Passive aerosol sampler for particle concentrations and size distributions

This research evaluated the UNC passive aerosol sampler as a tool to measure particle mass concentrations and size distributions. The exposure scenario represented high concentrations and exposure periods of a few hours. Mass concentrations measured with the passive sampler were compared to concentrations measured using both a dichotomous sampler and an aerodynamic particle sizer (APS). In addition, the size distributions measured with the passive sampler were compared to those measured using the APS. Mass concentrations measured using the dichotomous sampler and the APS agreed well. The passive sampler tracked, but tended to overestimate, mass concentrations measured by the other two instruments. Size distributions measured with the passive sampler followed the general pattern of those measured using the APS. Overall, the passive sampler demonstrated both its utility and its limitations in these tests. The concentration measurements and size distributions found using passive samplers were more variable than those of the other instruments, but generally followed the data taken using the other methods. The advantages of low cost and ease of use offset the limitations in data quality with the passive sampler; these advantages are particularly welcome for sampling situations where aerosol properties vary over space or time.     

A comparison of speciated atmospheric mercury at an urban center and an upwind rural location

Gaseous elemental mercury (GEM), particulate mercury (PHg) and reactive gaseous mercury (RGM) were measured every other hour at a rural location in south central Wisconsin (Devil's Lake State Park, WI, USA) between April 2003 and March 2004, and at a predominantly downwind urban site in southeastern Wisconsin (Milwaukee, WI, USA) between June 2004 and May 2005. Annual averages of GEM, PHg, and RGM at the urban site were statistically higher than those measured at the rural site. Pollution roses of GEM and reactive mercury (RM; sum of PHg and RGM) at the rural and urban sites revealed the influences of point source emissions in surrounding counties that were consistent with the US EPA 1999 National Emission Inventory and the 2003-2005 US EPA Toxics Release Inventory. Source-receptor relationships at both sites were studied by quantifying the impacts of point sources on mercury concentrations. Time series of GEM, PHg, and RGM concentrations were sorted into two categories; time periods dominated by impacts from point sources, and time periods dominated by mercury from non-point sources. The analysis revealed average point source contributions to GEM, PHg, and RGM concentration measurements to be significant over the year long studies. At the rural site, contributions to annual average concentrations were: GEM (2%; 0.04 ng m(-3)); and, RM (48%; 5.7 pg m(-3)). At the urban site, contributions to annual average concentrations were: GEM (33%; 0.81 ng m(-3)); and, RM (64%; 13.8 pg m(-3)).     

A complex investigation of the extent of pollution in sediments of the Sava River. Part 1: Selected elements

The Sava River is the biggest tributary to the Danube River. As a part of the 6th FW EU project, Sava River Basin: Sustainable Use, Management and Protection of Resources (SARIB), ecological status of sediments was investigated. In order to assess the geographical distribution in sediment contamination of the Sava River, inorganic and persistent organic pollutants were analyzed in sediments at 20 selected sampling sites along the Sava River from its spring to its outfall into the Danube River. For comparability of data to other river basins the sediment fraction below 63 μm was studied. Due to complexity of the work performed, the results are published separately (“Part I: Selected elements” and “Part II: Persistent organic pollutants”). In the present study, the extent of pollution was estimated by determination of the total element concentrations and by the identification of the most hazardous highly mobile element fractions and anthropogenic inputs of elements to sediments. To assess the mobile metal fraction extraction in 0.11 mol L^???1, acetic acid was performed (first step of the Community Bureau of Reference extraction procedure), while anthropogenic inputs of elements were estimated on the basis of normalization to aluminum (Al) concentration. According to the Water Framework Directive, the following elements were investigated in sediments: cadmium (Cd), lead (Pb), nickel (Ni), and mercury (Hg). Furthermore, copper (Cu), zinc (Zn), chromium (Cr), arsenic (As), and phosphorous (P) were determined. The analyses of sediments demonstrated slightly elevated values for Hg, Cr, and Ni in industrially exposed sites (concentrations up to 0.6, 380, and 210 mg kg^???1, respectively). However, the latter two elements exist in sparingly soluble forms and therefore do not represent an environmental burden. P concentrations were found in elevated concentrations at agricultural areas and big cities (up to 1,000 mg kg^???1).     

Modeling Acidification Recovery on Threatened Ecosystems: Application to the Evaluation of the Gothenburg Protocol in France

To evaluate the acid deposition reduction negotiated for 2010 within the UNECE LRTAP Gothenburg Protocol, sulphur and nitrogen deposition time-series (1880–2100) were compared to critical loads of acidity on five French ecosystems: Massif Central basalt (site 1) and granite (2); Paris Bassin tertiary sands (3); Vosges mountains sandstone (4) and Landes eolian sands (5). The SAFE model was used to estimate the response of soil solution pH and ratio to the deposition scenario. Among the five sites, critical loads were exceeded in the past at sites 3, 4 and 5. Sites 3 and 4 were still expected to exceed in 2010, the Protocol year. Further reduction of atmospheric deposition, mainly nitrogen, would be needed to achieve recovery on these ecosystems. At sites 3, 4 and 5, the delay between the critical load exceedance and the violation of the critical chemical criterion was estimated to be 10 to 30 years in the top soil and 50 to 90 years in the deeper soil. At site 5, a recovery was expected in the top soil in 2010 with a time lag of 10 years. Unexpectedly, soil pH continued to decrease after 1980 in the deeper soil at sites 2 and 5. This time lag indicated that acidification moved down the soil profile as a consequence of slow base cation depletion by ion exchange. This delayed response of the soil solution was the result of the combination of weathering rates and vegetation uptake but also of the relative ratio between base cation deposition and acid compounds.     

