Do We Understand What the Mercury Speciation Instruments Are

Jan 10, 2013 - From August 22 to September 16, 2012, atmospheric mercury (Hg) was measured from a common manifold in the field during the Reno ...
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Do We Understand What the Mercury Speciation Instruments Are Actually Measuring? Results of RAMIX Part of the “RAMIX: Reno Atmospheric Intercomparison eXperiment” group Mae Sexauer Gustin,†,* Jiaoyan Huang,† Matthieu B. Miller,† Christianna Peterson,† Daniel A. Jaffe,‡,§ Jesse Ambrose,‡ Brandon D. Finley,‡ Seth N. Lyman,‡,⧫ Kevin Call,‡ Robert Talbot,∥ Dara Feddersen,⊥ Huiting Mao,# and Steven E. Lindberg▽ †

Department of Natural Resources and Environmental Science, University of Nevada, Reno, 1664 N. Virginia Street, Reno, Nevada, United States, 89557 ‡ Science and Technology Program, University of Washington−Bothell, 18115 Campus Way NE, Bothell, Washington, United States, 98011 § Department of Atmospheric Sciences, University of Washington, Seattle, Washington, United States, 98195 ∥ Department of Earth and Atmospheric Science, University of Houston, Houston, Texas, United States, 77204 ⊥ Department of Chemistry, University of New Hampshire, Durham, New Hampshire, United States, 03824 # Department of Chemistry, State University of New York, College of Environmental Science and Forestry, Syracuse, New York, United States, 13210 ▽ Emeritus Fellow, Oak Ridge National Laboratory, Graeagle, California S Supporting Information *

ABSTRACT: From August 22 to September 16, 2012, atmospheric mercury (Hg) was measured from a common manifold in the field during the Reno Atmospheric Mercury Intercomparison eXperiment. Data were collected using Tekran systems, laser induced fluorescence, and evolving new methods. The latter included the University of Washington-Detector for Oxidized Mercury, the University of Houston Mercury instrument, and a filter-based system under development by the University of Nevada-Reno. Good transmission of total Hg was found for the manifold. However, despite application of standard protocols and rigorous quality control, systematic differences in operationally defined forms of Hg were measured by the sampling systems. Concentrations of reactive Hg (RM) measured with new methods were at times 2-to-3-fold higher than that measured by Tekran system. The low RM recovery by the latter can be attributed to lack of collection as the system is currently configured. Concentrations measured by all instruments were influenced by their sampling location in-the-manifold and the instrument analytical configuration. On the basis of collective assessment of the data, we hypothesize that reactions forming RM were occurring in the manifold. Results provide a new framework for improved understanding of the atmospheric chemistry of Hg.

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INTRODUCTION

The automated method widely used to measure atmospheric Hg is the Tekran 2537/1130/1135 system (Tekran Instrument Corp., Ontario, Canada). This system applies a specific set of collection and desorption procedures resulting in operationally defined quantification of GEM, GOM, and PBM, respectively (see Supporting Information, SI). A KCl-coated quartz annular denuder is used to collect GOM; PBM is collected on a column

Atmospheric mercury (Hg) is currently measured as gaseous elemental Hg (GEM, generally 1 to 3 ng m−3), gaseous oxidized (GOM), and particle bound (PBM).1,2 Gaseous elemental Hg is thought to constitute 90 to 99% of the Hg in the atmosphere and to be relatively inert. The chemical forms of GOM have not been identified and the mechanisms important for formation are uncertain. Suggested compounds include HgCl2, HgBr2, HgO, HgSO4, Hg(NO2)2, and Hg(OH)2.3−12 In general, our understanding of PBM is poor; however, temperature is considered to play an important role in partitioning between the gas and particle phase.13 © XXXX American Chemical Society

Received: September 26, 2012 Revised: December 31, 2012 Accepted: January 10, 2013

