Mercury Concentrations In Air Research Articles

Development of a High-Resolution Laser Absorption Spectroscopy Method with Application to the Determination of Absolute Concentration of Gaseous Elemental Mercury in Air.

Isotope dilution-cold-vapor-inductively coupled plasma mass spectrometry (ID-CV-ICPMS) has become the primary standard for measurement of gaseous elemental mercury (GEM) mass concentration. However, quantitative mass spectrometry is challenging for several reasons including (1) the need for isotopic spiking with a standard reference material, (2) the requirement for bias-free passive sampling protocols, (3) the need for stable mass spectrometry interface design, and (4) the time and cost involved for gas sampling, sample processing, and instrument calibration. Here, we introduce a high-resolution laser absorption spectroscopy method that eliminates the need for sample-specific calibration standards or detailed analysis of sample treatment losses. This technique involves a tunable, single-frequency laser absorption spectrometer that measures isotopically resolved spectra of elemental mercury (Hg) spectra of 6 1S0 ← 6 3P1 intercombination transition near λ = 253.7 nm. Measured spectra are accurately modeled from first-principles using the Beer-Lambert law and Voigt line profiles combined with literature values for line positions, line shape parameters, and the spontaneous emission Einstein coefficient to obtain GEM mass concentration values. We present application of this method for the measurement of the equilibrium concentration of mercury vapor near room temperature. Three closed systems are considered: two-phase mixtures of liquid Hg and its vapor and binary two-phase mixtures of Hg-air and Hg-N2 near atmospheric pressure. Within the experimental relative standard uncertainty, 0.9-1.5% congruent values of the equilibrium Hg vapor concentration are obtained for the Hg-only, Hg-air, Hg-N2 systems, in confirmation with thermodynamic predictions. We also discuss detection limits and the potential of the present technique to serve as an absolute primary standard for measurements of gas-phase mercury concentration and isotopic composition.

Green chemistry and sustainable development: approaches to chemical footprint analysis

Abstract The methods to monitor the distribution of chemicals in the biosphere and to estimate the impact of chemicals on the biosphere are necessary to reach Sustainable Development Goals (SDGs). The paper presents the examples of methods to measure the concentration of heavy metals (including rare earth elements) and to rank them by the level of hazard to human health on different scales. The megacity scale presents the investigation of the impact of heavy metals on the small water bodies using water contamination index (WCI); and the investigation of snow contamination to estimate the level of short-term seasonal emission of heavy metals and rare earth elements. The 2nd part of the paper presents approaches to mitigate the exposure to mercury on the regional scale: the estimation of the current concentrations of mercury in atmospheric air, natural soils, and fresh waters using UNEP/SETAC USEtox model, as well as the estimations of the variations in the concentrations of mercury for the year 2045 in the federal districts of the Russian Federation, based on representative concentration pathways (RCPs) scenario and Minamata Convention scenario.

MOBILITY OF MERCURY IN THE VOLCANIC/GEOTHERMAL AREA OF NISYROS (GREECE)

In the summer 2013, mercury concentrations in soils and air from Nisyros (Greece), an active volcanic island located in the Aegean Sea, were determined. Up to 102 samples of soil were collected in the Lakki plain caldera and analyzed for mercury by using a cold vapour atomic absorption analyzer, following 7473 US EPA method. Concentrations of mercury in air were also investigated in the same sites with a portable spectrophotometer (Lumex RA-915M). Soil mercury concentrations were in the range from 0.023 to 13.7 µg/g. The mercury concentrations in air showed high background values in the Lakki plain caldera, ranging from 21 to 36 ng/m3 and maximum values up to 493 ng/m3 in the proximity of the fumarolic areas, in contrast with the relatively low values (from 2 to 5 ng/m3 ) measured in the distal sites outside of the caldera. The positive correlation between mercury and CO2 and H2S in the atmosphere highlights the important role of fumarolic gases as carrier for gaseous mercury (Hg0 ). On the contrary, mercury does not show significant correlations with CO2 and H2S in the soil gases. This finding evidences the complexity of the processes affecting mercury in hydrothermal gases passing through the soil.

