skip to main content

Explore Research Products in the NSF-PAR

Title: Reactive mercury flux measurements using cation exchange membranes https://amt.copernicus.org/preprints/amt-2018-360/
A method was developed to measure gaseous oxidized mercury (GOM) air-surface exchange using 2 replicated dynamic flux chambers (DFCs) in conjunction with cation exchange membrane (CEM) filters. The experimental design and method was developed and tested in a laboratory setting, using materials collected from industrial scale open pit gold mines in central Nevada, USA. Materials used included waste rock, heap leach ore, and tailings, with substrate concentrations ranging from 100 to 40000 ng g-1 total mercury (THg). CEM filters were used to capture GOM from the DFC sample lines while a Tekran® 2537A analyzer measured GEM concurrently. Previous and ongoing work has demonstrated that CEM do not collect GEM and efficiently collect multiple compounds of GOM. GOM emission rates up to 4000 pg m- 2 h-1 were measured from tailings materials with high Hg substrate concentrations, and this has significant implication with respect to air-Hg surface exchange. GOM flux was variable for lower Hg concentration substrates, with both emission and deposition observed, and this was affected by ambient air GOM concentrations. For substrates that experienced GOM deposition, deposition velocities were in the range 0.01 – 0.07 cm s-1.  more » « less
Award ID(s):
1700711
NSF-PAR ID:
10216378
Author(s) / Creator(s):
; ;
Date Published:
Journal Name:
Atmospheric measurement techniques
ISSN:
1867-1381
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ; ; ( , Atmospheric Measurement Techniques)
    null (Ed.)
    Abstract. Reactive mercury (RM), the sum of both gaseous oxidized Hg and particulatebound Hg, is an important component of the global atmospheric mercury cycle,but measurement currently depends on uncalibrated operationally definedmethods with large uncertainty and demonstrated interferences and artifacts.Cation exchange membranes (CEMs) provide a promising alternative methodologyfor 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 becaptured and retained with high efficiency. In this study, the performance ofCEM material under exposure to high concentrations of GEM (1.43×106 to 1.85×106 pg m−3) and reactive gaseous mercurybromide (HgBr2 ∼5000 pg m−3) was explored using acustom-built mercury vapor permeation system. Quantification of totalpermeated Hg was measured via pyrolysis at 600 ∘C and detectionusing a Tekran® 2537A. Permeation tests wereconducted over 24 to 72 h in clean laboratory air, with absolute humiditylevels ranging from 0.1 to 10 g m−3 water vapor. GEM uptake by the CEMmaterial averaged no more than 0.004 % of total exposure for all testconditions, which equates to a non-detectable GEM artifact for typicalambient air sample concentrations. Recovery of HgBr2 on CEM filters wason average 127 % compared to calculated total permeated HgBr2 based onthe downstream Tekran® 2537A data. The lowHgBr2 breakthrough on the downstream CEMs (< 1 %) suggests thatthe elevated recoveries are more likely related to suboptimal pyrolyzerconditions or inefficient collection on the Tekran® 2537A gold traps. 
    more » « less
  2. ; ; ; ; ( , Biogeosciences)
    Abstract. The tundra plays a pivotal role in the Arctic mercury(Hg) cycle by storing atmospheric Hg deposition and shuttling it to theArctic Ocean. A recent study revealed that 70 % of the atmospheric Hgdeposition to the tundra occurs through gaseous elemental mercury (GEM or Hg(0))uptake by vegetation and soils. Processes controlling land–atmosphereexchange of Hg(0) in the Arctic tundra are central, but remainunderstudied. Here, we combine Hg stable isotope analysis of Hg(0) in theatmosphere, interstitial snow air, and soil pore air, with Hg(0) fluxmeasurements in a tundra ecosystem at Toolik Field Station in northernAlaska (USA). In the dark winter months, planetary boundary layer (PBL)conditions and Hg(0) concentrations were generally stable throughout the dayand small Hg(0) net deposition occurred. In spring, halogen-inducedatmospheric mercury depletion events (AMDEs) occurred, with the fastre-emission of Hg(0) after AMDEs resulting in net emission fluxes of Hg(0).During the short snow-free growing season in summer, vegetation uptake ofatmospheric Hg(0) enhanced atmospheric Hg(0) net deposition to the Arctictundra. At night, when PBL conditions were stable, ecosystem uptake ofatmospheric Hg(0) led to a depletion of atmospheric Hg(0). The night-timedecline of atmospheric Hg(0) was concomitant with a depletion of lighterHg(0) isotopes in the atmospheric Hg pool. The enrichment factor,ε202Hgvegetationuptake=-4.2 ‰ (±1.0 ‰) was consistentwith the preferential uptake of light Hg(0) isotopes by vegetation. Hg(0)flux measurements indicated a partial re-emission of Hg(0) during daytime,when solar radiation was strongest. Hg(0) concentrations in soil pore airwere depleted relative to atmospheric Hg(0) concentrations, concomitant withan enrichment of lighter Hg(0) isotopes in the soil pore air, ε202Hgsoilair-atmosphere=-1.00 ‰(±0.25 ‰) and E199Hgsoilair-atmosphere=0.07 ‰ (±0.04 ‰). Thesefirst Hg stable isotope measurements of Hg(0) in soil pore air areconsistent with the fractionation previously observed during Hg(0) oxidationby natural humic acids, suggesting abiotic oxidation as a cause for observedsoil Hg(0) uptake. The combination of Hg stable isotope fingerprints withHg(0) flux measurements and PBL stability assessment confirmed a dominantrole of Hg(0) uptake by vegetation in the terrestrial–atmosphere exchange ofHg(0) in the Arctic tundra. 
