A Quantitative Method to Measure the Kinetics of Elemental Mercury Emissions From Black Shale (Nova Scotia, Canada).

A controlled chamber method using continuous gold trap atomic fluorescence spectroscopy (AFS) (Tekran 2537X) for the analysis of Hg(0) emissions from moderate mass rock samples was developed and tested. A series of black shale and other bedrock samples from Nova Scotia, Canada, were used to test the method and its reproducibility. Hg(0) emissions at 170°C were measured to quantify both free surficial Hg(0) and Hg(0) that had penetrated the rock structure. High volumes of chamber air (45 L) were sampled using 30 min collection times to achieve detectable elemental mercury (Hg(0)) emissions. We found higher percentage masses of Hg(0) were released (1.1%-4.1% of total Hg mass present) in black shale samples as compared to granite and basalt samples from the same region (0.0%-0.3% released) over 350 h of continuous analysis time. The pseudo first order emission rate constants ranged from 0.015-0.245 h-1 (mean 0.063 h-1, standard deviation (SD) 0.102) for the black shale samples analyzed and was 0.004 h-1 for the granite sample. The 24-h zero-order emission rate constants ranged between 0.41 and 3.54 ng h-1 (mean 1.4 ng h-1, SD 1.3) for the black shale samples analyzed and were ~ 0.01 ng h-1 for the granite and basalt samples. This technique has useful implications for examining rock properties and Hg(0) emission rates.

Temporal Changes in Photoreducible Mercury, Photoreduction Rates, and the Role of Dissolved Organic Matter in Freshwater Lakes.

Total photoreducible mercury [Hg(II)RED] and photoreduction rates in the surface waters of four lakes in Kejimkujik National Park, Nova Scotia were measured monthly over a summer. The percent of THg that was photoreducible [%Hg(II)RED] decreased significantly in two of the four lakes from early to late summer: North Cranberry (maximum 42% to minimum 14%) and Big Dam East (maximum 51% to minimum 6%). Hg(II)RED was found to have a linear relationship with THg for all combined site data. THg and Hg(II)RED were found to have positive linear relationships with DOC concentrations (R2 = 0.97; n = 36; p < 0.01 and R2 = 0.75; n = 36; p < 0.01, respectively). A smaller proportion of THg was found to be photoreducible with increasing DOC concentration.

Total mercury, methylmercury, phosphate, and sulfate inputs to a bog ecosystem from herring gull (Larus smithsoniansus) guano.

Avian biovector transport is an important mechanism for the movement of contaminants and nutrients to remote locations, usually bird colonies, through excretion, molting and decomposition of carcasses. Methylmercury (MeHg) is a bioaccumulative neurotoxin and endocrine disruptor which is present in many remote ecosystems. We collected guano samples biweekly from a herring gull (Larus smithsoniansus) colony over two summers and analyzed MeHg, total mercury (THg), water-extractable phosphate (PO43-) and sulfate (SO42-). Concentrations of THg in guano declined through the summer months while %MeHg significantly increased (ranging from 12% to 100% of THg), suggesting a switch in diet as gull nutritional needs or food availability changed through the summer. The percentage of PO43- in dry guano increased throughout the summer (ranging from 2.8% to 4.4% of dry weight) and SO42- varied throughout the season (ranging from 0.1% to 0.8% of dry weight). These data indicate that gulls are transporting considerable amounts of MeHg, PO43-, and likely other contaminants to Big Meadow Bog, Nova Scotia.

Increasing chloride concentration causes retention of mercury in melted Arctic snow due to changes in photoreduction kinetics.

Mercury (Hg) in the Arctic is a significant concern due to its bioaccumulative and neurotoxic properties, and the sensitivity of Arctic environments. Previous research has found high levels of Hg in snowpacks with high chloride (Cl-) concentrations. We hypothesised that Cl- would increase Hg retention by decreasing Hg photoreduction to Hg(0) in melted Arctic snow. To test this, changes in Hg photoreduction kinetics in melted Alert, NU snow were quantified with changing Cl- concentration and UV intensity. Snow was collected and melted in Teflon bottles in May 2014, spiked with 0-10µg/g Cl-, and irradiated with 3.52-5.78W·m-2 UV (280-400nm) radiation in a LuzChem photoreactor. Photoreduction rate constants (k) (0.14-0.59hr-1) had positive linear relationships with [Cl-], while photoreduced Hg amounts (Hg(II)red) had negative linear relationships with [Cl-] (1287-64pg in 200g melted snow). Varying UV and [Cl-] both altered Hg(II)red amounts, with more efficient Hg stabilisation by Cl- at higher UV intensity, while k can be predicted by Cl- concentration and/or UV intensity, depending on experimental parameters. Overall, with future projections for greater snowpack Cl- loading, our experimental results suggest that more Hg could be delivered to Arctic aquatic ecosystems by melted snow (smaller Hg(II)red expected), but the Hg in the melted snow that is photoreduced may do so more quickly (larger k expected).

