Performance of a new diffusive sampler for Hg0 determination in the troposphere

2007 ◽  
Vol 4 (2) ◽  
pp. 75 ◽  
Author(s):  
Henrik Skov ◽  
Britt T. Sørensen ◽  
Matthew S. Landis ◽  
Matthew S. Johnson ◽  
Paolo Sacco ◽  
...  
Keyword(s):  
Detection Limit ◽  
Elemental Mercury ◽  
Ambient Air ◽  
Atmospheric Mercury ◽  
Point Sources ◽  
Gaseous Elemental Mercury ◽  
Marine Predators ◽  
Diffusive Sampler ◽  
Ambient Concentrations ◽  
Areas Of Interest

Environmental context. Mercury is of concern to both the public and to the scientific community because it is found at high levels in some marine predators, prompting the US EPA and others to make guidelines restricting the consumption of some species. Most mercury in the environment is emitted to the atmosphere, but it is not known how it is transferred from the atmosphere to the marine environment. Therefore, it is important to study the connection between emission of mercury, its transport and removal from the atmosphere. We have developed a new sampler that is inexpensive, easy to use and with a sufficiently high detection limit that it can be used to measure the low mercury concentrations in the atmosphere at a reasonable time resolution. Abstract. Mercury behaves uniquely in the atmosphere due to its volatility and long lifetime. The existing methods for measuring atmospheric mercury are either expensive or labour intensive. The present paper presents a new measurement technique, the diffusive sampler, that is portable, inexpensive, easy to use, and does not need a power supply. The sampler is sufficiently sensitive that it can measure mercury at low ambient levels with an exposure time of 1 to 3 days. The sampler is based on the Radiello diffusive sampler, which was used to collect volatile organic compounds. In the present paper, the method is validated under controlled laboratory conditions. The uptake rate of the Radiello diffusive sampler is determined using known concentrations of gaseous elemental mercury, and is measured as a function of wind speed, relative humidity and temperature. The Radiello sampler has a detection limit of 0.14 ng m–3 for 1 day of exposure and thus can be used to measure mercury concentrations at the low levels found in ambient air. The Radiello sampler is therefore useful for mapping concentrations close to sources and sinks, in addition to ambient concentrations. For example, the sampler can be used to describe the geographical extent of Arctic mercury depletion episodes where gaseous elemental mercury is removed and stays close to 0 ng m–3 for days, and it can be a powerful tool for mapping gradients around point sources and other areas of interest.

scholarly journals Evaluation of cation exchange membrane performance under exposure to high Hg<sup>0</sup> and HgBr<sub>2</sub> concentrations

2019 ◽  
Vol 12 (2) ◽  
pp. 1207-1217 ◽  
Author(s):  
Matthieu B. Miller ◽  
Sarrah M. Dunham-Cheatham ◽  
Mae Sexauer Gustin ◽  
Grant C. Edwards
Keyword(s):  
Cation Exchange ◽  
High Efficiency ◽  
Absolute Humidity ◽  
Elemental Mercury ◽  
Mercury Vapor ◽  
Ambient Air ◽  
Atmospheric Mercury ◽  
Promising Alternative ◽  
Gaseous Elemental Mercury ◽  
High Concentrations

Abstract. Reactive mercury (RM), the sum of both gaseous oxidized Hg and particulate bound Hg, is an important component of the global atmospheric mercury cycle, but measurement currently depends on uncalibrated operationally defined methods with large uncertainty and demonstrated interferences and artifacts. Cation exchange membranes (CEMs) provide a promising alternative methodology for quantification of RM, but method validation and improvements are ongoing. For the CEM material to be reliable, uptake of gaseous elemental mercury (GEM) must be negligible under all conditions and RM compounds must be captured and retained with high efficiency. In this study, the performance of CEM material under exposure to high concentrations of GEM (1.43×106 to 1.85×106 pg m−3) and reactive gaseous mercury bromide (HgBr2 ∼5000 pg m−3) was explored using a custom-built mercury vapor permeation system. Quantification of total permeated Hg was measured via pyrolysis at 600 ∘C and detection using a Tekran® 2537A. Permeation tests were conducted over 24 to 72 h in clean laboratory air, with absolute humidity levels ranging from 0.1 to 10 g m−3 water vapor. GEM uptake by the CEM material averaged no more than 0.004 % of total exposure for all test conditions, which equates to a non-detectable GEM artifact for typical ambient air sample concentrations. Recovery of HgBr2 on CEM filters was on average 127 % compared to calculated total permeated HgBr2 based on the downstream Tekran® 2537A data. The low HgBr2 breakthrough on the downstream CEMs (< 1 %) suggests that the elevated recoveries are more likely related to suboptimal pyrolyzer conditions or inefficient collection on the Tekran® 2537A gold traps.