Mercury concentrations in environmental media at a hazardous solid waste landfill site and mercury emissions from the site

Mercury (Hg) concentrations in air, effluent water, landfill gas, leachate, groundwater, and soil at a hazardous solid waste landfill site in Korea were measured along with air–soil surface Hg exchange fluxes at the site. The concentrations and fluxes were considerably higher than have been found elsewhere in Korea. Gaseous Hg concentrations in the air peaked during the day, coinciding with Hg being released from the landfill surface. This suggests that air–soil exchange increased the Hg concentrations in the atmosphere. The air–soil exchange flux increased abruptly when solar radiation reached the soil surface. The Hg flux peaked about 3 h before the solar radiation peaked, possibly because reducible Hg was abundant at the soil surface. The Hg emission flux activation energy (E a) was low, indicating that the Hg species present and Hg–soil binding were probably not as important (because of the high Hg content of the soil) as in previous studies. The methylmercury to total Hg ratios in the discharged effluent, groundwater, and leachate was clearly higher than typically found in coastal water and freshwater, suggesting bacteria caused active methylation to occur under the reducing conditions in the anaerobic landfill. The results suggested that considerable amounts of Hg are probably transported from the landfill to nearby environmental media and that this will continue if waste with a high Hg content continues to be added to the landfill without being pretreated.

Characterization of Mercury Contamination Surrounding a Chloralkali Production Facility in Tuzla, Bosnia and Herzegovina

ABSTRACTTuzla is among the most polluted cities of Bosnia and Herzegovina. The main source of pollution in the area is soil heavily contaminated by mercury released from a former chloralkali plant. This paper is focused on the characterization of mercury contaminated soil and air surrounding the chloralkali plant. In soil, the mobility and transformation of mercury were investigated by sequential extraction, while the methylation and reduction potentials were determined by the use of a radioactive tracer. Mercury emission from soil was determined by laboratory and by flux chamber measurements in the field. In addition, mercury concentrations in air were estimated by the analysis of air and the transplanted lichen Hypogymnia physodes. Mercury in soils in the vicinity of the chloralkali plant exceeded the background value by a factor of more than 3000. The fractionation of mercury in surface soil by sequential extraction showed that the mercury in soil was primarily bound to organic matter and a fraction containing elemental mercury and mercury (I) chloride is also significant. The obtained methylation and reduction potentials are low. The mercury flux from soil was estimated by two approaches. Fluxes of up to 8000 ng/m2/day were measured at the most polluted site; evaporation from soil was shown to be the primary source of elevated mercury in air. Air concentration mapping also revealed other sources of mercury; the most likely is the 715 MW coal power plant in the vicinity of former chloralkali facility.

Identifying occupational and nonoccupational exposure to mercury in dental personnel

ABSTRACTThe objective of this study was to investigate the occupational and nonoccupational exposure to mercury (Hg) vapor in dental personnel by examining the relationships between blood mercury, urine mercury, and their ratio with air mercury. The method was performed on 50 occupational exposed and 50 unexposed controls (25 men and 25 women). The mercury concentrations in air and human biological samples were determined based on the National Institute for Occupational Safety and Health (NIOSH) method and standard method (SM) by a new mode of liquid-phase microextraction, respectively. The mean mercury concentrations in urine (μg Hg0/g creatinine) and blood were significantly higher than control group, respectively (19.41 ± 5.18 vs 2.15 ± 0.07 μg/g and 16.40 ± 4.97 vs 2.50 ± 0.02 μg/L) (p <.001). The relationships between mercury concentration in blood/urine ratio (r = .380) with dental office air are new indicators for assessing occupational exposure in dental personnel.

How incense and joss paper burning during the worship activities influences ambient mercury concentrations in indoor and outdoor environments of an Asian temple?