Mercury in Arctic snow: quantifying the kinetics of photochemical oxidation and reduction.

Controlled experiments were performed with frozen and melted Arctic snow to quantify relationships between mercury photoreaction kinetics, ultra violet (UV) radiation intensity, and snow ion concentrations. Frozen (-10°C) and melted (4°C) snow samples from three Arctic sites were exposed to UV (280-400 nm) radiation (1.26-5.78 W · m(-2)), and a parabolic relationship was found between reduction rate constants in frozen and melted snow with increasing UV intensity. Total photoreduced mercury in frozen and melted snow increased linearly with greater UV intensity. Snow with the highest concentrations of chloride and iron had larger photoreduction and photooxidation rate constants, while also having the lowest Hg(0) production. Our results indicate that the amount of mercury photoreduction (loss from snow) is the highest at high UV radiation intensities, while the fastest rates of mercury photoreduction occurred at both low and high intensities. This suggests that, assuming all else is equal, earlier Arctic snow melt periods (when UV intensities are less intense) may result in less mercury loss to the atmosphere by photoreduction and flux, since less Hg(0) is photoproduced at lower UV intensities, thereby resulting in potentially greater mercury transport to aquatic systems with snowmelt.

Dissolved gaseous mercury concentrations and mercury volatilization in a frozen freshwater fluvial lake.

In situ mesocosm experiments were performed to examine dissolved gaseous mercury (DGM), mercury volatilization, and sediment interactions in a frozen freshwater fluvial lake (Lake St. Louis, Beauharnois, QC). Two large in situ mesocosm cylinders, one open-bottomed and one close-bottomed (no sediment diffusion), were used to isolate the water column and minimize advection. Mercury volatilization over the closed-bottom mesocosm did not display a diurnal pattern and was low (mean = -0.02 ng m(-2) h(-1), SD = 0.28, n=71). Mercury volatilization over the open-bottom mesocosm was also low (mean = 0.24 ng m(-2) h(-1), SD = 0.08, n=96) however a diurnal pattern was observed. Low and constant concentrations of DGM were observed in surface water in both the open-bottomed and close-bottomed mesocosms (combined mean = 27.6 pg L(-1), SD = 7.2, n=26). Mercury volatilization was significantly correlated with solar radiation in both the close-bottomed (Pearson correlation = 0.33, significance = 0.005) and open-bottomed (Pearson correlation = 0.52, significance = 0.001) mesocosms. However, DGM and mercury volatilization were not significantly correlated (at the 95% level) in either of the mesocosms (significance = 0.09 in the closed mesocosm and significance = 0.9 in the open mesocosm). DGM concentrations decreased with depth (from 62 to 30 pg L(-1)) in the close-bottomed mesocosm but increased with depth (from 30 to 70 pg L(-1)) in the open-bottomed mesocosm suggesting a sediment source. DGM concentrations were found to be high in samples of ice melt (mean 73.6 pg L(-1), SD = 18.9, n=6) and snowmelt (mean 368.2 pg L(-1), SD = 115.8, n=4). These results suggest that sediment diffusion of mercury and melting snow and ice are important to DGM dynamics in frozen Lake St. Louis. These processes may also explain the lack of significant correlations observed in the DGM and mercury volatilization data.

Continuous analysis of dissolved gaseous mercury and mercury volatilization in the upper St. Lawrence River: exploring temporal relationships and UV attenuation.