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of quartz chips and a quartz filter; and GEM is concentrated on patented dual gold cartridges, in this order. Once collected, Hg is thermally desorbed from each unit and quantified as GEM using Cold Vapor Atomic Fluorescence Spectroscopy (CVAFS).14,15 There are no standard reference materials for GOM or PBM, and interferences for this instrument have not been adequately explored.16,17 Reported precision between colocated instruments is 0.4 to 20%, 15 to 40%, and up to 70% for GEM, GOM, and PBM, respectively.18−23 The 2537 unit alone is often used to measure atmospheric Hg independent of the 1130 and 1135 units. There is debate as to whether data collected using the 2537 unit are total atmospheric Hg (TM = GEM + GOM + PBM), GEM, or some fraction of all forms.16,24−26 Over time, multiple researchers have tested components of this system and compared observations with those obtained using other methods (see discussion and references in the SI). Concerns raised include passivation of the gold surface used to collect GEM, the impact of ozone (O3) and water vapor on the collection of GOM by the denuder and particle collecting units, the ability of the denuder to collect all forms of GOM, and artifacts associated with the PBM measurement. Without accurate, precise measurements of atmospheric Hg, we cannot understand the chemistry, interpret observed spatial and temporal patterns, or improve models. Here, we present the results of a comparison of data collected using two Tekran 2537/1130/1135 systems, two Tekran 2537 units, the Detector for Oxidized Hg Species (DOHGS) designed by University of Washington-Bothell (UW), and the University of Houston Mercury instrument (UHMERC) system operated by a team from the University of Houston, the State University of New York, and the University of New Hampshire. These instruments measured air Hg concentrations from a common manifold 27 in the field during the Reno Atmospheric Mercury Intercomparison eXperiment (RAMIX). Additional free-standing (adjacent but not connected to the manifold) measurements were made using the Tekran systems during and after RAMIX. Limited measurements were also made using a nylon filter system designed by the University of Nevada-Reno (UNR).28 Desert Research Institute operated a cavity ring-down spectroscopy system;29 however, because of strong drifts in baseline extinction due to laser problems, they did not obtain any data that could be used for the comparisons presented in this work. Here, we present free-standing and in-the-manifold data collected using the Tekran system, and compare with new methods. These are applied collectively to investigate the atmospheric chemistry of Hg during RAMIX. Field Setting. The RAMIX project was held at an inactive Hg Deposition Network (MDN, http://nadp.sws.uiuc.edu/ mdn) site, MDN NV98, located on the UNR Agricultural Experiment Station property (39.51° latitude, −119.72° longitude, elevation 1340 m) (ref 30 and SI). The designated RAMIX sampling time period occurred over four weeks from August 22 to September 16, 2012. Air Sampling Methods. All units sampled from a common manifold system consisting of 2.54 cm outer diameter (O.D.) insulated Teflon PFA tubing (see SI27) situated between four trailers housing equipment (only two shown in Figure 1). The upstream end of the manifold was a Teflon-coated cyclone inlet (URG-2000−30EA) with a cut size of 1 μm (50%) at a flow rate of 200 L min−1 (manufacturer communication). Mean flow in-the-manifold was 210 ± 4 L min−1, and ranged from 187 to

Figure 1. Schematic map of the trailers housing the equipment described in this paper (top panel) and a vertical profile of the manifold system (bottom panel). Note two other trailers were also present at the site. The CO instrument was located below the Spiking System in the large trailer. Circles indicate gas cylinders.

238 L min−1. The first 6 m of the manifold, including the cyclone inlet and the active sampling area, were insulated and heated to 115 ± 2 °C (Figure 1; see SI and ref 27 for details). Prior to RAMIX, testing of a manifold system of similar configuration, but ∼75% shorter length, was done at UW using laboratory air. Finley et al. 27 described the estimated transmission efficiency as 83 to 102% for GEM, 96 ± 3% for O3, and 78 ± 4% (range 73 to 88%) for HgBr2. During this laboratory study and RAMIX, GEM spikes were observed within 5 min based on the Tekran analytical cycle. Laboratory tests at UW prior to RAMIX indicated that 10 min were needed for HgBr2 concentrations to become stable, and to be removed from the system.27 To account for this in the data analyses, the first 5 min of GEM spikes were not included when assessing recoveries and instrument responses, and HgBr2 spikes were started 1 h before sampling. Gaseous elemental Hg was added to the manifold during Weeks 1 to 4 of the experiment. HgBr2, O3, and H2O vapor were added in Weeks 3 and 4. During Week 4, data were collected simultaneously using a free-standing Tekran system, and one sampling from the manifold. Limited simultaneous spikes were done, and conclusions regarding these are not possible; however, to help future researchers the details are provided in the SI. On the basis of temperature sensitivity of the flow sensor at the end of the manifold, spike recovery values have an uncertainty of ±15%. During RAMIX, UNR operated two Tekran 2537/1130/ 1135 atmospheric Hg speciation systems, hereafter referred to as Spec 1, the first in the line moving down flow, and Spec 2, the second in-line. In addition, to these Tekran systems UNR operated a Tekran 2537 unit, two O3 analyzers, a carbon monoxide (CO) analyzer, and meteorological equipment B