scholarly journals Evaluation of cation exchange membrane performance under exposure to high Hg<sup>0</sup> and HgBr<sub>2</sub> concentrations

2018 ◽  
Author(s):  
Matthieu B. Miller ◽  
Mae S. Gustin ◽  
Sarrah M. Dunham-Cheatham ◽  
Grant C. Edwards
Keyword(s):  
Cation Exchange ◽  
High Efficiency ◽  
Collection Efficiency ◽  
Absolute Humidity ◽  
Elemental Mercury ◽  
Ambient Air ◽  
Atmospheric Mercury ◽  
Promising Alternative ◽  
Gaseous Elemental Mercury ◽  
Mercury Uptake

Abstract. Reactive mercury (RM) is an important component of the global atmospheric mercury cycle, but measurement currently depends on un-calibrated, operationally defined methods with large uncertainty and demonstrated interferences and artifacts. Cation exchange membranes (CEM) provide a promising alternative methodology for quantification of RM, but method validation and improvement are ongoing. For the CEM material to be reliable, uptake of gaseous elemental mercury (GEM) must be negligible for all conditions, and RM compounds must be captured and retained with high efficiency. In this study the performance of CEM material under exposure to high concentrations of GEM (1.43 × 106–1.85 × 106 pg m−3) and reactive gaseous mercury bromide (HgBr2 ~ 5000 pg m−3) was explored, using a custom-built mercury vapor permeation system, with quantification of total permeated Hg accomplished via pyrolysis at 600 °C and detection using a Tekran® 2537A. Permeation tests were conducted for 24 to 72 hours in clean laboratory air, with absolute humidity levels ranging from 0.1–10 g m−3 water vapor. Gaseous elemental mercury uptake by the CEM material averaged no more than 0.004 % of total exposure for all test conditions, which equates to a non-detectable GEM artifact for typical ambient air sample concentrations. Recovery of HgBr2 on CEM filters was > 100 % compared to calculated total permeated HgBr2, suggesting incomplete thermal decomposition at the pyrolyzer, as the CEM material collected HgBr2 with less than 1 % downstream breakthrough on average, implying a high collection efficiency.

scholarly journals Estimation of speciated and total mercury dry deposition at monitoring locations in eastern and central North America

2012 ◽  
Vol 12 (9) ◽  
pp. 4327-4340 ◽  
Author(s):  
L. Zhang ◽  
P. Blanchard ◽  
D. A. Gay ◽  
E. M. Prestbo ◽  
M. R. Risch ◽  
...  
Keyword(s):  
North America ◽  
Dry Deposition ◽  
Regional Scale ◽  
Elemental Mercury ◽  
Field Studies ◽  
Relative Magnitude ◽  
Point Sources ◽  
Gaseous Elemental Mercury ◽  
Surrogate Surface ◽  
Ambient Concentrations

Abstract. Dry deposition of speciated mercury, i.e., gaseous oxidized mercury (GOM), particulate-bound mercury (PBM), and gaseous elemental mercury (GEM), was estimated for the year 2008–2009 at 19 monitoring locations in eastern and central North America. Dry deposition estimates were obtained by combining monitored two- to four-hourly speciated ambient concentrations with modeled hourly dry deposition velocities (Vd) calculated using forecasted meteorology. Annual dry deposition of GOM+PBM was estimated to be in the range of 0.4 to 8.1 μg m−2 at these locations with GOM deposition being mostly five to ten times higher than PBM deposition, due to their different modeled Vd values. Net annual GEM dry deposition was estimated to be in the range of 5 to 26 μg m−2 at 18 sites and 33 μg m−2 at one site. The estimated dry deposition agrees very well with limited surrogate-surface dry deposition measurements of GOM and PBM, and also agrees with litterfall mercury measurements conducted at multiple locations in eastern and central North America. This study suggests that GEM contributes much more than GOM+PBM to the total dry deposition at the majority of the sites considered here; the only exception is at locations close to significant point sources where GEM and GOM+PBM contribute equally to the total dry deposition. The relative magnitude of the speciated dry deposition and their good comparisons with litterfall deposition suggest that mercury in litterfall originates primarily from GEM, which is consistent with the limited number of previous field studies. The study also supports previous analyses suggesting that total dry deposition of mercury is equal to, if not more important than, wet deposition of mercury on a regional scale in eastern North America.

