Martin M. Shafer

Influences of Watershed Characteristics on Mercury Levels in Wisconsin Rivers

Total and monomethyl mercury were measured at 39 river sites in Wisconsin during fall 1992 and spring 1993. Using a Geographic Information System (GIS), we delineated watersheds with unique and homogeneous physical characteristics. Mean unfiltered total Hg (Hg T ) was higher in spring (7.94 ng L -1 ) than in fall (3.45 ng L -1 ). Major differences in Hg T yields were observed among various land-use groupings. In wetland/forest watersheds, elevated Hg T fluxes were associated with the filtered phase, while in agricultural watersheds, increased Hg T fluxes were due to particle loading. Monomethylmercury (MeHg) yields from wetland/forest sites were higher than agricultural/forest sites and agricultural only sites. Percent wetland surface area was positively correlated with MeHg yield. These results identify the importance of land use and land cover in influencing Hg concentrations, speciaton, and transport in rivers.

Seasonal influences on partitioning and transport of total and methylmercury in rivers from contrasting watersheds

Seven Wisconsin rivers with contrasting, relativelyhomogeneous watershed composition were selected toassess the factors controlling mercury transport.Together, these watersheds allow comparisons ofwetland, forest, urban and agricultural land-uses.Each site was sampled nine times between September1993 and September 1994 to establish seasonalsignatures and transport processes of total mercury(HgT) and methylmercury (MeHg). Our resultsclearly show that land use and land cover stronglyinfluence mercury transport processes. Under base-flowconditions, unfiltered MeHg yield varies by a factorof sixteen (12–195 mg km-2 d-1), andincreases with the fraction of wetland area in thewatershed. Elevated mercury yields during high floware particle-phase associated in agricultural sites,but filtered-phase associated in wetland sites.Methylmercury represented less than 5% of totalmercury mobilized during the spring thaw across allwatersheds. Autumn MeHg yield was generally 11–15%of HgT in wetland influenced watersheds, thougha maximum of 51% was observed. In some cases, singlehigh-flow events may dominate the annual export ofmercury from a watershed. For example, one high-flowevent on the agricultural Rattlesnake Creek had thelargest HgT and MeHg yield in the study (107 and2.32 mg km-2 d-1, respectively). The mass ofmercury transported downstream by this single eventwas an order of magnitude larger than the eight other(non-event) sampling dates combined. These resultsunderscore the importance of watershed characteristicsand seasonal events on the fate of mercury in freshwater rivers.

The influence of dissolved organic carbon, suspended particulates, and hydrology on the concentration, partitioning and variability of trace metals in two contrasting Wisconsin watersheds (U.S.A.)

Factors controlling the levels and forms of trace metals in streams, and transport from watersheds into streams, are poorly understood. We determined levels of filtrable ( Zn > Cd > Cu, whereas relationships to DOC indicated essentially the reverse order for metal binding to DOC. SPM was a good predictor of particulate metal levels, especially in the Milwaukee River (> 94% of variance in particulate Cd, Pb, and Zn was accounted for, vs. 44–69% in Wolf River). While DOC was able to account for a significant portion of the variation in certain filtrable metal levels (r2 = 0.52–0.65), other metals showed poorer correlations, probably due to variability in the composition of DOC and SPM and to variability in the forms of metal (aqueous complexes, colloid-bound) in the filtrable fraction.

Associations of primary and secondary organic aerosols with airway and systemic inflammation in an elderly panel cohort.

Background: Exposure-response information about particulate air-pollution constituents is needed to protect sensitive populations. Particulate matter <2.5 mm (PM2.5) components may induce oxidative stress through reactive-oxygen-species generation, including primary organics from combustion sources and secondary organics from photochemically oxidized volatile organic compounds. We evaluated differences in airway versus systemic inflammatory responses to primary versus secondary organic particle components, particle size fractions, and the potential of particles to induce cellular production of reactive oxygen species. Methods: A total of 60 elderly subjects contributed up to 12 weekly measurements of fractional exhaled nitric oxide (NO; airway inflammation biomarker), and plasma interleukin-6 (IL-6; systemic inflammation biomarker). PM2.5 mass fractions were PM0.25 (<0.25 &mgr;m) and PM0.25–2.5 (0.25–2.5 &mgr;m). Primary organic markers included PM2.5 primary organic carbon, and PM0.25 polycyclic aromatic hydrocarbons and hopanes. Secondary organic markers included PM2.5 secondary organic carbon, and PM0.25 water soluble organic carbon and n-alkanoic acids. Gaseous pollutants included carbon monoxide (CO) and nitrogen oxides (NOx; combustion emissions markers), and ozone (O3; photochemistry marker). To assess PM oxidative potential, we exposed rat alveolar macrophages in vitro to aqueous extracts of PM0.25 filters and measured reactive-oxygen-species production. Biomarker associations with exposures were evaluated with mixed-effects models. Results: Secondary organic markers, PM0.25–2.5, and O3 were positively associated with exhaled NO. Primary organic markers, PM0.25, CO, and NOx were positively associated with IL-6. Reactive oxygen species were associated with both outcomes. Conclusions: Particle effects on airway versus systemic inflammation differ by composition, but overall particle potential to induce generation of cellular reactive oxygen species is related to both outcomes.