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Figure 2. Diel bin plots of mean GEM, GOM, TM (GEM + GOM + PBM), and RM (GOM + PBM), concentrations measured directly from the manifold. No spike data are included. Spec 2 adjusted represent the measurements by Spec 2 divided by 0.72. GEM_RPD is the relative percent difference between the Spec 1 and Spec 2 GEM data. The error bar indicates 1 standard deviation. Free standing CO and O3 data are also presented. The order of the legend and the error bars correspond to the order of these instruments in the manifold.

manifold and Tekran system pumps, and the low atmospheric pressure associated with the high elevation of Reno (1340 m), these two units were operated at 4 L min−1 instead of the 10 L min−1 suggested. The lower flow rate would not significantly affect denuder performance based on the capture efficiency calculated using the equation in Allegrini et al.31 The UNRoperated 2537 unit sampling line included a 0.2 μm pore size Teflon filter, and was 5 m long, covered, and heated to 50 °C. For more details on Tekran operation, configuration, and quality control procedures, see the SI. The University of Miami operated a Tekran 2537 unit and a Laser Induced Fluorescence (LIF) system for the measurement of GEM.32 The former sampled through 7.6 m of uncovered Teflon tubing with a 0.25 μm pore size particle filter in-line

(Figure 1, for details see SI, Table SI 1). The protocol developed for the Tekran system by the Atmospheric Mercury Network (AMNet) of the National Atmospheric Deposition Network (NADP)15 was applied with differences described below. Because a cyclone was attached to the inlet of the manifold system to remove particulate matter larger than 1 μm, the Tekran elutriator, designed to remove those larger than 2.5 μm, was replaced with 1.5 m of Teflon PFA tubing (1.27 cm O.D.). This tubing was connected to the manifold with a Teflon National Pipe Thread tapered head fitting. This connection and the glass inlets to the Tekran 2537/1130/ 1135 systems were heated to 100 °C. With this setting, when the air entered the Tekran 1130/1135 unit, a temperature drop of 50 °C occurred. Due to the competition between the C

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RESULTS AND DISCUSSION Setting the Stage. Overall, atmospheric chemistry at MDN NV98 will be influenced by planetary boundary layer (PBL) height, inputs from the free troposphere, nearby agricultural activities, roadways, and industry (cf. ref 30). During RAMIX, two fronts moved through the area and influenced overall atmospheric chemistry (Figures SI 1−5). A stable high pressure system persisted during Weeks 1 and 2. At the end of Week 2, a low pressure system moved into the area. A new system moved into the area at the end of Week 3, bringing precipitation across the area. As a result, higher mean relative humidity (RH) was observed during Week 4 than Weeks 1 to 3 (∼40 to 50% versus 30%, Figure SI 2). All instruments applied during RAMIX were operated under a stringent set of quality control procedures, as defined by each research team for their respective systems (see SI and the corresponding refs 27 and 32−34). Additionally, each sampling method, as applied, had a unique configuration with respect to data collected. Lastly, all measurements were made using ambient air, and previous tests of a similar manifold were made in the laboratory.27 Data Comparisons. Tekran 2537/1130/1135 Measurements. Comparison of Tekran 2537/1130/1135 data (including: manifold, free-standing, and during spikes; Table SI 2, Figures SI 6 and 7) showed systematically lower GEM and TM concentrations (GEM + GOM + PBM) measured by Spec 2. Despite repeated calibrations and quality assurance measures, this bias persisted throughout the experiment. Additionally, the RPD between mean hourly GEM concentrations, measured by Spec 1 and 2, consistently showed the latter to be lower by 25 to 35% (Figure 2). Because of this, the data collected using Spec 2 was adjusted based on the relationship between this unit and Spec 1 collected during the GEM spikes [Spec 2 (GEM ng m−3) = 0.72 × Spec 1 + 0.08; r2 = 0.89, n = 149, p < 0.001] (Figure SI 6). Thus, Spec 2 data are divided by 0.72 and described as “Spec 2 adjusted” from here on. Application of this adjustment factor resulted in comparable mean GEM concentrations overall measured by the two Tekran systems, when they were free-standing (Table SI 2). Application of this factor, however, resulted in the mean GOM and PBM concentrations for Spec 2 adjusted being higher than that calculated for Spec 1 when in-the-manifold (by 30 and 10 pg m−3, respectively), but not when free-standing. The same two denuders, coated by the same operator, were used from Sept 2 to 13, and these were switched between instruments on September 9. Prior to switching the slope for the equation comparing GOM as measured by Spec 1 versus Spec 2 adjusted was 1.7 (r2 = 0.57, p < 0.5, n = 76) after switching this was 1.2 (r2 = 0.62, p < 0.05, n = 42). This indicates that although there may have been some systematic bias between denuders Spec 2 adjusted consistently measured more GOM than Spec 1. We hypothesize that this trend is due to production of RM in the manifold (discussed later). Spike Recoveries. Using the Tekran 2537/1130/1135 data, and applying the Spec 2 adjustment factor, mean GEM ESrecovery% obtained during Week 4 was 76 ± 7%, and GEM ESresponse% for Weeks 1 to 3 were 76, 72, and 76% as measured by the UNR 2537 unit, Spec 1, and Spec 2 adjusted, respectively (Table SI 3). These units were situated in this order moving down flow in-the-manifold (Figure 1). Combining these over the entire RAMIX campaign, the ESrecovery/response% for Spec 1 (that was in-the-manifold over all