scholarly journals Concentration-weighted trajectory approach to identifying potential sources of speciated atmospheric mercury at an urban coastal site in Nova Scotia, Canada

2013 ◽  
Vol 13 (12) ◽  
pp. 6031-6048 ◽  
Author(s):  
I. Cheng ◽  
L. Zhang ◽  
P. Blanchard ◽  
J. Dalziel ◽  
R. Tordon
Keyword(s):  
Nova Scotia ◽  
Elemental Mercury ◽  
Atmospheric Mercury ◽  
Point Sources ◽  
Grid Cells ◽  
Coastal Site ◽  
Northern Ontario ◽  
Gaseous Elemental Mercury ◽  
Source Areas ◽  
Local Sources

Abstract. Regional and local sources contributing to gaseous elemental mercury (GEM), gaseous oxidized mercury (GOM), and particle-bound mercury (PBM) at an urban coastal site in Dartmouth, Nova Scotia, Canada were investigated using the Concentration-Weighted Trajectory model (CWT) and Conditional Probability Function. From 2010–2011, GEM, GOM, and PBM concentrations were 1.67 ± 1.01 ng m−3, 2.07 ± 3.35 pg m−3, and 2.32 ± 3.09 pg m−3, respectively. Seasonal variability was observed, with statistically higher GEM and PBM concentrations in winter and spring and higher GOM in spring. In the CWT, concentrations are the weighting factors for the trajectory residence time in modeled grid cells, which results in the identification of source areas based on the CWT values in the grid cells. Potential source areas were identified in regions with known industrial Hg sources particularly in the fall season, but also in regions without these sources (e.g. Atlantic Ocean, northern Ontario and Quebec). CWTs for GOM and PBM that were associated with ≥ 5 kg industrial Hg emissions from 2010–2011 were statistically larger than those with zero Hg emissions, despite a lack of strong correlations. A large proportion of elevated CWTs (85–97%) was in regions with zero industrial Hg sources indicating the potential role of non-point sources, natural emissions, and residential-scale combustion. Analysis of wind data suggests that a commercial harbor and vehicular traffic were potential local sources. Evaluating modeled source areas against Hg emissions inventories was not an ideal method for assessing the CWT model accuracy because of insufficient data on Hg emissions at more precise locations.

scholarly journals Concentration-weighted trajectory approach to identifying sources of Speciated Atmospheric Mercury at an Urban Coastal Site in Nova Scotia, Canada

2013 ◽  
Vol 13 (2) ◽  
pp. 4183-4219
Author(s):  
I. Cheng ◽  
L. Zhang ◽  
P. Blanchard ◽  
J. Dalziel ◽  
R. Tordon
Keyword(s):  
Nova Scotia ◽  
Elemental Mercury ◽  
Atmospheric Mercury ◽  
Point Sources ◽  
Grid Cells ◽  
Coastal Site ◽  
Northern Ontario ◽  
Gaseous Elemental Mercury ◽  
Source Areas ◽  
Local Sources