This study firstly investigated the species, concentration variation, and emission factors of mercury emitted from the burning of incenses and joss papers in an Asian temple. Both indoor and outdoor speciated mercury (GEM, GOM, and PHg) were sampled by manual samplers, while ambient GEM at an indoor site was in-situ monitored by a continuous GEM monitor. Field measurement results showed that the total atmospheric mercury (TAM) concentrations in indoor and outdoor environments were in the range of 8.03–35.72 and 6.03–31.35 ng/m3, respectively. The indoor and outdoor ratios (I/O) of TAM in the daytime and at nighttime were in the range of 0.64–0.90 and 1.50–2.04, respectively. The concentrations of GEM, GOM, and PHg during the holiday periods were approximately 1–4 times higher than those during the non-holiday periods. GEM was the dominant mercury species in the indoor and outdoor environments and accounted for 63–81% of TAM, while the oxidized mercury accounted for 19–37% of TAM. Burning incenses and joss papers in a combustion chamber showed that the concentration of GEM from joss paper burning ranged from 4.07 to 11.62 μg/m3, or about 13.97 times higher than that of incense burning, while the concentration of PHg from incense burning ranged from 95.91 to 135.07 ng/m3, or about 3.29 times higher than that of joss paper burning. The emission factors of incense burning were 10.39 ng/g of GEM and 1.40 ng/g of PHg, while those of joss paper burning were 12.65 ng/g of GEM and 1.27 ng/g of PHg, respectively. This study revealed that speciated mercury emitted from worship activities had significant influence on the indoor and outdoor mercury concentrations in an Asian temple. Higher intensity of worship activities during holidays resulted in a higher concentration of speciated mercury in indoor and outdoor air, which might cause health threats to worshipers, staffs, and surrounding inhabitants through long-term exposure.

Mercury risk assessment combining internal and external exposure methods for a population living near a municipal solid waste incinerator

Risk assessments for human health have been conducted for municipal solid waste incinerators (MSWIs) in many western countries, whereas only a few risk assessments have been performed for MSWIs in developing countries such as China where the use of waste incineration is increasing rapidly. To assess the mercury exposure risks of a population living near the largest MSWI in South China, we combined internal exposure and external exposure assessment with an individual–specific questionnaire. The mercury concentrations in air, soil, and locally collected food around the MSWI were assessed. The total mercury (T-Hg) and methylmercury (MeHg) of 447 blood samples from a control group, residential exposure group, and MSWI workers were measured. The internal and external exposures of the subject population were analyzed. Significant difference in MeHg concentrations was observed between the control group and the exposed group, between the control group and the MSWI workers, and between the exposed group and the MSWI workers (median levels: 0.70 μg/L, 0.81 μg/L, and 1.02 μg/L for the control group, exposed group, and MSWI workers, respectively). The MeHg/T-Hg ratio was 0.51 ± 0.19, 0.59 ± 0.17 and 0.58 ± 0.25, respectively. Multiple linear regression analysis indicated that MeHg concentrations were positively correlated with the gaseous mercury in the air. Combining internal and external exposure assessment showed that the direct contribution of MSWI emissions was minor compared with the dietary contribution. The external and internal exposures were well matched with each other. This study also suggested that an integrated method combining internal and external exposure assessment with an individual–specific questionnaire is feasible to assess the risks for a population living near a MSWI.

Evaluation of environmental conditions: air, water and soil in areas of mining activity in Boyacá, Colombia

Objectives To determine concentrations of PM10, mercury and lead in indoor air of homes, water sources and soil in municipalities near mining operations. Method 6 points were evaluated in areas of influence and 2 in control areas. For measurements of indoor air, we used the NIOSH 600 method (PM10), NIOSH 6009 (mercury) and NIOSH 7300 (lead). For water analysis we used the IDEAM Guide for monitoring discharges. For soil analysis, we used the cold vapor technique (mercury) and atomic absorption (lead). Results In almost all selected households, the average PM10 and mercury concentrations in indoor air exceeded applicable air quality standards. Concentrations of lead were below standard levels. In all water sources, high concentrations of lead were found and in some places within the mining areas, high levels of iron, aluminum and mercury were also found. In soil, mercury concentrations were below the detection level and for lead, differences between the monitored points were observed. Conclusions The results do not establish causal relationships between mining and concentration of these pollutants in the evaluated areas because of the multiplicity of sources in the area. However, such studies provide important information, useful to agents of the environmental health system and researchers. Installation of networks for environmental monitoring to obtain continuous reports is suggested.