before the air entered the analyzer. Air entering this unit was cooled to 20 °C as it entered the sampling trailer. The DOHGS system operationally quantifies TM and GEM using two Tekran 2537 units. The TM measurement was made by pulling air through a quartz tube (2.2 cm diameter ×17.2 cm long) packed with quartz wool and heated to 650 °C, while the GEM measurement was made by pulling the air through a quartz wool packed trap at ∼25 °C 33. This data is applied to calculate reactive Hg (RM = GOM + PBM) by subtracting the GEM measurement from the TM measurement. The UHMERC instrument applies the same general collection and analyses method as the Tekran system,34 and measured GEM during the first week of the experiment. This instrument was connected to the manifold using a custom Teflon port connection that sampled air from the center of the manifold. The inlet to this instrument included 1.5 m of Restek Silco-Steel Sulfinert tubing heated to 50 °C. A Teflon filter was situated at the sample inlet to remove fine particles ( 0.7); poorly correlated with CO; and strongly correlated with relative humidity (r = 0.8). Gaseous oxidized Hg was significantly positively correlated with O3 (r = 0.65), temperature (r = 0.65), and solar radiation (r = 0.37 to 0.45), and negatively correlated with relative humidity (r = 0.75). These results suggest local production of GEM during the night and GOM during the day (Table SI 6). On most days a significant increase in mean hourly O3 concentrations was observed from 0800 to 1100 h (Figure 2). After 1100 h, concentrations decreased and remained fairly constant at 45 ppbv throughout the afternoon (Figure 2). Over this time modeled PBL height also showed a dramatic increase (from 100 to 1000 m above ground level; Figure SI 1). Carbon monoxide concentrations increased from 0600 to 0800 h when wind speeds were lowest and direction shifted from south to west, and then declined reaching a minimum in late afternoon (Figure 2; Figures SI 4 and SI 5). Ozone and CO concentrations were negatively correlated; however, this relationship only explained ∼50% of the variance (Table SI 6). Carbon monoxide was positively correlated with RH, explaining 45% of the variability. This suggests that some CO, but not all, was due to local pollution. For more than 50% of the days during Weeks 1, 2, and 4, a secondary peak in the 5min CO was observed at ∼1100 h (detailed data not shown). The high CO concentrations in the morning reflect inputs to a shallow boundary layer from vehicle traffic on a nearby heavily traveled roadway. The peaks of CO, O3, and GOM (Figure 2) in the late morning reflect mixing of polluted parcels of air to the surface from the free troposphere (cf. ref 43). The highest in-the-manifold values of GOM (400 pg m−3) were measured by the Tekran systems at the start of the experiment (Figure SI 8). Since new tubing was used for the manifold, this is thought to be due to flushing of contamination as the tubing was heated. Over the experiment both systems measured higher GOM (50 to 200 pg m−3) in the afternoon and at times these were greater for Spec 2 adjusted data by 50 to 100 pg m−3. This suggests that during the day a form of GOM was being produced in-the-manifold that was not being measured by Spec 1 (cf. Figure 2 and Figures SI 8 and 9). Concentrations of PBM were higher and more variable during Weeks 1 and 2 (25 to 100 pg m−3) relative to Weeks 3 F

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Figure 5. Hourly mean RM concentrations measured by the Tekran speciation systems and DOHGS during HgBr2 spikes. In the upper panel, during Week 3 both Spec 1 and 2 were sampling from the manifold. In the lower panel, that shows Week 4 data, only Spec 1 was sampling from the manifold. Speciation 1 and 2 data represent a single hourly measurement. The error bar on DOHGS data represents 1 standard deviation.

and 4 (