Abstract. Regional and local sources contributing to gaseous elemental mercury (GEM), gaseous oxidized mercury (GOM), and particle-bound mercury (PBM) at an urban coastal site in Dartmouth, Nova Scotia, Canada were investigated using the Concentration-Weighted Trajectory model (CWT) and Conditional Probability Function. From 2010–2011, GEM, GOM, and PBM concentrations were 1.67 ± 1.01 ng m−3, 2.07 ± 3.35 pg m−3, and 2.32 ± 3.09 pg m−3, respectively. Seasonal variability was observed, with statistically higher GEM and PBM concentrations in winter and spring and higher GOM in spring. In the CWT, concentrations are the weighting factors for the trajectory residence time in modeled grid cells, which results in the identification of source areas based on the CWT values in the grid cells. Source areas were identified in regions with known industrial Hg sources particularly in the fall season, but also in regions without these sources (e.g. Atlantic Ocean, northern Ontario and Quebec). CWTs for GOM and PBM that were associated with ≥5 kg industrial Hg emissions from 2010–2011 were statistically larger than those with zero Hg emissions, despite a lack of strong correlations. A large proportion of elevated CWTs (85–97%) was in regions with zero industrial Hg sources indicating the potential role of non-point sources, natural emissions, and residential-scale combustion. Analysis of wind data suggests that a commercial harbour and vehicular traffic were potential local sources. Evaluating modeled source areas against Hg emissions inventories was not an ideal method for assessing the CWT model accuracy because of insufficient data on Hg emissions at more precise locations.

scholarly journals A field intercomparison of three passive air samplers for gaseous mercury in ambient air

2021 ◽  
Vol 14 (5) ◽  
pp. 3657-3672
Author(s):  
Attilio Naccarato ◽  
Antonella Tassone ◽  
Maria Martino ◽  
Sacha Moretti ◽  
Antonella Macagnano ◽  
...  
Keyword(s):  
Activated Carbon ◽  
National Research Council ◽  
Elemental Mercury ◽  
Weather Conditions ◽  
Ambient Air ◽  
Atmospheric Mercury ◽  
Ease Of Use ◽  
Environmental Research ◽  
Gaseous Elemental Mercury ◽  
Gaseous Mercury

Abstract. Passive air samplers (PASs), which provide time-averaged concentrations of gaseous mercury over the timescale of weeks to months, are promising for filling a gap in the monitoring of atmospheric mercury worldwide. Their usefulness will depend on their ease of use and robustness under field conditions, their availability and affordability, and most notably, their ability to provide results of acceptable precision and accuracy. Here we describe a comparative evaluation of three PASs with respect to their ability to precisely and accurately record atmospheric background mercury concentrations at sites in both southern Italy and southern Ontario, Canada. The study includes the CNR-PAS with gold nanoparticles as a sorbent, developed by the Italian National Research Council, the IVL-PAS using an activated carbon-coated disk, developed by the Swedish Environmental Research Institute, and the MerPAS® using a sulfur-impregnated activated carbon sorbent, developed at the University of Toronto and commercialized by Tekran. Detection limits are deduced from the variability in the amount of mercury quantified in more than 20 field blank samples for each PAS. Analytical and sampling precision is quantified through 22 triplicate deployments for each PAS, ranging in duration from 2 to 12 weeks. Accuracy and bias are assessed through comparison with gaseous elemental mercury concentrations recorded by Tekran 2537 automated mercury analyzers operating alongside the PASs at both locations. The performance of the PASs was significantly better in Italy, with all of them providing concentrations that are not significantly different from the average concentrations of the Tekran 2537 instruments. In Canada, where weather conditions were much harsher and more variable during the February through April deployment period, there are differences amongst the PASs. At both sites, the MerPAS® is currently the most sensitive, precise, and accurate among the three PASs. A key reason for this is the larger size and the radial configuration of the MerPAS®, which results in lower blank levels relative to the sequestered amounts of mercury when compared to the other two PASs, which rely on axial diffusion geometries. Since blank correction becomes relatively smaller with longer deployments, performance tends to be closer amongst the PASs during deployments of 8 and 12 weeks.

scholarly journals A field intercomparison of three passive air samplers for gaseous mercury in ambient air

2020 ◽  
Author(s):  
Attilio Naccarato ◽  
Antonella Tassone ◽  
Maria Martino ◽  
Sacha Moretti ◽  
Antonella Macagnano ◽  
...  
Keyword(s):  
Activated Carbon ◽  
National Research Council ◽  
Elemental Mercury ◽  
Weather Conditions ◽  
Ambient Air ◽  
Atmospheric Mercury ◽  
Ease Of Use ◽  
Environmental Research ◽  
Gaseous Elemental Mercury ◽  
Gaseous Mercury