Elevated Mercury in Ambient Air and Soils Impacts of Historical Air Emissions (1897-1991) from a Chlor-Alkali Plant (CAP)

Mercury contamination was found to be widespread in soils at a property in Upstate New York. Historical site use suggested that the mercury did not result from prior industrial use of the property. Soil contamination may have resulted from atmospheric deposition of mercury released from properties in close proximity to the contaminated property. The purpose of this forensics investigation was to examine to what extent atmospheric deposition of elemental mercury may have influenced mercury levels found in surficial soils on the contaminated property and further to identify the source(s) of the mercury. Work efforts included an examination of historical records available for a chlor-alkali plant (CAP) upwind of the contaminated property to establish historical use and disposal practices for elemental mercury. Mercury emissions test data from the Upstate New York chlor-alkali facility were modeled (USEPA ISC3) as a means of estimating impacts on ambient air and soils vicinal to the facility. Mercury emissions from the facility were modeled as both a point source and volume source. For example, at a location 305 meters to the east and 30 meters to the north of the modeled source centerline elemental mercury concentrations in ambient air were estimated at 270 ng/m3 (average results based upon 5 years of meteorological data). This value is contrasted to a background concentration of 1.6 ng/m3 (USEPA Report to Congress 1997). As a result of the modeling data in combination with findings related to mercury use and disposal practices at the NY CAP documented from the records review, it was concluded that emissions from the CAP facility during the period of operation (1897-1991) most likely accounted for the concentrations of elemental mercury found in surficial soils at properties situated downwind of the CAP. These findings were further corroborated by information available in the open literature for CAPs world-wide.

Who should take responsibility for decisions on internationally recommended datasets? The case of the mass concentration of mercury in air at saturation

This paper considers how decisions on internationally recommended datasets are made and implemented and, further, how the ownership of these decisions comes about. Examples are given of conventionally agreed data and values where the responsibility is clear and comes about through official designation or by common usage and practice over long time periods. The example of the dataset describing the mass concentration of mercury in air at saturation is discussed in detail. This is a case where there are now several competing datasets that are in disagreement with each other, some with historical authority and some more recent but, arguably, with more robust metrological traceability to the SI. Further, it is elaborated that there is no body charged with the responsibility to make a decision on an international recommendation for such a dataset. This has led to the situation where several competing datasets are in use simultaneously. Close parallels are drawn with the current debate over changes to the ozone absorption cross section, which has equal importance to the measurement of ozone amount fraction in air and to subsequent compliance with air quality legislation. It is noted that in the case of the ozone cross section there is already a committee appointed to deliberate over any change. We make the proposal that a similar committee, under the auspices of IUPAC or the CIPM’s CCQM (if it adopted a reference data function) could be formed to perform a similar role for the mass concentration of mercury in air at saturation.

Comparison of mercury concentrations measured at several sites in the Southern Hemisphere

Abstract. Our knowledge of the distribution of mercury concentrations in air of the Southern Hemisphere was until recently based mostly on intermittent measurements made during ship cruises. In the last few years continuous mercury monitoring has commenced at several sites in the Southern Hemisphere, providing new and more refined information. In this paper we compare mercury measurements at several remote sites in the Southern Hemisphere made over a period of at least 1 year at each location. Averages of monthly medians show similar although small seasonal variations at both Cape Point and Amsterdam Island. A pronounced seasonal variation at Troll research station in Antarctica is due to frequent mercury depletion events in the austral spring. Due to large scatter and large standard deviations of monthly average median mercury concentrations at Cape Grim, no systematic seasonal variation could be found there. Nevertheless, the annual average mercury concentrations at all sites during the 2007–2013 period varied only between 0.85 and 1.05 ng m−3. Part of this variability is likely due to systematic measurement uncertainties which we propose can be further reduced by improved calibration procedures. We conclude that mercury is much more uniformly distributed throughout the Southern Hemisphere than the distributions suggested by measurements made onboard ships. This finding implies that smaller trends can be detected in shorter time periods. We also report a change in the trend sign at Cape Point from decreasing mercury concentrations in 1996–2004 to increasing concentrations since 2007.