The formation and volatilization of dissolved gaseous mercury (DGM) is an important mechanism by which freshwaters may naturally reduce their mercury burden. Continuous analysis of surface water for diurnal trends in DGM concentration (ranging from 0 to 60.4 pg L(-1); n=613), mercury volatilization (ranging from 0.2 to 1.1 ng m(-2) h(-1); n=584), and a suite of physical and chemical measurements were performed during a 68 h period in the St. Lawrence River near Cornwall (Ontario, Canada) to examine the temporal relationships governing mercury volatilization. No lag-time was observed between net radiation and OGM concentrations (highest cross-correlation of 0.817), thus supporting previous research indicating faster photoreduction kinetics in rivers as compared to lakes. A significant lag-time (55-145 min; maximum correlation = 0.625) was observed between DGM formation and mercury volatilization, which is similar to surface water Eddy diffusion times of 42-132 min previously measured in the St. Lawrence River. A depth-integrated DGM model was developed using the diffuse integrated vertical attenuation coefficients for UVA and UVB (K(dI UVA) = 1.45 m(-1) K(dI UVB)= 3.20 m(-1)) Low attenuation of solar radiation was attributed to low concentrations of dissolved organic carbon (mean = 2.58 mg L(-1) and particulate organic carbon (mean = 0.58 mg L(-1) in the St. Lawrence River. The depth-integrated DGM model developed found that the top 0.3 m of the water column accounted for only 26% of the total depth-integrated DGM. A comparison with volatilization data indicated that a large portion (76% or 10.5 ng m(-2) of the maximum depth-integrated DGM (13.8 ng m(-2))is volatilized over a 24 h period. Therefore, at least 50% of all DGM volatilized was produced at depths below 0.3 m. These results highlight the importance of solar attenuation in regulating DGM formation with depth. The results also demonstrate both the fast formation of DGM in rivers and the importance of understanding DGM dynamics with depth as opposed to surface waters.

Gross photoreduction kinetics of mercury in temperate freshwater lakes and rivers: application to a general model of DGM dynamics.

Previous published measurements of mercury photoreduction are for net-photoreduction, since photooxidation processes occur simultaneously. In this research we combine continuous dissolved-gaseous mercury (DGM) analysis with a photoreactor and a quartz sparger in order to derive mercury gross photoreduction rate constants for UVB and UVA irradiations. The DGM concentration in each filter-sterilized freshwater was measured at 5 min intervals over a period of 23 h. Photoreduction proceeded for the initial 200 min, after which, reducible mercury was depleted in the sample. Substantial losses in DOC fluorescence were observed during the incubations for UVA radiation but not for UVB; therefore, UVB photoreduction dynamics are not linked to a loss in DOC fluorescence. Pseudo first-order reaction kinetics fit the data well (r2 > 0.87). The rate constants appear divided between lakes and rivers with the mean lake UVB rate constant (kUVB = 8.91 x 10(-5) s(-1)), significantly less than the mean rate constant (kUVB = 1.81 x 10(-4) s(-1)) for the river samples. However, while there were differences for the UVB rates between lakes and rivers, the mean and median rate constants for UVA in lakes (kUVA = 7.76 x 10(-5) s(-1)) did not differ significantly from the mean rate constant forthe river sites (kUVA = 1.78 x 10(-4) s(-1)). Here, we propose a model for mercury photoredox dynamics for both temperate lake and river systems. The lake model was validated using principal axis analysis to compare observed and predicted DGM data (n=279) from a variety of lake sites in Nova Scotia and Central Quebec. Principal axis analysis found a linear fit (correlation = 0.81; slope = 2.13) between predicted and observed environmental DGM values when log-normalized. The constant bias on the predicted values was attributed to estimates of available reducible mercury and the effect of DGM volatilization on observed data.

The influence of forestry activity on the structure of dissolved organic matter in lakes: implications for mercury photoreactions.

It is well known that dissolved organic matter (DOM) increases in lakes associated with forestry activity but characterization of the DOM structure is incomplete. Twenty-three lakes with a wide range of forestry activities located in central Quebec, Canada were sampled and analyzed for dissolved organic carbon (DOC) concentration, DOC fluorescence, and ultra violet-visible (UV-VIS) absorption spectra. The results show that DOC increases (as does the associated DOC fluorescence) with increased logging (slope=0.122, r2=0.581, p<0.001; and slope=0.283, r2=0.308, p<0.01, respectively) in the 23 lakes sampled however, the aromaticity of the DOM does not change with changes in logging (as found by UV-VIS ratios, absorbance slope in the UV region, and DOC normalized fluorescence (slope=1.42x10(-2), r2=0.331, p<0.01). The DOM from four of these lakes was concentrated using reverse osmosis (RO) followed by freeze-drying. The structures of the concentrated dissolved organic matter (DOM) samples were analyzed using X-ray analysis of near edge structures (XANES), X-ray diffraction (XRD), and 13C solid-state nuclear magnetic resonance (13C NMR) analysis. XANES analysis of functional groups in the four concentrated samples shows that there are significant differences in reduced sulphur between the samples, however there was no clear relationship with forestry activity in the associated catchment. XRD data showed the presence of amorphous sulphide minerals associated with the DOM concentrate that may be important sites for mercury binding. The 13C NMR spectra of these samples show that the percentage of carbon present in carboxylic functional groups increases with increasing logging. Such structures are important for binding photo-reducible mercury and their presence may limit mercury photo-reduction and volatilization. We propose a mechanism by which increased logging leads to increased carboxylic groups in DOM and thereby increased weak binding of photo-reducible mercury. These results, in part, explain the decrease in dissolved gaseous mercury (DGM) production rates with increased logging found in our previous work.