Comparison of total mercury and methylmercury cycling at five sites using the small watershed approach

The small watershed approach is well-suited but underutilized in mercury research. We applied the small watershed approach to investigate total mercury (THg) and methylmercury (MeHg) dynamics in streamwater at the five diverse forested headwater catchments of the US Geological Survey Water, Energy, and Biogeochemical Budgets (WEBB) program. At all sites, baseflow THg was generally less than 1ng L(-1) and MeHg was less than 0.2ng L(-1). THg and MeHg concentrations increased with streamflow, so export was primarily episodic. At three sites, THg and MeHg concentration and export were dominated by the particulate fraction in association with POC at high flows, with maximum THg (MeHg) concentrations of 94 (2.56)ng L(-1) at Sleepers River, Vermont; 112 (0.75)ng L(-1) at Rio Icacos, Puerto Rico; and 55 (0.80)ng L(-1) at Panola Mt., Georgia. Filtered (<0.7microm) THg increased more modestly with flow in association with the hydrophobic acid fraction (HPOA) of DOC, with maximum filtered THg concentrations near 5ng L(-1) at both Sleepers and Icacos. At Andrews Creek, Colorado, THg export was also episodic but was dominated by filtered THg, as POC concentrations were low. MeHg typically tracked THg so that each site had a fairly constant MeHg/THg ratio, which ranged from near zero at Andrews to 15% at the low-relief, groundwater-dominated Allequash Creek, Wisconsin. Allequash was the only site with filtered MeHg consistently above detection, and the filtered fraction dominated both THg and MeHg. Relative to inputs in wet deposition, watershed retention of THg (minus any subsequent volatilization) was 96.6% at Allequash, 60% at Sleepers, and 83% at Andrews. Icacos had a net export of THg, possibly due to historic gold mining or frequent disturbance from landslides. Quantification and interpretation of Hg dynamics was facilitated by the small watershed approach with emphasis on event sampling.

A Macrophage-Based Method for the Assessment of the Reactive Oxygen Species (ROS) Activity of Atmospheric Particulate Matter (PM) and Application to Routine (Daily-24 h) Aerosol Monitoring Studies

Both short- and long-term exposure to particulate matter (PM) air pollution have been demonstrated to cause increases in cardiovascular disease, cancer, and respiratory disorders. Although the specific mechanisms by which exposure to PM cause these affects are unclear, significant evidence has accumulated to suggest that PM exposure leads to increased inflammation as the result of excessive production of reactive oxygen species (ROS) in critical cell types. In order to better understand how real-world PM exposure causes adverse health effects, there is a need to efficiently integrate metrics of PM toxicity into large scale air monitoring and health effects/epidemiology studies. Here we describe a rapid, inexpensive, method that can be employed to assess the potential of sub-mg masses of PM to generate oxidative stress in alveolar macrophage cells. Importantly, the approach is compatible with routine daily PM sampling programs such as those administered by EPA (Speciation trends network (STN), IMPROVE network, PM2.5 mass monitoring network), allowing for multiple samples to be assessed simultaneously with low volumes and brief exposure periods. We apply the method to a set of water extracts of daily PM2.5 samples (25–350 μ g PM mass) collected in the Denver-Metro area. Variations in the magnitude of the ROS response observed between the samples were only partially explained by differences in mass loading, with the highest levels of ROS being observed in samples collected during the summer months. This assay provides a very useful tool that can be coupled with detailed chemical analysis and statistical models to work towards the goal of attributing PM toxicity to specific real-world chemical sources.

Aerosol chemical, physical, and radiative characteristics near a desert source region of northwest China during ACE‐Asia

in both sap and ssp, resulting from diurnal changes in the mixing height as well as from local combustion sources in the morning and dust sources in the afternoon. Two distinct populations of aerosol mass scattering efficiencies Escat_2.5, one for aerosols dominated by desert dust (� 1.0 m 2 g � 1 ) and the other for aerosols composed primarily of local pollutants (� 3.0 m 2 g � 1 ), are observed. During the field study there were three significant dust events that occurred for, on average, several days at a time. The most significant dust storm resulted in a 24-hour-average PM2.5 concentration (mass concentration of particles having aerodynamic diameters less than 2.5 mm) of 453 m gm � 3 and a peak ssp of 2510 Mm � 1 on 8 April. The mean PM2.5 mass concentration during the dust storm periods is approximately 169 m gm � 3 , about 4 times greater than the mean value of 44 m gm � 3 observed during local pollution periods. When local pollution is the dominant source of fine particulate mass, organic matter (OM) is the major chemical component, contributing 41% to the PM2.5 mass, followed by crustal material (29%), sulfate (17%), and elemental carbon (EC) (13%). During sand storm periods, � 51% of PM2.5 mass is crustal material, followed by CO3� (11%) and OM (9.5%). The element enrichment factors indicate that coal combustion, biomass burning, and mobile source emissions are important local pollution sources. Overall, our results indicate that in addition to dust, local pollution also has a significant influence on aerosol properties in the region. INDEX TERMS: 0305 Atmospheric Composition and Structure: Aerosols and particles (0345, 4801); 0345 Atmospheric Composition and Structure: Pollution—urban and regional (0305); 0360 Atmospheric Composition and Structure: Transmission and scattering of radiation; 9320 Information Related to Geographic Region: Asia; KEYWORDS: aerosol, dust, ACE-Asia

Toxic metals in the atmosphere in Lahore, Pakistan.