Effect of atmospheric mercury deposition on selenium accumulation in rice (Oryza sativa L.) at a mercury mining region in southwestern China.

Selenium (Se) is an important trace element for human nutrition and has an interactive effect on mercury (Hg) uptake by plants and Hg toxicity in animals. Rice (Oryza sativa L.) is the dominant source of dietary Se in China, however the effect of soil Hg contamination on the Se concentration in rice is unknown. We collected 29 whole rice plant samples and corresponding soils from an active artisanal mercury mining area and an abandoned commercial mercury mining area. The soil Se concentration was similar across the two mining areas and greater than the background concentration for China. However, the Se concentration in rice grain was dramatically different (artisanal area 51±3 ng g(-1); abandoned area 235±99 ng g(-1)). The total gaseous mercury (TGM) concentration in ambient air at the artisanal mining site was significantly greater than at the abandoned area (231 and 34 ng m(-3), respectively) and we found a negative correlation between TGM and the Se concentration in grain for the artisanal area. Principal component analysis indicated that the source of Se in rice was the atmosphere for the artisanal area (no contribution from soil), and both the atmosphere and soil for the abandoned area. We propose that TGM falls to soil and reacts with Se, inhibiting the translocation of Se to rice grain. Our data suggest that Se intake by the artisanal mining community is insufficient to meet Se dietary requirements, predisposing this community to greater risk from Hg poisoning.

International System of Units Traceable Results of Hg Mass Concentration at Saturation in Air from a Newly Developed Measurement Procedure

Data most commonly used at present to calibrate measurements of mercury vapor concentrations in air come from a relationship known as the "Dumarey equation". It uses a fitting relationship to experimental results obtained nearly 30 years ago. The way these results relate to the international system of units (SI) is not known. This has caused difficulties for the specification and enforcement of limit values for mercury concentrations in air and in emissions to air as part of national or international legislation. Furthermore, there is a significant discrepancy (around 7% at room temperature) between the Dumarey data and data calculated from results of mercury vapor pressure measurements in the presence of only liquid mercury. As an attempt to solve some of these problems, a new measurement procedure is described for SI traceable results of gaseous Hg concentrations at saturation in milliliter samples of air. The aim was to propose a scheme as immune as possible to analytical biases. It was based on isotope dilution (ID) in the liquid phase with the (202)Hg enriched certified reference material ERM-AE640 and measurements of the mercury isotope ratios in ID blends, subsequent to a cold vapor generation step, by inductively coupled plasma mass spectrometry. The process developed involved a combination of interconnected valves and syringes operated by computer controlled pumps and ensured continuity under closed circuit conditions from the air sampling stage onward. Quantitative trapping of the gaseous mercury in the liquid phase was achieved with 11.5 μM KMnO4 in 2% HNO3. Mass concentrations at saturation found from five measurements under room temperature conditions were significantly higher (5.8% on average) than data calculated from the Dumarey equation, but in agreement (-1.2% lower on average) with data based on mercury vapor pressure measurement results. Relative expanded combined uncertainties were estimated following a model based approach. They ranged from 2.2% to 2.8% (k = 2). The volume of air samples was traceable to the kilogram via weighing of water for the calibration of the sampling syringe. Procedural blanks represented on average less than 0.1% of the mass of Hg present in 7.4 cm(3) of air, and correcting for these blanks was not an important source of uncertainty.

