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.

Ambient concentrations and total deposition of inorganic sulfur, inorganic nitrogen and base cations in the Athabasca Oil Sands Region.

Trace gas, particulate matter and deposition data collected in the Athabasca Oil Sands Region (AOSR) from 2000 to 2017 were evaluated as part of a broad scientific programmatic review. Results showed significant spatial patterns and temporal trends across the region. Concentrations of reactive gases were highest near the center of surface oil sands production operations and decreased towards the edges of the monitoring domain by factors of 8, 20, 4 and 3 for SO2, NO2, HNO3 and NH3, respectively. 18 of 30 sites showed statistically significant (p < 0.05) negative trends in SO2 concentrations suggesting an ~40% decrease since 2000. In contrast, only 2 of 30 sites showed statistically significant temporal trends (1 positive, 1 negative) for NO2. NH3 data showed (i) intermittent wildfire impacts, and (ii) high seasonality, with low concentrations during winter and significantly higher values during the summer. PM10 measurements were more limited, but also showed significant spatio-temporal variability. Comparison of PM10 and PM2.5 data showed that >80% of SO42- was in the PM2.5 fraction, while > 60% of Ca2+, Mg2+, Na+ and Cl- were in the PM10-2.5 fraction. Ion balances of both PM10 and PM2.5 contained cation excesses at near-field oil sand sites, but PM2.5 samples at forest health sites >20 km from surface production locations contained anion excesses. Monthly average concentrations of PM10 ions showed peak Ca2+ during March-April to November, but peak SO42-, NH4+ and NO3- from November-March. Deposition estimates showed rapid declines as a function of distance to oil sand operations. Estimated total N and total S deposition to forest health monitoring sites ranged from 2.0 to 5.7 kg ha-1 a-1 and 2.1-14.0 kg ha-1 a-1, respectively. Potential acid input (PAI) ranged from -0.46 to 0.79 keq ha-1 a-1 and was mostly 0.1-0.2 keq ha-1 a-1 throughout the domain, except for two clusters of sites near oil sand operations.

Use of an epiphytic lichen and a novel geostatistical approach to evaluate spatial and temporal changes in atmospheric deposition in the Athabasca Oil Sands Region, Alberta, Canada.

Temporal and spatial atmospheric deposition trends of elements to the boreal forest surrounding bitumen production operations in the Athabasca Oil Sands Region (AOSR), Alberta, Canada were investigated as part of a long-term lichen bioindicator study. The study focused on eight elements (sulfur, nitrogen, aluminum, calcium, iron, nickel, strontium, vanadium) that were previously identified as tracers for the major oil sand production sources. Samples of the in situ epiphytic lichen Hypogymnia physodes were collected in 2002, 2004, 2008, 2011, 2014, and 2017 within a ~150 km radius from the center of surface oil sand production operations in the AOSR. Site-specific time series analysis conducted at eight jack pine upland sites that were repeatedly sampled generally showed significant trends of increasing lichen concentrations for fugitive dust linked elements, particularly at near-field (<25 km from a major oil sands production operation) sample locations. Multiple regional scale geostatistical models were developed and evaluated to characterize broad-scale changes in atmospheric deposition based on changes in H. physodes elemental concentrations between 2008 and 2014. Empirical Bayesian kriging and cokriging lichen element concentrations with oil sands mining, bitumen upgrading, coke materials handling, and limestone quarry/crushing influence variables produced spatial interpolation estimates with the lowest validation errors. Gridded zonal mean lichen element concentrations were calculated for the two comprehensive sampling years (2008, 2014) and evaluated for spatial and temporal change. Lichen sulfur concentrations significantly increased in every grid cell within the domain with the largest increases (44-88%) in the central valley in close proximity to the major surface oil sand production operations, while a minor nitrogen concentration decrease (-20%) in a single grid cell was observed. The areal extent of fugitive dust element deposition generally increased with significantly higher deposition to lichens restricted to the outer grids of the enhanced deposition field, reflecting new and expanding surface mining activity.

Source apportionment of an epiphytic lichen biomonitor to elucidate the sources and spatial distribution of polycyclic aromatic hydrocarbons in the Athabasca Oil Sands Region, Alberta, Canada.