Integrated biomarker response index as a useful tool for environmental assessment evaluated using transplanted mussels

Mytilus galloprovincialis mussels from a clean area were transplanted from 2003 to 2005 to several stations in the Bay of Cannes (North-Western Mediterranean Sea) including a site considered as reference, for 1 month at the end of spring (May). Several biomarkers (AChE, GST and CAT activities, TBARS and MT concentrations) were measured in the transplanted organisms. The concentrations of metals (Cd, Cu and Zn) were determined in the transplanted mussels, PAH and PCB analyses were performed in the mussels caged in 2004. The integrated biomarker response (IBR) was calculated; pollutant concentrations in mussels were displayed as star plots and compared to IBR star plots. Visualization was thus possible between sites for comparison with exposure conditions. Results demonstrated that the mussels from the Old harbour site (VP) are characterized by elevated copper and PCB concentrations, those from Canto harbour (PC) presented high PCB contents and those from the mouth of the Siagne River (ES) high PAH concentrations compared to the animals transplanted in the reference site (IL). In 2003, there was a visual correlation between the copper gradient measured in the transplanted mussels and the IBR variation. In 2004, the agreement between the copper gradient and the PCB gradient measured in the caged mussels and the IBR variation was good whereas the PAH gradient did not seem to contribute to the IBR demonstrating that the chosen biomarkers did not respond to PAHs. In 2005, IBR showed that other contaminants, not measured might be present in VP, PC and ES compared to the reference station (IL).     

Preliminary evidence of a decline in perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) concentrations in American Red Cross blood donors

The purpose of this pilot study was to determine whether perfluorooctanesulfonate (PFOS,C(8)F(17)SO(3)(-)) and perfluorooctanoate (PFOA,C(7)F(15)CO(2)(-)) concentrations in American Red Cross blood donors from Minneapolis-St. Paul, Minnesota have declined after the 2000-2002 phase-out of perfluorooctanesulfonyl-fluoride (POSF, C(8)F(17)SO(2)F)-based materials by the primary global manufacturer, 3M Company. Forty donor plasma samples, categorized by age and sex, were collected in 2005, and PFOS and PFOA concentrations were compared to 100 (non-paired) donor serum samples collected in 2000 from the same general population that were analyzed at the time using ion-pair extraction methods with tetrahydroperfluorooctanesulfonate as an internal standard. Eleven of the 100 samples originally collected were reanalyzed with present study methods that involved (13)C- labeled PFOA spiked into the donor samples, original samples, control human plasma, and the calibration curve prior to extraction, and was used as a surrogate to monitor extraction efficiency. Quantification was performed by high performance liquid chromatography tandem mass spectrometry methods. Among the 100 serum samples analyzed for PFOS, the geometric mean was 33.1 ng ml(-1) (95% CI 29.8-36.7) in 2000 compared to 15.1 ng ml(-1) (95% CI 13.3-17.1) in 2005 (p<0.0001) for the 40 donor plasma samples. The geometric mean concentration for PFOA was 4.5 ng ml(-1) (95% CI 4.1-5.0) in 2000 compared to 2.2 ng ml(-1) (95% CI 1.9-2.6) in 2005 (p<0.0001). The decrease was consistent across donors' age and sex. To confirm these preliminary findings, additional sub-sets of year 2000 samples will be analyzed, and a much larger biomonitoring study of other locations is planned.     

Ozone pre-treatment as improver of PAH removal during anaerobic digestion of urban sludge

Polycyclic aromatic hydrocarbons are ubiquitous persistent pollutants. They may accumulate in sludge during wastewater treatment because of their low biodegradability and their hydrophobic characteristics. Combination of ozonation and anaerobic digestion may be efficient to remove PAHs naturally present in sludge. The objective of this study was to investigate the impact of ozone pre-treatment, with and without surfactant addition, on the anaerobic degradation of 12 PAHs (from low to high molecular weight). Under anaerobic digestion without ozonation pre-treatment, the highest removals were obtained for the lightest PAHs (3-aromatic rings). Ozonation pre-treatment of sludge allowed to increase biodegradability or bioavailability of each PAH, and the PAH removals were well correlated to the PAH solubility. Finally, addition of tyloxapol before sludge ozone pre-treatment had antagonist effects on PAH removal during anaerobic digestion: negative impact on anaerobic ecosystem activity and improvement of PAH bioaccessibility (particularly the PAHs with the highest octanol water partition coefficients).     

Enhanced degradation of benzo[a]pyrene by Mycobacterium sp. in conjunction with green alga

Previous work in this laboratory has confirmed that the bacteria Mycobacterium sp. strain RJGII.135 and Sphingomonas yanoikuyae strain B1 and the green alga Selanastrum capricornutum strain UTEX 1648 degrade benzo[a]pyrene (BaP) to various BaP intermediates. S. capricornutum was first grown with BaP for 4 days. The organic extract of this media was then introduced into separate cultures of strain RJGII.135 and strain B1; separate cultures were grown with BaP for comparison. Cultures grown with BaP and those grown with the algal/BaP extract showed similar mineralization patterns. The quantity of total metabolites formed was greater in bacterial cultures grown with the algal/BaP extract than those grown with BaP alone. For strain RJGII.135, only 27% of the original BaP remained in cultures grown with the algal/BaP extract; 59% remained in cultures grown with BaP. For strain B1, only 6% of the original BaP remained in cultures grown with the algal/BaP extract; 38% remained in cultures grown with BaP. These results indicate that strategies utilizing organisms together may be necessary in being able to degrade large, recalcitrant polycyclic aromatic hydrocarbons (PAHs) such as BaP.