Abstract. Passive air samplers (PASs), providing time-averaged concentration of gaseous mercury over the time scale of weeks to months, are promising to fill a gap in the monitoring of atmospheric mercury worldwide. Their usefulness will depend on their ease-of-use and robustness under field conditions, their availability and affordability, and most notably, their ability to provide results of acceptable precision and accuracy. Here we describe a comparative evaluation of three PASs with respect to their ability to record precisely and accurately atmospheric background concentrations at sites in both southern Italy and southern Ontario. The study includes the CNR-PAS with gold nanoparticles as a sorbent, developed by the Italian National Research Council, the IVL-PAS using an activated carbon-coated disk, developed by the Swedish Environmental Research Institute, and the MerPAS® using a sulfur-impregnated activated carbon sorbent, developed at the University of Toronto and commercialized by Tekran. Detection limits are deduced from the variability in the amount of mercury quantified in more than 20 field blank samples for each PAS. Analytical and sampling precision is quantified through 22 triplicated deployments for each PAS ranging in length from two to twelve weeks. Accuracy and bias are assessed through comparison with gaseous elemental mercury concentrations recorded by Tekran 2537 automated mercury analyzers operating alongside the PASs at both locations. The performance of the PASs was significantly better in Italy, with all of them providing concentrations that are not statistically significantly different from the average of the active sampling results. In Canada, where weather conditions were much harsher and more variable during the February through April deployment period, differences were observed amongst PASs. At both sites, the MerPAS® is currently the most sensitive, precise and accurate among the three PASs. A key reason for this is the larger size and the radial configuration of the MerPAS®, which results in blank levels that are lower relative to the sequestered amounts of mercury than in the other two PASs, which rely on axial diffusion geometries. Because the blank-correction becomes relatively smaller with longer deployment, sampler performance tends to be better during deployments of 8 and 12 weeks.

scholarly journals Behavior of KCl sorbent traps and KCl trapping solutions used for atmospheric mercury speciation: stability and specificity

2021 ◽  
Vol 14 (10) ◽  
pp. 6619-6631
Author(s):  
Jan Gačnik ◽  
Igor Živković ◽  
Sergio Ribeiro Guevara ◽  
Radojko Jaćimović ◽  
Jože Kotnik ◽  
...  
Keyword(s):  
Elemental Mercury ◽  
Ambient Air ◽  
Atmospheric Mercury ◽  
Mercury Speciation ◽  
Atomic Fluorescence Spectrometry ◽  
Atomic Fluorescence ◽  
Gaseous Elemental Mercury ◽  
Specificity Test ◽  
Sorbent Materials ◽  
The Stability

Abstract. Atmospheric mercury speciation is of paramount importance for understanding the behavior of mercury once it is emitted into the atmosphere as gaseous elemental mercury (GEM), gaseous oxidized mercury (GOM) and particulate-bound mercury (PBM). GOM and PBM can also be formed in the atmosphere; their sampling is the most problematic step in the atmospheric mercury speciation. GOM sampling with speciation traps composed of KCl sorbent materials and KCl trapping solutions are commonly used sampling methods, although the research conducted with them at ambient air concentrations is limited. The results of the specificity test demonstrated that the KCl sorbent traps are highly specific when using new traps, while their specificity drops dramatically when they are reused. The results of the stability test indicated that the highest Hg2+ losses (up to 5.5 % of Hg2+ loss) occur when low amounts of Hg2+ (< 1 ng) are loaded, due to a reduction of Hg2+ to Hg0. KCl trapping solutions have also been considered as a selective trapping media for GOM in atmospheric samples. A dimensionless Henry law constant was experimentally derived and was used to calculate the solubility of elemental Hg in KCl solution. The degree of GEM oxidation was established by purging elemental Hg calibration gas into a KCl solution and determining the GOM trapped using aqueous-phase propylation liquid–liquid extraction and gas chromatography–atomic fluorescence spectrometry (GC-AFS) measurement. A positive GOM bias was observed due to the solubility and oxidation of GEM in KCl trapping solutions, strongly suggesting that this approach is unsuitable for atmospheric mercury speciation measurements.

scholarly journals Air Concentrations of Gaseous Elemental Mercury and Vegetation–Air Fluxes within Saltmarshes of the Tagus Estuary, Portugal

