Dissolved Gaseous Mercury Production Research Articles

Dissolved gaseous mercury production and sea-air gaseous exchange in impacted coastal environments of the northern Adriatic Sea

The northern Adriatic Sea is well known for mercury (Hg) contamination mainly due to historical Hg mining which took place in Idrija (Slovenia). The formation of dissolved gaseous mercury (DGM) and its subsequent volatilisation can reduce the amount of Hg available in the water column. In this work, the diurnal patterns of both DGM production and gaseous elemental Hg (Hg0) fluxes at the water-air interface were seasonally evaluated in two selected environments within this area, a highly Hg-impacted, confined fish farm (VN: Val Noghera, Italy) and an open coastal zone less impacted by Hg inputs (PR: Bay of Piran, Slovenia). A floating flux chamber coupled with a real-time Hg0 analyser was used for flux estimation in parallel with DGM concentrations determination through in-field incubations. Substantial DGM production was observed at VN (range = 126.0–711.3 pg L−1) driven by both strong photoreduction and possibly dark biotic reduction, resulting in higher values in spring and summer and comparable concentrations throughout both day and night. Significantly lower DGM was observed at PR (range = 21.8–183.4 pg L−1). Surprisingly, comparable Hg0 fluxes were found at the two sites (range VN = 7.43–41.17 ng m−2 h−1, PR = 0–81.49 ng m−2 h−1), likely due to enhanced gaseous exchanges at PR thanks to high water turbulence and to the strong limitation of evasion at VN by water stagnation and expected high DGM oxidation in saltwater. Slight differences between the temporal variation of DGM and fluxes indicate that Hg evasion is more controlled by factors such as water temperature and mixing conditions than DGM concentrations alone. The relative low Hg losses through volatilisation at VN (2.4–4.6% of total Hg) further confirm that static conditions in saltwater environments negatively affect the ability of this process in reducing the amount of Hg retained in the water column, therefore potentially leading to a greater availability for methylation and trophic transfer.

Gaseous Mercury Exchange from Water-Air Interface in Differently Impacted Freshwater Environments.

Gaseous exchanges of mercury (Hg) at the water–air interface in contaminated sites strongly influence its fate in the environment. In this study, diurnal gaseous Hg exchanges were seasonally evaluated by means of a floating flux chamber in two freshwater environments impacted by anthropogenic sources of Hg, specifically historical mining activity (Solkan Reservoir, Slovenia) and the chlor-alkali industry (Torviscosa dockyard, Italy), and in a pristine site, Cavazzo Lake (Italy). The highest fluxes (21.88 ± 11.55 ng m−2 h−1) were observed at Solkan, coupled with high dissolved gaseous mercury (DGM) and dissolved Hg (THgD) concentrations. Conversely, low vertical mixing and saltwater intrusion at Torviscosa limited Hg mobility through the water column, with higher Hg concentrations in the deep layer near the contaminated sediments. Consequently, both DGM and THgD in surface water were generally lower at Torviscosa than at Solkan, resulting in lower fluxes (19.01 ± 12.65 ng m−2 h−1). However, at this site, evasion may also be limited by high atmospheric Hg levels related to dispersion of emissions from the nearby chlor-alkali plant. Surprisingly, comparable fluxes (15.56 ± 12.78 ng m−2 h−1) and Hg levels in water were observed at Cavazzo, suggesting a previously unidentified Hg input (atmospheric depositions or local geology). Overall, at all sites the fluxes were higher in the summer and correlated to incident UV radiation and water temperature due to enhanced photo production and diffusivity of DGM, the concentrations of which roughly followed the same seasonal trend.

Enhanced mercury reduction in the South Atlantic Ocean during carbon remineralization

Mercury (Hg) in seawater is subject to interconversions via (photo)chemical and (micro)biological processes that determine the extent of dissolved gaseous mercury (DGM) (re)emission and the production of monomethylmercury. We investigated Hg speciation in the South Atlantic Ocean on a GEOTRACES cruise along a 40°S section between December 2011 and January 2012 (354 samples collected at 24 stations from surface to 5250 m maximum depth). Using statistical analysis, concentrations of methylated mercury (MeHg, geometric mean 35.4 fmol L−1) were related to seawater temperature, salinity, and fluorescence. DGM concentrations (geometric mean 0.17 pmol L−1) were related to water column depth, concentrations of macronutrients and dissolved inorganic carbon (DIC). The first-ever observed linear correlation between DGM and DIC obtained from high-resolution data indicates possible DGM production by organic matter remineralization via biological or dark abiotic reactions. DGM concentrations projected from literature DIC data using the newly discovered DGM–DIC relationship agreed with published DGM observations.

