Atmospheric Dry and Wet Deposition of Total Phosphorus to the Great Lakes.

Quantifying atmospheric loadings of total phosphorus (TP) to freshwater environments is essential to improve understanding of its fate and transport, and to mitigate the effects of excessive levels in freshwater ecosystems. To date, atmospheric deposition of TP in the U.S. is poorly characterized due to the lack of long-term deposition observations. Here, we integrate several historical datasets to develop an estimate of dry and wet deposition to the Great Lakes region. For dry deposition, we use TP concentrations in fine particulate matter (PM2.5) samples from fourteen land-based IMPROVE sites (2013-2020) upwind of the Great Lakes to provide new fine particle phosphorus dry deposition estimates. For wet deposition, we use TP concentrations in wet-only precipitation samples collected at eleven land-based sites (2001-2009) in the Great Lakes region. For both wet and dry deposition, a seasonal cycle is evident with higher concentrations in warmer and wetter months when compared to colder months. Additionally, there is an increasing gradient from north to south in wet deposition, likely driven by both higher precipitation and increased emissions near southern sites. Despite different sampling time periods, these updated observations can provide further constraints on the TP loadings to each of the five Great Lakes. We estimate annual deposition of TP to Lakes Superior, Michigan, Huron, Erie and Ontario at 526, 702, 495, 212, and 185 MTA per year, which is lower than prior estimates for Lakes Superior, Erie and Ontario, comparable for Lake Huron, and about two times greater for Lake Michigan. When considering only the contribution of fine particulate PM to the dry deposition, wet deposition dominated over dry at all lakes except for Lake Huron. However, prior global estimates suggest greater contributions from larger particles (PM10 and PM100), yet observations to validate these estimates over the Great Lakes are not available. Our findings indicate that dry deposition of a range of particle sizes are needed to constrain the total atmospheric deposition of TP over the Great Lakes.

Combustion-Related Organic Species in Temporally Resolved Urban Airborne Particulate Matter.

Accurate characterization of the chemical composition of particulate matter (PM) is essential for improved understanding of source attribution and resultant health impacts. To explore this we conducted ambient monitoring of a suite of 15 combustion-related organic species in temporally resolved PM 2.5 samples during an ongoing animal exposure study in a near source environment in Detroit, MI. All of the 15 species detected were above the method detection limit in 8 hour samples. This study focused on two molecular classes: Polycyclic Aromatic Hydrocarbons (PAHs) and Hopanes measured in samples. Of the 12 PAHs studied, benzo[b]fluoranthene (169 pg m-3), benzo[g,h,i]perylene (124 pg m-3), and benzo[e]pyrene (118, pg m-3) exhibited the three highest mean concentrations while 17α(H),21ß(H)-Hopane (189 pg m-3) and 17α(H),21ß(H)-30-Norhopane (145 pg m-3) had the highest mean concentrations of the 3 Hopanes analyzed in samples. Ratios of individual compound concentrations to total compound concentrations (∑ 15 compounds) showed the greatest daily variation for 17α(H),21ß(H)-Hopane (11-28%) and 17α(H),21ß(H)-30-Norhopane (8-20%). Diagnostic PAH concentration ratios ([IP]/[IP + BP] (range 0.30 - 0.45), [BaP]/[BaP+BeP] (range 0.26 - 0.44), [BaP]/[BP] (range 0.41 - 0.82), [Bb]/[Bk] (range 2.07 - 2.66), in samples reflected impacts froma mixture of combustion sources consistent with greater prevalence of petroleum combustion source emissions (gasoline, diesel, kerosene, and crude oil) compared to coal or wood combustion emissions impacts at this urban site. Results from this study demonstrate that short duration sampling for organic speciation provides temporally relevant exposure information.

Oil sands development and its impact on atmospheric wet deposition of air pollutants to the Athabasca Oil Sands Region, Alberta, Canada.

Characterization of air pollutant deposition resulting from Athabasca oil sands development is necessary to assess risk to humans and the environment. To investigate this we collected event-based wet deposition during a pilot study in 2010-2012 at the AMS 6 site 30 km from the nearest upgrading facility in Fort McMurray, AB, Canada. Sulfate, nitrate and ammonium deposition was (kg/ha) 1.96, 1.60 and 1.03, respectively. Trace element pollutant deposition ranged from 2 × 10(-5) - 0.79 and exhibited the trend Hg < Se < As < Cd < Pb < Cu < Zn < S. Crustal element deposition ranged from 1.4 × 10(-4) - 0.46 and had the trend: La < Ce < Sr < Mn < Al < Fe < Mg. S, Se and Hg demonstrated highest median enrichment factors (130-2020) suggesting emissions from oil sands development, urban activities and forest fires were deposited. High deposition of the elements Sr, Mn, Fe and Mg which are tracers for soil and crustal dust implies land-clearing, mining and hauling emissions greatly impacted surrounding human settlements and ecosystems.