The sources and spatial distribution of polycyclic aromatic hydrocarbons (PAHs) atmospheric deposition in the boreal forests surrounding bitumen production operations in the Athabasca Oil Sands Region (AOSR), Alberta, Canada were investigated as part of a 2014 passive in-situ bioindicator source apportionment study. Epiphytic lichen species Hypogymnia physodes samples (n = 127) were collected within a 150 km radius of the main surface oil sand production operations and analyzed for total sulfur, total nitrogen, forty-three elements, twenty-two PAHs, ten groups of C1-C2-alkyl PAHs and dibenzothiophenes (polycyclic aromatic compounds; PACs), five C1- and C2-alkyldibenzothiophenes, and retene. The ΣPAH + PAC in H. physodes ranged from 54 to 2778 ng g-1 with a median concentration of 317 ng g-1. Source apportionment modeling found an eight-factor solution that explained 99% of the measured ΣPAH + PAC lichen concentrations from four anthropogenic oil sands production sources (Petroleum Coke, Haul Road Dust, Stack Emissions, Raw Oil Sand), two local/regional sources (Biomass Combustion, Mobile Source), and two lichen biogeochemical factors. Petroleum Coke and Raw Oil Sand dust were identified as the major contributing sources of ΣPAH + PAC in the AOSR. These two sources accounted for 63% (43.2 µg g-1) of ΣPAH + PAC deposition to the entire study domain. Of this overall 43.2 µg g-1 contribution, approximately 90% (39.9 µg g-1) ΣPAH + PAC was deposited within 25 km of the closest oil sand production facility. Regional sources (Biomass Combustion and Mobile Sources) accounted for 19% of ΣPAH + PAC deposition to the entire study domain, of which 46% was deposited near-field to oil sand production operations. Source identification was improved over a prior lichen-based study in the AOSR through incorporation of PAH and PAC analytes in addition to inorganic analytes.

Source apportionment of ambient fine and coarse particulate matter polycyclic aromatic hydrocarbons at the Bertha Ganter-Fort McKay community site in the Oil Sands Region of Alberta, Canada.

A comprehensive filter-based particulate matter polycyclic aromatic hydrocarbon (PAH) source apportionment study was conducted at the Wood Buffalo Environmental Association Bertha Ganter-Fort McKay (BGFM) community monitoring station from 2014 to 2015 to quantify ambient concentrations and identify major sources. The BGFM station is located in close proximity to several surface oil sands production facilities and was previously found to be impacted by their air emissions. 24-hour integrated PM2.5 and PM10-2.5 samples were collected on a 1-in-3-day schedule yielding 108 complete organic/inorganic filter sets for source apportionment modeling. During the study period PM2.5 averaged 8.6 ±â€¯11.8 µg m-3 (mean ±â€¯standard deviation), and PM10-2.5 averaged 8.5 ±â€¯9.5 µg m-3. Wind regression analysis indicated that the oil sands production facilities were significant sources of PM2.5 mass and black carbon (BC), and that wildland fires were a significant source of the highest PM2.5 (>10 µg m-3) and BC events. A six-factor positive matrix factorization (PMF) model solution explained 95% of the measured PM2.5 and 78% of the measured ΣPAH. Five sources significantly contributed to PM2.5 including: Biomass Combustion (3.57 µg m-3; 40%); Fugitive Dust (1.86 µg m-3; 28%); Upgrader Stack Emissions (1.44 µg m-3; 21%); Petrogenic PAH (1.20 µg m-3; 18%); and Transported Aerosol (0.43 µg m-3 and 6%). However, the analysis indicated that only the pyrogenic PAH source factor significantly contributed (78%) to the measured ΣPAH. A five-factor PMF model dominated by fugitive dust sources explained 98% of PM10-2.5 mass and 86% of the ΣPAH. The predominant sources of PM10-2.5 mass were (i) Haul Road Dust (4.82 µg m-3; 53%), (ii) Mixed Fugitive Dust (2.89 µg m-3; 32%), (iii) Fugitive Oil Sand (0.88 µg m-3; 10%), Mobile Sources (0.23 µg m-3; 2%), and Organic Aerosol (0.06 µg m-3; 1%). Only the Organic Aerosol source significantly contributed (86%) to the measured ΣPAH.

The impact of the 2016 Fort McMurray Horse River Wildfire on ambient air pollution levels in the Athabasca Oil Sands Region, Alberta, Canada.

