceptible soil microbes.     

Engineered nanomaterials in rivers--exposure scenarios for Switzerland at high spatial and temporal resolution

Probabilistic material flow analysis and graph theory were combined to calculate predicted environmental concentrations (PECs) of engineered nanomaterials (ENMs) in Swiss rivers: 543 river sections were used to assess the geographical variability of nano-TiO₂, nano-ZnO and nano-Ag, and flow measurements over a 20-year period at 21 locations served to evaluate temporal variation. A conservative scenario assuming no ENM removal and an optimistic scenario covering complete ENM transformation/deposition were considered. ENM concentrations varied by a factor 5 due to uncertain ENM emissions (15%-85% quantiles of ENM emissions) and up to a factor of 10 due to temporal river flow variations (15%-85% quantiles of flow). The results indicate highly variable local PECs and a location- and time-dependent risk evaluation. Nano-TiO₂ median PECs ranged from 11 to 1′623 ng L⁻¹ (conservative scenario) and from 2 to 1′618 ng L⁻¹ (optimistic scenario). The equivalent values for nano-ZnO and nano-Ag were by factors of 14 and 240 smaller.