Atmosphere ◽  
2021 ◽  
Vol 12 (2) ◽  
pp. 228
Author(s):  
Rute Cesário ◽  
Nelson J. O’Driscoll ◽  
Sara Justino ◽  
Claire E. Wilson ◽  
Carlos E. Monteiro ◽  
...  
Keyword(s):  
Leaf Area ◽  
Elemental Mercury ◽  
Ambient Air ◽  
Tagus Estuary ◽  
Contaminated Site ◽  
Gaseous Elemental Mercury ◽  
Mercury Flux ◽  
Sarcocornia Fruticosa ◽  
Air Concentrations

In situ air concentrations of gaseous elemental mercury (Hg(0)) and vegetation–atmosphere fluxes were quantified in both high (Cala Norte, CN) and low-to-moderate (Alcochete, ALC) Hg-contaminated saltmarsh areas of the Tagus estuary colonized by plant species Halimione portulacoides (Hp) and Sarcocornia fruticosa (Sf). Atmospheric Hg(0) ranged between 1.08–18.15 ng m−3 in CN and 1.18–3.53 ng m−3 in ALC. In CN, most of the high Hg(0) levels occurred during nighttime, while the opposite was observed at ALC, suggesting that photoreduction was not driving the air Hg(0) concentrations at the contaminated site. Vegetation–air Hg(0) fluxes were low in ALC and ranged from −0.76 to 1.52 ng m−2 (leaf area) h−1 for Hp and from −0.40 to 1.28 ng m−2 (leaf area) h−1 for Sf. In CN, higher Hg fluxes were observed for both plants, ranging from −9.90 to 15.45 ng m−2 (leaf area) h−1 for Hp and from −8.93 to 12.58 ng m−2 (leaf area) h−1 for Sf. Mercury flux results at CN were considered less reliable due to large and fast variations in the ambient air concentrations of Hg(0), which may have been influenced by emissions from the nearby chlor-alkali plant, or historical contamination. Improved experimental setup, the influence of high local Hg concentrations and the seasonal activity of the plants must be considered when assessing vegetation–air Hg(0) fluxes in Hg-contaminated areas.

scholarly journals Simulation of atmospheric mercury depletion events (AMDEs) during polar springtime using the MECCA box model

2008 ◽  
Vol 8 (23) ◽  
pp. 7165-7180 ◽  
Author(s):  
Z.-Q. Xie ◽  
R. Sander ◽  
U. Pöschl ◽  
F. Slemr
Keyword(s):  
Aqueous Phase ◽  
Ozone Depletion ◽  
Elemental Mercury ◽  
Atmospheric Mercury ◽  
Box Model ◽  
Rate Coefficients ◽  
Mercury Species ◽  
Phase Reaction ◽  
Gaseous Elemental Mercury ◽  
Sea Salt Aerosol

Abstract. Atmospheric mercury depletion events (AMDEs) during polar springtime are closely correlated with bromine-catalyzed tropospheric ozone depletion events (ODEs). To study gas- and aqueous-phase reaction kinetics and speciation of mercury during AMDEs, we have included mercury chemistry into the box model MECCA (Module Efficiently Calculating the Chemistry of the Atmosphere), which enables dynamic simulation of bromine activation and ODEs. We found that the reaction of Hg with Br atoms dominates the loss of gaseous elemental mercury (GEM). To explain the experimentally observed synchronous depletion of GEM and O3, the reaction rate of Hg+BrO has to be much lower than that of Hg+Br. The synchronicity is best reproduced with rate coefficients at the lower limit of the literature values for both reactions, i.e. kHg+Br≈3×10−13 and kHg+BrO≤1×10−15 cm3 molecule−1 s−1, respectively. Throughout the simulated AMDEs, BrHgOBr was the most abundant reactive mercury species, both in the gas phase and in the aqueous phase. The aqueous-phase concentrations of BrHgOBr, HgBr2, and HgCl2 were several orders of magnitude larger than that of Hg(SO3)22−. Considering chlorine chemistry outside depletion events (i.e. without bromine activation), the concentration of total divalent mercury in sea-salt aerosol particles (mostly HgCl42−) was much higher than in dilute aqueous droplets (mostly Hg(SO3)22−), and did not exhibit a diurnal cycle (no correlation with HO2 radicals).

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