An unprecedented wildfire impacted the northern Alberta city of Fort McMurray in May 2016 causing a mandatory city wide evacuation and the loss of 2,400 homes and commercial structures. A two-hectare wildfire was discovered on May 1, grew to ~157,000ha by May 5, and continued to burn an estimated ~590,000ha by June 13. A comprehensive air monitoring network operated by the Wood Buffalo Environmental Association (WBEA) in and around Fort McMurray provided essential health-related real-time air quality data to firefighters during the emergency, and provided a rare opportunity to elucidate the impact of gaseous and particulate matter emissions on near-field communities and regional air pollution concentrations. The WBEA network recorded 188 fire-related exceedances of 1-hr and 24-hr Alberta Ambient Air Quality Objectives. Two air monitoring sites within Fort McMurray recorded mean/maximum 1-hr PM2.5 concentrations of 291/5229µgm-3 (AMS-6) and 293/3259µgm-3 (AMS-7) during fire impact periods. High correlations (r2=0.83-0.97) between biomass combustion related gases (carbon monoxide (CO), non-methane hydrocarbons (NMHC), total hydrocarbons (THC), total reduced sulfur (TRS), ammonia) and PM2.5 were observed at the sites. Filter-based 24-hr integrated PM2.5 samples collected every 6 days showed maximum concentrations of 267µgm-3 (AMS-6) and 394µgm-3 (AMS-7). Normalized excess emission ratios relative to CO were 149.87±3.37µgm-3ppm-1 (PM2.5), 0.274±0.002ppmppm-1 (THC), 0.169±0.001ppmppm-1 (NMHC), 0.104±0.001ppmppm-1 (CH4), 0.694±0.007ppbppm-1 (TRS), 0.519±0.040ppbppm-1 (SO2), 0.412±0.045ppbppm-1 (NO), 1.968±0.053ppbppm-1 (NO2), and 2.337±0.077ppbppm-1 (NOX). A subset of PM2.5 filter samples was analyzed for trace elements, major ions, organic carbon, elemental carbon, and carbohydrates. Sample mass reconstruction and fire specific emission profiles are presented and discussed. Potential fire-related photometric ozone instrument positive interferences were observed and were positively correlated with NO and NMHC.

Source apportionment of ambient fine and coarse particulate matter at the Fort McKay community site, in the Athabasca Oil Sands Region, Alberta, Canada.

An ambient air particulate matter sampling study was conducted at the Wood Buffalo Environmental Association (WBEA) AMS-1 Fort McKay monitoring station in the Athabasca Oil Sand Region (AOSR) in Alberta, Canada from February 2010 to July 2011. Daily 24h integrated fine (PM2.5) and coarse (PM10-2.5) particulate matter was collected using a sequential dichotomous sampler. Over the duration of the study, 392 valid daily dichotomous PM2.5 and PM10-2.5 sample pairs were collected with concentrations of 6.8±12.9µgm-3 (mean±standard deviation) and 6.9±5.9µgm-3, respectively. A subset of 100 filter pairs was selected for element analysis by energy dispersive X-ray fluorescence and dynamic reaction cell inductively coupled plasma mass spectrometry. Application of the U.S. EPA positive matrix factorization (PMF) receptor model to the study data matrix resolved five PM2.5 sources explaining 96% of the mass including oil sands upgrading (32%), fugitive dust (26%), biomass combustion (25%), long-range Asian transport lead source (9%), and winter road salt (4%). An analysis of historical PM2.5 data at this site shows that the impact of smoke from wildland fires was particularly high during the summer of 2011. PMF resolved six PM10-2.5 sources explaining 99% of the mass including fugitive haul road dust (40%), fugitive oil sand (27%), a mixed source fugitive dust (16%), biomass combustion (12%), mobile source (3%), and a local copper factor (1%). Results support the conclusion of a previous epiphytic lichen biomonitor study that near-field atmospheric deposition in the AOSR is dominated by coarse fraction fugitive dust from bitumen mining and upgrading operations, and suggest that fugitive dust abatement strategies targeting the three major sources of PM10-2.5 (e.g., oil sand mining, haul roads, bulk material stockpiles) would significantly reduce near-field atmospheric deposition gradients in the AOSR and reduce ambient PM concentrations in the Fort McKay community.

Investigation of mercury wet deposition physicochemistry in the Ohio River Valley through automated sequential sampling.