Aerosol mass (PM(10) and PM(2.5)) and detailed elemental composition were measured in monthly composites during the calendar year of 2007 at a site in Lahore, Pakistan. Elemental analysis revealed extremely high concentrations of Pb (4.4microg m(-3)), Zn (12microg m(-3)), Cd (0.077microg m(-3)), and several other toxic metals. A significant fraction of the concentration of Pb (84%), Zn (98%), and Cd (90%) was contained in the fine particulate fraction (PM(2.5) and smaller); in addition, Zn and Cd were largely (>or=60%) water soluble. The 2007 annual average PM(10) mass concentration was 340microg m(-3), which is well above the WHO guideline of 20microg m(-3). Dust sources were found to contribute on average (maximum) 41% (70%) of PM(10) mass and 14% (29%) of PM(2.5) mass on a monthly basis. Seasonally, concentrations were found to be lowest during the monsoon season (July-September). Principle component analysis identified seven factors, which combined explained 91% of the variance of the measured components of PM(10). These factors included three industrial sources, re-suspended soil, mobile sources, and two regional secondary aerosol sources likely from coal and/or biomass burning. The majority of the Pb was found to be associated with one industrial source, along with a number of other toxic metals including As and Cr. Cadmium, another toxic metal, was found at concentrations 16 times higher than the maximum exposure level recommended by the World Health Organization, and was concentrated in one industrial source that was also associated with Zn. These results highlight the importance of focusing control strategies not only on reducing PM mass concentration, but also on the reduction of toxic components of the PM as well, to most effectively protect human health and the environment.

Airway inflammation and oxidative potential of air pollutant particles in a pediatric asthma panel

Airborne particulate matter (PM) components from fossil fuel combustion can induce oxidative stress initiated by reactive oxygen species (ROS). Reported associations between worsening asthma and PM2.5 mass could be related to PM oxidative potential to induce airway oxidative stress and inflammation (hallmarks of asthma pathology). We followed 45 schoolchildren with persistent asthma in their southern California homes daily over 10 days with offline fractional exhaled nitric oxide (FENO), a biomarker of airway inflammation. Ambient exposures included daily average PM2.5, PM2.5 elemental and organic carbon (EC, OC), NO2, O3, and endotoxin. We assessed PM2.5 oxidative potential using both an abiotic and an in vitro bioassay on aqueous extracts of daily particle filters: (1) dithiothreitol (DTT) assay (abiotic), representing chemically produced ROS; and (2) ROS generated intracellularly in a rat alveolar macrophage model using the fluorescent probe 2′7′-dicholorohidroflourescin diacetate. We analyzed relations of FENO to air pollutants in mixed linear regression models. FENO was significantly positively associated with lag 1-day and 2-day averages of traffic-related markers (EC, OC, and NO2), DTT and macrophage ROS, but not PM2.5 mass. DTT associations were nearly twice as strong as other exposures per interquartile range: median FENO increased 8.7–9.9% per 0.43 nmole/min/m3 DTT. Findings suggest that future research in oxidative stress-related illnesses such as asthma and PM exposure would benefit from assessments of PM oxidative potential and composition.

Increased biomass burning due to the economic crisis in Greece and its adverse impact on wintertime air quality in Thessaloniki.

The recent economic crisis in Greece resulted in a serious wintertime air pollution episode in Thessaloniki. This air quality deterioration was mostly due to the increased price of fuel oil, conventionally used as a source of energy for domestic heating, which encouraged the residents to burn the less expensive wood/biomass during the cold season. A wintertime sampling campaign for fine particles (PM2.5) was conducted in Thessaloniki during the winters of 2012 and 2013 in an effort to quantify the extent to which the ambient air was impacted by the increased wood smoke emissions. The results indicated a 30% increase in the PM2.5 mass concentration as well as a 2-5-fold increase in the concentration of wood smoke tracers, including potassium, levoglucosan, mannosan, and galactosan. The concentrations of fuel oil tracers (e.g., Ni and V), on the other hand, declined by 20-30% during 2013 compared with 2012. Moreover, a distinct diurnal variation was observed for wood smoke tracers, with significantly higher concentrations in the evening period compared with the morning. Correlation analysis indicated a strong association between reactive oxygen species (ROS) activity and the concentrations of levoglucosan, galactosan, and potassium, underscoring the potential impact of wood smoke on PM-induced toxicity during the winter months in Thessaloniki.