A time-dependent risk assessment for broken compact fluorescent lamps.

Environmental Protection Agency (EPA) ambient air quality guidelines are meant to limit long-term exposures of toxins to safe levels. Unfortunately, there is little guidance for what constitutes a safe level from a one-time (or very infrequent) short exposure(s). In the case of mercury, a review of the derivation of the EPA ambient air quality standard shows that it implicitly assumes a tissue burden model. The time dependence of the tissue burden is commonly described in terms of a half-life, a modeling assumption that presumes that the decline in the tissue burden after a single exposure can be approximately described as an exponential decay. In this article, we use a simple exponential tissue burden model to derive a time-dependent no observable adverse effect level (NOAEL) for mercury concentrations in air. The model predicts that tissue body burden will asymptotically approach the EPA air quality level for long exposure times, and reach workplace standard levels for exposures of a few hours. The model was used along with data on mercury levels from experimental work done by the Maine Department of Environmental Protection to evaluate the risks from a broken compact fluorescent lamp in a residential setting. Mercury levels approached the NOAEL only when the debris was left in an almost sealed room. Normal common-sense cleaning measures: removal of debris to an outside area, and ventilation of the room for several minutes, reduced exposures to less than 1% of the NOAEL.

Application of tree rings [dendrochemistry] for detecting historical trends in air Hg concentrations across multiple scales

Tree rings are a useful long term monitor of climate change indicators and certain atmospheric constituents. Since we have no long-term historical record of air mercury (Hg) concentrations, and previous research demonstrates atmospheric uptake of Hg into vegetative biomass, we hypothesized that tree rings would be a useful archive for monitoring changes in local, regional, and global air Hg concentrations. We developed and tested a method for measurement of Hg in tree rings, and then investigated our hypothesis using species within the genus Pinus. Mercury concentrations declined along a coast-to-interior (California-to-Nevada, USA) gradient with highest mean concentrations (5.7 ng/g) at the coast, and lowest (<1.2 ng/g) at inland locations. Tree ring Hg concentrations recorded the impact of local sources and indicate increasing global concentrations over time. The data also indicate that concentrations are higher in areas impacted by marine air, and this suggests that the atmospheric chemistry is influencing assimilation. Future research should address species- and age-specific variation in the sensitivity of tree-ring samples as proxy data for atmospheric Hg concentrations. Tree rings show great potential as passive recorders of atmospheric Hg for long time periods (centuries to millennia) at time steps of ≤5 years.

Evaluating relationships between mercury concentrations in air and in Spanish moss (Tillandsia usneoides L.)

Measurement of mercury vapor is essential given that it is transported globally, and once deposited can be converted to methylmercury, a dangerous neurotoxin. A study was conducted in southeastern Georgia and northern Florida, USA to determine whether Spanish moss, an epiphytic vascular plant common to the southeastern United States, has the ability to retain mercury in its tissues over time, and to detect atmospheric mercury at relatively low concentrations from nonpoint sources. Spanish moss plants exposed to 10× and 100× ambient concentrations of mercury vapor increased tissue concentrations by 13.7±11% and 74.1±17% respectively, and then retained the mercury over two weeks following removal from the source. There was a strong trend of increasing Spanish moss mercury concentrations with increasing air concentration in resident populations across urban, rural inland, coastal and industrial sites. Transplanted Spanish moss around an industrial site contaminated with mercury exhibited a 164.8±8.7% increase in mercury concentration after two weeks. Mercury concentration of Spanish moss transplanted to rural inland sites also increased after two weeks, while the change in transplant concentration at coastal sites was more variable. This study shows that Spanish moss possesses characteristics important for use as a bioindicator of atmospheric mercury, and can potentially be adapted as a tool for obtaining time-integrated atmospheric mercury data to add to existing atmospheric mercury monitoring programs.