Spatial patterns in wet and dry deposition of atmospheric mercury and trace elements in central Illinois, USA.

An intensive 1-month atmospheric sampling campaign was conducted concurrently at eight monitoring sites in central Illinois, USA, from June 9 to July 3, 2011 to assess spatial patterns in wet and dry deposition of mercury and other trace elements. Summed wet deposition of mercury ranged from 3.1 to 5.4 µg/m(2) across sites for the total study period, while summed dry deposition of reactive mercury (gaseous oxidized mercury plus particulate bound mercury) ranged from 0.7 to 1.6 µg/m(2), with no statistically significant differences found spatially between northern and southern sites. Ratios of summed wet to summed dry mercury deposition across sites ranged from 2.2 to 4.9 indicating that wet deposition of mercury was dominant during the study period. Volume-weighted mean mercury concentrations in precipitation were found to be significantly higher at northern sites, while precipitation depth was significantly higher at southern sites. These results showed that substantial amounts of mercury deposition, especially wet deposition, occurred during the study period relative to typical annual wet deposition levels. Summed wet deposition of anthropogenic trace elements was much higher, compared to summed dry deposition, for sulfur, selenium, and copper, while at some sites summed dry deposition dominated summed wet deposition for lead and zinc. This study highlights that while wet deposition of Hg was dominant during this spring/summer-season study, Hg dry deposition also contributed an important fraction and should be considered for implementation in future Hg deposition monitoring studies.

Automated speciated mercury measurements in Michigan.

Automated speciated mercury measurements were made at a rural (Dexter, MI) and an urban (Detroit, MI) site in Michigan during selected times from 1999 to 2002 to assess the concentrations of elemental (Hg0), reactive gaseous (RGM), and particulate mercury (Hgp) in these environments. Here we present the first-ever reported values for RGM in Michigan. Median RGM concentrations were 2.21-2.93 pg m(-3) at Dexter and were 3-11 times higher in Detroit at 6.41-22.0 pg m(-3). Maximum RGM concentrations of 38.7 pg m(-3) and 270 pg m(-3) were observed in Dexter and Detroit, respectively. Measured RGM/Hg0 ratios were in the range of 0.04-11.60% indicating that at times RGM comprises greater than the currently held view of 5% of total gaseous mercury in the air. Well-pronounced diurnal patterns of RGM were observed at the rural site, whereas the urban site exhibited patterns that were influenced by nighttime emissions and regional transport. An analysis of RGM/Hgp ratios at the urban site when combined with trajectory analysis suggests that the site receives mercury inputs from both local and regional sources. Episodes of elevated ozone concentrations which were accompanied by increases in RGM concentrations were observed to occur in the late afternoon and overnight. These may be evidence of advection of ozone and RGM over long distances to the site.

Comparison of methods for particulate phase mercury analysis: sampling and analysis.

Accurate and reliable sampling and analysis of mercury forms is an overriding aim of any atmospheric monitoring effort which seeks to understand the fate and transport of the metal in the environment. Although a fraction of the total mercury forms found in the atmosphere, particulate phase mercury, Hg(p), is believed to play a prominent role in both wet and dry deposition to the terrestrial and aquatic environments. Currently, microwave acid extraction and thermoreductive methodologies for analysis of Hg(p) samples are widely used. We report on the potential for the use of a thermoreductive method for Hg(p) analysis to evaluate and optimize it for use in routine monitoring networks. Pre-baked quartz filters can be placed in particulate samplers with well-characterized size cuts, such as dichotomous samplers and microoriface impactors. The thermoreductive methodology facilitates rapid analysis after sample collection. It requires no chemical extraction thereby eliminating the potential for contamination and generation of hazardous waste. Our results indicate that, on average, the thermoreductive method yields 30% lower values for fine fraction Hg(p) when compared with microwave acid digestion. This may be due to matrix interferents that reduce the collection efficiency of mercury onto gold preconcentration traps. Results for total particulate mercury samples indicate that on average the thermoreductive method yields 56% lower values for the coarse fraction when compared with microwave acid digestion. Experiments were also conducted in Detroit, MI, USA to investigate whether elevated reactive gaseous mercury (Hg(2+)(g)) in an urban environment can lead to an artifact during the collection of filters for Hg(p) analysis. Our results indicate a significantly higher amount of Hg(p) collected onto a filter using the conventional methodology as compared to a filter collected downstream of KCl-coated annular denuders in the absence of Hg(2+)(g). These results point to the presence of Hg(2+)(g) as an artifact during Hg(p) measurement. These results indicate that a denuder must be utilized upstream of a filter for Hg(p) collection to prevent significant Hg(2+)(g) artifact formation.