Effect of dissolved organic carbon on the photoproduction of dissolved gaseous mercury in lakes: potential impacts of forestry.

The production of dissolved gaseous mercury (DGM) in freshwater lakes is induced by solar radiation and is also thought to be linked to processes mediated by dissolved organic carbon (DOC). Studies investigating these processes using comparisons between lakes are often confounded by differences in DOC content and structure. In this study, we investigated the link between DOC concentrations and DGM production by using tangential ultrafiltration to manipulate DOC concentrations in water samples taken from a given lake. In this way, a range of samples with different DOC concentrations was produced without substantial changes to DOC structure or dissolved ions. This was repeated for four lakes in central Quebec: two with highly logged drainage basins and two with minimally logged drainage basins. On two separate days for each lake, water samples (filtered to remove >99% of microorganisms) with varying DOC concentrations were incubated in clear and dark Teflon bottles on the lake surface. DGM concentrations were measured at 3.5-h intervals over the course of 10.5 h. Levels of DGM concentrations increased with increasing cumulative irradiation for all lakes until approximately 4000 kJ m(-2) (400-750 nm, photosynthetically active radiation (PAR)), when DGM concentrations reached a plateau (between 20 and 200 pg L(-1)). When we assumed that DGM production was limited by the amount of photoreducible mercury, reversible first-order reaction kinetics fitted the observed data well (r2 ranging between 0.59 and 0.98, p < 0.05 with the exception of N70 100% DOC, 0% DOC, and K2 0% DOC with p = 0.06, 0.10, and 0.11, respectively). The DGM plateaus were independent of DOC concentrations but differed between lakes. In contrast, photoproduction efficiency (DGMprod) (i.e., the amount of DGM produced per unit radiation (fg L(-1) (kJ/m2)(-1)) below 4000 kJ m(-2) PAR) was linearly proportional to DOC concentration for both logged lakes (r2 = 0.97, p < 0.01) and nonlogged lakes (r2 = 0.52, p = 0.018) studied. Furthermore, logged lakes had a lower DGMprod per unit DOC (p < 0.01) than the nonlogged lakes. In these four lakes, the rate of DGM production per unit PAR was dependent on the concentration of DOC. The DGM plateau was independent of DOC concentration; however, there was a significant difference in DGM plateaus between lakes presumably due to different DOC structures and dissolved ions. This research demonstrates an important mechanism by which logging may exacerbate mercury levels in biota.

Continuous analysis of dissolved gaseous mercury in freshwater lakes.

The concentration of dissolved gaseous mercury (DGM) in freshwaters changes more quickly than the 40-min processing time of current analytical methods. A new method for continuous field analysis of DGM was developed using a Tekran 2537A to achieve a DGM analysis time of 5 min. Samples were concurrently analyzed for temperature, oxygen, conductivity, pH, and oxidation-reduction potential using a Hydrolab. The detection limit for DGM ranged between 5 and 20 fmolL(-1) with 99% removal efficiency. Control experiments showed that there was no interference due to methyl mercury, which is present in similar concentrations to DGM. Controlled experiments comparing continuous DGM analysis with discrete DGM analysis showed that the results are not significantly affected by typical variations in water temperature (4-30 degrees C), oxidation-reduction potential (135-355 mV), dissolved organic carbon (4.5-10.5 mgL(-1)), or pH (3.5-7.8). The continuous analysis was within 4.5% of the discrete analysis when compared across 12 samples analyzed in triplicate. The field performance of this method was tested over two 48-h periods in two lakes in Kejimkujik Park, Nova Scotia where over 1000 data points were collected.