Historic Hg Legacy

Environmental Science![Figure][1] CREDIT: CHRIS ECKLEY Industrial operations such as metal smelters and coal-burning power plants release mercury (Hg) into the atmosphere, where it can remain for up to 2 years before it is deposited. Recent efforts to regulate these emissions have led to the Minamata Convention, an international treaty due to be signed in October 2013, which aims to address the toxic effects of mercury in the environment. Yet many aspects of the emission and dispersal of mercury remain unclear. Eckley et al. have undertaken a detailed study of local ground-level air mercury concentrations near the Flin Flon, Manitoba, copper smelter. Until its closure in 2010, this was Canada's largest point source of mercury emissions. The closure provided the opportunity to study atmospheric mercury concentrations before and after the shutdown of a large point source. Although atmospheric mercury concentrations fell after the closure, they remained higher than at other Canadian monitoring stations, both in the atmosphere and in precipitation. Surface-to-air flux from local polluted soils is thus the most likely source of the elevated atmospheric mercury concentrations after closure. Environ. Sci. Technol. 10.1021/es401352n (2013). [1]: pending:yes

Impact of Closing Canada’s Largest Point-Source of Mercury Emissions on Local Atmospheric Mercury Concentrations

The Flin Flon, Manitoba copper smelter was Canada's largest point source of mercury emissions until its closure in 2010 after ~80 years of operation. The objective of this study was to understand the variables controlling the local ground-level air mercury concentrations before and after this major point source reduction. Total gaseous mercury (TGM) in air, mercury in precipitation, and other ancillary meteorological and air quality parameters were measured pre- and postsmelter closure, and mercury speciation measurements in air were collected postclosure. The results showed that TGM was significantly elevated during the time period when the smelter operated (4.1 ± 3.7 ng m(-3)), decreased only 20% during the year following its closure, and remained ~2-fold above background levels. Similar trends were observed for mercury concentrations in precipitation. Several lines of evidence indicated that while smelter stack emissions would occasionally mix down to the surface resulting in large spikes in TGM concentrations (up to 61 ng m(-3)), the largest contributor to elevated TGM concentrations before and after smelter closure was from surface-air fluxes from mercury-enriched soils and/or tailings. These findings highlight the ability of legacy mercury, deposited to local landscapes over decades from industrial activities, to significantly affect local air concentrations via emissions/re-emissions.

Cavity ring-down spectroscopy sensor development for high-time-resolution measurements of gaseous elemental mercury in ambient air

Abstract. We describe further development of a previous laboratory prototype pulsed cavity ring-down spectroscopy (CRDS) sensor into a field-deployable system for high-time-resolution, continuous, and automated measurement of gaseous elemental mercury (GEM) concentrations in ambient air. We employed an external, isotopically enriched Hg cell for automated locking and stabilization of the laser wavelength on the GEM peak absorption during measurements. Further, we describe implementation of differential absorption measurements via a piezoelectric tuning element for pulse-by-pulse tuning of the laser wavelength onto and off of the GEM absorption line. This allowed us to continuously correct (at 25 Hz) for system baseline extinction losses unrelated to GEM absorption. Extensive measurement and calibration data obtained with the system were based on spike addition in both GEM-free air and ambient air. Challenges and interferences that occurred during measurements (particularly in ambient air) are discussed including temperature and ozone (O3) concentration fluctuations, and steps taken to reduce these. CRDS data were highly linear (r2 ≥ 0.98) with data from a commercial Tekran 2537 Hg analyzer across a wide range of GEM concentrations (0 to 127 ng m−3) in Hg-free and ambient air. Measurements during periods of stable background GEM concentrations provided a conservative instrument sensitivity estimate of 0.35 ng m−3 for the CRDS system when time averaged for 5 min. This sensitivity, along with concentration patterns observed in ambient air (with the CRDS system and verified with the Tekran analyzer), showed that the sensor was capable of characterizing GEM fluctuations in ambient air. The value of fast-response GEM measurements was shown by a series of GEM spike additions – highlighting that high-temporal-resolution measurement allowed for detailed characterization of fast concentration fluctuations not possible with traditional analyzers.