Intra-storm variability and soluble fractionation was explored for summer-time rain events in Steubenville, Ohio to evaluate the physical processes controlling mercury (Hg) in wet deposition in this industrialized region. Comprehensive precipitation sample collection was conducted from July through September 2006 using three different methods to evaluate both soluble and insoluble fractions as well as scavenging and washout properties of Hg and a suite of trace elements. Real-time filtration of event total precipitation revealed that 61±17% (mean±standard deviation) of Hg in wet deposition was in a soluble form. Comparison of total and dissolved element concentrations (solubility fractionation) showed the following order of decreasing solubility: S>Na>Se>Ca>Mg>Hg>As>Mn>V>Cr>Fe>La≈Ce ranging from 95% (S) to 4% (Ce). To examine removal mechanisms occurring during the course of a precipitation event, discrete, sequential sub-event precipitation samples were collected. Results indicated that Hg had lower "scavenging coefficients" (the rate of Hg concentration decrease throughout the events) than the majority of elements analyzed, indicating that either (i) Hg is incorporated into rain via gas phase inclusion or particulate nucleation within cloud, or (ii) Hg is available in the boundary layer for scavenging, even in the latter stages of precipitation. The Hg scavenging coefficient (-0.39) was low compared to S (-0.73), a co-pollutant of Hg. When compared to an upwind, regionally representative site, the scavenging coefficient of Hg for the locally influenced precipitation was 25% lower. This observation suggests that a continuous feed of soluble Hg was the reason for the low scavenging coefficient. Overall, this investigation of Hg wet deposition in Steubenville indicates that the physical and chemical properties of Hg emissions are driving the elevated deposition rates observed near point sources.

Relationship and variation of qPCR and culturable Enterococci estimates in ambient surface waters are predictable.

The quantitative polymerase chain reaction (qPCR) method provides rapid estimates of fecal indicator bacteria densities that have been indicated to be useful in the assessment of water quality. Primarily because this method provides faster results than standard culture-based methods, the U.S. Environmental Protection Agency is currently considering its use as a basis for revised ambient water quality criteria. In anticipation of this possibility, we sought to examine the relationship between qPCR-based and culture-based estimates of enterococci in surface waters. Using data from several research groups, we compared enterococci estimates by the two methods in water samples collected from 37 sites across the United States. A consistent linear pattern in the relationship between cell equivalents (CCE), based on the qPCR method, and colony-forming units (CFU), based on the traditional culturable method, was significant (P < 0.05) at most sites. A linearly decreasing variance of CCE with increasing CFU levels was significant (P < 0.05) or evident for all sites. Both marine and freshwater sites under continuous influence of point-source contamination tended to reveal a relatively constant proportion of CCE to CFU. The consistency in the mean and variance patterns of CCE versus CFU indicates that the relationship of results based on these two methods is more predictable at high CFU levels (e.g., log(10)CFU > 2.0/100 mL) while uncertainty increases at lower CFU values. It was further noted that the relative error in replicated qPCR estimates was generally higher than that in replicated culture counts even at relatively high target levels, suggesting a greater need for replicated analyses in the qPCR method to reduce relative error. Further studies evaluating the relationship between culture and qPCR should take into account analytical uncertainty as well as potential differences in results of these methods that may arise from sample variability, different sources of pollution, and environmental factors.

Spatial variability of mercury wet deposition in eastern Ohio: summertime meteorological case study analysis of local source influences.

Extensive exploration of event precipitation data in the Ohio River Valley indicates that coal combustion emissions play an important role in mercury (Hg) wet deposition. During July-September 2006, an intensive study was undertaken to discern the degree of local source influence. Source-receptor relationships were explored by establishing a set of wet deposition sites in and around Steubenville, Ohio. For the three month period of study, volume-weighted mean Hg concentrations observed at the eight sites ranged from 10.2 to 223 ng L(-1), but this range increased drastically on an event basis with a maximum concentration of 89.4 ng L(-1) and a minimum concentration of 4.1 ng L(-1). A subset of events was explored in depth, andthe degree of variability in Hg concentrations between sites was linked to the degree of local source enhancement. Samples collected at sites less than 1 km from coal-fired utility stacks (near-field) exhibited up to 72% enhancement in Hg concentrations over regionally representative samples on an event basis. Air mass transport and precipitating cell histories were traced in order to evaluate relationships between local point sources and receptor sites. It was found that the interaction of several dynamic atmospheric parameters combined to favor local Hg concentration enhancement over the more regional contribution. When significant meteorological factors (wind speed at time of maximum rain rate, wind speed 24 h prior to precipitation, mixing height, and observed ceiling) were explored, it was estimated that during summertime precipitation, 42% of Hg concentration in near-field samples could be attributed to the adjacent coal-fired utility source.