    more » « less
  3. ; ; ; ; ( , Environmental Science: Processes & Impacts)
    To simulate global mercury (Hg) dynamics in chemical transport models (CTMs), surface-atmosphere exchange of gaseous elemental mercury, Hg 0 , is often parameterized based on resistance-based dry deposition schemes coupled with a re-emission function, mainly from soils. Despite extensive use of this approach, direct evaluations of this implementation against field observations of net Hg 0 exchange are lacking. In this study, we evaluate an existing net exchange parameterization (referred to here as the base model) by comparing modeled fluxes of Hg 0 to fluxes measured in the field using micrometeorological techniques. Comparisons were performed in two terrestrial ecosystems: a grassland site in Switzerland and an Arctic tundra site in Alaska, U.S., each including summer and winter seasons. The base model included the dry deposition and soil re-emission parameterizations from Zhang et al. (2003) and the global CTM GEOS-Chem, respectively. Comparisons of modeled and measured Hg 0 fluxes showed large discrepancies, particularly in the summer months when the base model overestimated daytime net deposition by approximately 9 and 2 ng m −2 h −1 at the grassland and tundra sites, respectively. In addition, the base model was unable to capture a measured nighttime net Hg 0 deposition and wintertime deposition. We conducted a series of sensitivity analyses and recommend that Hg simulations using CTMs: (i) reduce stomatal uptake of Hg 0 over grassland and tundra in models by a factor 5–7; (ii) increase nighttime net Hg 0 deposition, e.g. , by increasing ground and cuticular uptake by reducing the respective resistance terms by factors of 3–4 and 2–4, respectively; and (iii) implement a new soil re-emission parameterization to produce larger daytime emissions and lower nighttime emissions. We also compared leaf Hg 0 uptake over the growing season estimated by the dry deposition model against foliar Hg measurements, which revealed good agreement with the measured leaf Hg concentrations after adjusting the base model as suggested above. We conclude that the use of resistance-based models combined with the new soil re-emission flux parameterization is able to reproduce observed diel and seasonal patterns of Hg 0 exchange in these ecosystems. This approach can be used to improve model parameterizations for other ecosystems if flux measurements become available. 
    more » « less
  4. ; ; ; ; ; ; ; ; ; ; et al ( , Environmental Science: Atmospheres)
    Terrestrial volcanism is known to emit mercury (Hg) into the atmosphere. However, despite many years of investigation, its net impact on the atmospheric Hg budget remains insufficiently constrained, in part because the transformations of Hg in volcanic plumes as they age and mix with background air are poorly understood. Here we report the observation of complete gaseous elemental mercury (GEM) depletion events in dilute and moderately aged (∼3–7 hours) volcanic plumes from Piton de la Fournaise on Réunion Island. While it has been suggested that co-emitted bromine could, once photochemically activated, deplete GEM in a volcanic plume, we measured low bromine concentrations in both the gas- and particle-phase and observed complete GEM depletion even before sunrise, ruling out a leading role of bromine chemistry here. Instead, we hypothesize that the GEM depletions were mainly caused by gas–particle interactions with sulfate-rich volcanic particles (mostly of submicron size), abundantly present in the dilute plume. We consider heterogeneous GEM oxidation and GEM uptake by particles as plausible manifestations of such a process and derive empirical rate constants. By extrapolation, we estimate that volcanic aerosols may scavenge 210 Mg y−1 (67–480 Mg y−1) of Hg from the atmosphere globally, acting effectively as atmospheric mercury sink. While this estimate is subject to large uncertainties, it highlights that Hg transformations in aging volcanic plumes must be better understood to determine the net impact of volcanism on the atmospheric Hg budget and Hg deposition pathways. 
    more » « less
  5. ; ; ; ; ; ; ; ; ; ( , Proceedings of the National Academy of Sciences)
    null (Ed.)
    Mercury is toxic to wildlife and humans, and forests are thought to be a globally important sink for gaseous elemental mercury (GEM) deposition from the atmosphere. Yet there are currently no annual GEM deposition measurements over rural forests. Here we present measurements of ecosystem–atmosphere GEM exchange using tower-based micrometeorological methods in a midlatitude hardwood forest. We measured an annual GEM deposition of 25.1 µg ⋅ m −2 (95% CI: 23.2 to 26.7 1 µg ⋅ m −2 ), which is five times larger than wet deposition of mercury from the atmosphere. Our observed annual GEM deposition accounts for 76% of total atmospheric mercury deposition and also is three times greater than litterfall mercury deposition, which has previously been used as a proxy measure for GEM deposition in forests. Plant GEM uptake is the dominant driver for ecosystem GEM deposition based on seasonal and diel dynamics that show the forest GEM sink to be largest during active vegetation growing periods and middays, analogous to photosynthetic carbon dioxide assimilation. Soils and litter on the forest floor are additional GEM sinks throughout the year. Our study suggests that mercury loading to this forest was underestimated by a factor of about two and that global forests may constitute a much larger global GEM sink than currently proposed. The larger than anticipated forest GEM sink may explain the high mercury loads observed in soils across rural forests, which impair water quality and aquatic biota via watershed Hg export. 
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email