Coupling atmospheric mercury isotope ratios and meteorology to identify sources of mercury impacting a coastal urban‐industrial region near Pensacola, Florida, USA

Identifying the anthropogenic and natural sources of mercury (Hg) emissions contributing to atmospheric mercury on local, regional, and global scales continues to be a grand challenge. The relative importance of various direct anthropogenic emissions of mercury, in addition to natural geologic sources and reemission of previously released and deposited mercury, differs regionally and temporally. In this study, we used local‐scale, mesoscale, and synoptic‐scale meteorological analysis to couple the isotopic composition of ambient atmospheric mercury with potential sources of mercury contributing to a coastal urban‐industrial setting near a coal‐fired power plant in Pensacola, Florida, USA. We were able to broadly discern four influences on the isotopic composition of ambient atmospheric mercury impacting this coastal urban‐industrial region: (1) local to regional urban‐industrial anthropogenic emissions (mean δ202Hg = 0.44 ± 0.05‰, 1SD, n = 3), (2) marine‐influenced sources derived from the Gulf of Mexico (mean δ202Hg = 0.77 ± 0.15‰, 1SD, n = 4), (3) continental sources associated with north‐northwesterly flows from within the planetary boundary layer (mean δ202Hg = 0.65 ± 0.04‰, 1SD, n = 3), and (4) continental sources associated with north‐northeasterly flows at higher altitudes (i.e., 2000 m above ground level; mean δ202Hg = 1.10 ± 0.21‰, 1SD, n = 8). Overall, these data, in conjunction with previous studies, suggest that the background global atmospheric mercury pool is characterized by moderately positive δ202Hg values; that urban‐industrial emissions drive the isotopic composition of ambient atmospheric mercury toward lower δ202Hg values; and that air‐surface exchange dynamics across vegetation and soils of terrestrial ecosystems drive the isotopic composition of ambient atmospheric mercury toward higher positive δ202Hg values. The data further suggest that mass‐independent fractionation (MIF) of both even‐mass‐ and odd‐mass‐number isotopes, likely generated by photochemical reactions in the atmosphere or during reemission from terrestrial and aquatic ecosystems, can be obscured by mixing with anthropogenic emissions having different MIF signatures.Key PointsIsotopic composition of TGM differed among meteorologically identified sourcesBackground atmospheric TGM displayed moderately positive δ202Hg valuesAnthropogenic emissions drive TGM isotopic composition to lower δ202Hg valuesPeer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/136364/1/gbc20349-sup-0001-Supplementary.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/136364/2/gbc20349.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/136364/3/gbc20349_am.pd

A Case Study of Laser Wind Sensor Performance Validation by Comparison to an Existing Gage

A case study concerning validation of wind speed measurements made by a laser wind sensor mounted on a 190 square foot floating platform in Muskegon Lake through comparison with measurements made by pre-existing cup anemometers mounted on a met tower on the shore line is presented. The comparison strategy is to examine the difference in measurements over time using the paired-t statistical method to identify intervals when the measurements were equivalent and to provide explanatory information for the intervals when the measurements were not equivalent. The data was partitioned into three sets: not windy (average wind speed measured by the cup anemometers ≤ 6.7m/s) windy but no enhanced turbulence (average wind speed measured by the cup anemometers \u3e 6.7m/s), and windy with enhanced turbulence associated with storm periods. For the not windy data set, the difference in the average wind speeds was equal in absolute value to the precision of the gages and not statistically significant. Similar results were obtained for the windy with no enhanced turbulence data set and the average difference was not statistically significant (α=0.01). The windy with enhanced turbulence data set showed significant differences between the buoy mounted laser wind sensor and the on-shore mast mounted cup anemometers. The sign of the average difference depended on the direction of the winds. Overall, validation evidence is obtained in the absence of enhanced turbulence. In addition, differences in wind speed during enhanced turbulence were isolated in time, studied and explained

Reactive mercury in the troposphere: Model formation and results for Florida, the northeastern United States, and the Atlantic Ocean

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/95402/1/jgrd13669.pd

Laser Wind Sensor Performance Validation with an Existing Gage

A new approach to laser wind sensor measurement validation is described and demonstrated. The new approach relies on the paired-t statistical method to generate a time series of differences between two sets of measurements. This series of differences is studied to help identify and explain time intervals of operationally significant differences, which is not possible with the traditional approach of relying on the squared coefficient of variation as the primary metric. The new approach includes estimating a confidence interval for the mean difference and establishing a level of meaningful difference for the mean difference, and partitioning the data set based on wind speed. To demonstrate the utility of the new approach, measurements made by a laser wind sensor mounted on a floating buoy are compared first with those made by a second laser wind sensor mounted on a nearby small island for which the co-efficient of variation is high (\u3e 99%). It was found that time intervals when high differences in wind speed occurred corresponded to high differences in wind direction supporting a hypothesis that the two laser wind sensor units are not always observing the same wind resource. Furthermore, the average difference for the 100m range gate is positive, statistically significant (α=0.01) and slightly larger than the precision of the gages, 0.1m/s. One possible cause of this difference is that the surface roughness over land is slowing the wind at 100m slightly. A second comparison was made with previously existing cup anemometers mounted on a metrological mast located on-shore. The cup anemometers are about 8m lower than the center of the lowest range gate on the laser wind sensor. The data was partitioned into three sets: not windy (average wind speed at the cup anemometers ≤ 6.7m/s) windy but no enhanced turbulence (average wind speed at the cup anemometers \u3e 6.7m/s), and windy with enhanced turbulence. Periods of enhanced turbulence are associated with the passage of a cold frontal boundary. The paired-t analysis for the not windy data set showed a difference in the average wind speeds of -0.096m/s, less in absolute value than the precision of the gages. The negative sign indicates slower wind speed over land as well as at a lower height, which is expected. Similar results were obtained for the windy with no enhanced turbulence data set. In addition, the average difference was not statistically significant (α=0.01). The windy with enhanced turbulence data set showed significant differences between the buoy mounted laser wind sensor and the on-shore mast mounted cup anemometers. The sign of the average difference depended on the direction of the winds in the periods of enhanced turbulence. Mean turbulent kinetic energy was measured to be greater when air flow into Muskegon Lake was predominantly from over land versus when air flow was predominantly from Lake Michigan. The higher mean turbulent kinetic energy for flow originating over land would likely be due to greater surface roughness experienced by the overland flow. Overall, the value of the new approach in obtaining validation evidence has been demonstrated. In this case, validation evidence is obtained in periods of no enhanced turbulence. Differences in wind speed during periods of enhanced turbulence are isolated in time, studied and are correlated in time with differences in wind direction

Estimation of Dry Deposition of Atmospheric Mercury in Nevada by Direct and Indirect Methods

Atmospheric models and limited measurements indicate that dry deposition of atmospheric mercury is an important process by which mercury is input to ecosystems. To begin to fill the measurement data gap, multiple methods were used simultaneously during seasonal campaigns conducted in 2005 and 2006 to estimate dry deposition of atmospheric mercury at two Mercury Deposition Network (MDN) sites in rural Nevada and in Reno, Nevada. Gaseous elemental mercury (Hg0), reactive gaseous mercury (RGM), and particulate-bound mercury (Hgp) concentrations were measured using Tekran 2537A/1130/1135 systems. These speciated measurements were combined with on-site meteorological measurements to estimate depositional fluxes of RGM and Hgp using dry deposition models. Modeled fluxes were compared with more direct measurements obtained using polysulfone cation-exchange membranes and foliar surfaces. Dynamic flux chambers were used to measure soil mercury exchange. RGM concentrations were higher during warmer months at all sites, leading to seasonal variation in the modeled importance of RGM as a component of total depositional load. The ratio of dry to wet deposition was between 10 and 90%, and varied with season and with the methods used for dry deposition approximations. This work illustrates the variability of mercury dry deposition with location and time and highlights the need for direct dry deposition measurements

An Artificial Turf-Based Surrogate Surface Collector for the Direct Measurement of Atmospheric Mercury Dry Deposition

This paper describes the development of a new artificial turf surrogate surface (ATSS) sampler for use in the measurement of mercury (Hg) dry deposition. In contrast to many existing surrogate surface designs, the ATSS utilizes a three-dimensional deposition surface that may more closely mimic the physical structure of many natural surfaces than traditional flat surrogate surface designs (water, filter, greased Mylar film). The ATSS has been designed to overcome several complicating factors that can impact the integrity of samples with other direct measurement approaches by providing a passive system which can be deployed for both short and extended periods of time (days to weeks), and is not contaminated by precipitation and/or invalidated by strong winds. Performance characteristics including collocated precision, in-field procedural and laboratory blanks were evaluated. The results of these performance evaluations included a mean collocated precision of 9%, low blanks (0.8 ng), high extraction efficiency (97%–103%), and a quantitative matrix spike recovery (100%)