Spatial Differences and Influencing Factors of Dissolved Gaseous Mercury in the Yellow Sea and Bohai Sea in Spring

From 28 March to 17 April, 2018, different forms of mercury (Hg) in the Yellow Sea and Bohai Sea were measured to study the influencing factors on the distribution and transformation of Hg in spring using a shared cruise. The mean concentration of dissolved gaseous mercury (DGM) in the surface water of the Yellow and Bohai Seas was (44.3 ± 43.9) pg/L, which was close to that in mid-latitude oceans and deep seas. The ratio of DGM to THg (total mercury) was lower than in the oceans and in the Yellow and Bohai Seas in summer or fall. DGM concentrations in surface water were highest in the central part of the South Yellow Sea and were higher than those in the Bohai Sea, and their spatial distributions were consistent with RHg (reactive mercury). DGM and RHg correlated positively with water temperature in surface seawater (r = 0.506, P < 0.01; r = 0.278, P < 0.05). The concentrations of both DGM and RHg in surface water were controlled by solar radiation and water temperature. Foggy weather did not benefit the production of DGM and RHg. DGM in the bottom seawater was mainly affected by Dissolved Oxygen and water temperature (r = −0.366, P < 0.01; r = 0.331, P < 0.01), produced mainly by anaerobic reactions of the bottom seawater and sediment microorganisms. The bottom DGM concentrations in the Yellow and Bohai Seas were the highest, and DGM produced in bottom seawater and sediment plays a more important role than the surface water in spring. The concentrations of DGM and RHg in the surface and bottom water in the South Yellow Sea were all higher than those in the middle layer. Vertical variations in the North Yellow Sea and the Bohai Sea were small. The production and distribution of DGM and RHg were influenced by differences of latitude and by the Yellow Sea warm current in spring.

Dissolved Gaseous Mercury Production at a Marine Aquaculture Site in the Mercury-Contaminated Marano and Grado Lagoon, Italy.

Dissolved gaseous mercury (DGM) production was examined in relation to ultraviolet radiation within a marine aquaculture site in the contaminated Marano and Grado Lagoon (Italy). The measured rates of DGM production relative to time elapsed (17.06 and 20.68pgh-1, respectively) were substantially (6-20 times) higher than what has been observed in other marine Hg studies. We measured similar levels of DGM relative to dissolved total mercury (THgD) (0.84%-8.91%) at these sites in comparison to uncontaminated marine sites, however relative to other moderately-contaminated marine sites in Portugal the % DGM/THgD was high. These results suggest a substantial capacity for Hg volatilization from these highly contaminated lagoons to the atmosphere due to photoreduction mechanisms.

Relations between mercury fractions and microbial community components in seawater under the presence and absence of probable phosphorus limitation conditions

Microbial transformations of toxic monomethylmercury (MMHg) and dissolved gaseous mercury (DGM) at the lower levels of the marine food web are not well understood, especially in oligotrophic and phosphorus-limited seas. To examine the effects of probable phosphorus limitation (PP-limitation) on relations between mercury (Hg) fractions and microorganisms, we determined the total mercury (THg), total methylated mercury (MeHg), DGM, and microbiological and chemical parameters in the Central Adriatic Sea. Using statistical analysis, we assessed the potential microbial effects on Hg transformations and bioaccumulation. Only in the absence of PP-limitation conditions (NO–PP-limitation) is MeHg significantly related to most chemical and microbial parameters, indicating metabolism-dependent Hg transformations. The heterotrophic activity of low nucleic acid bacteria (abundant in oligotrophic regions) seems responsible for most of Hg methylation under NO–PP-limitation. Under these conditions, DGM is strongly related to microbial fractions and chlorophyll a, indicating biological DGM production, which is probably not metabolically induced, as most of these relations are also observed under PP-limitation. MMHg biomagnification was observed through an increased bioaccumulation factor from microseston to mesozooplankton. Our results indicate that Hg transformations and uptake might be enhanced under NO–PP-limitation conditions, emphasizing their impact on the transfer of Hg to higher trophic levels.

Dissolved gaseous mercury formation and mercury volatilization in intertidal sediments

Intertidal sediments of Tagus estuary regularly experiences complex redistribution due to tidal forcing, which affects the cycling of mercury (Hg) between sediments and the water column. This study quantifies total mercury (Hg) and methylmercury (MMHg) concentrations and fluxes in a flooded mudflat as well as the effects on water-level fluctuations on the air-surface exchange of mercury. A fast increase in dissolved Hg and MMHg concentrations was observed in overlying water in the first 10min of inundation and corresponded to a decrease in pore waters, suggesting a rapid export of Hg and MMHg from sediments to the water column. Estimations of daily advective transport exceeded the predicted diffusive fluxes by 5 orders of magnitude. A fast increase in dissolved gaseous mercury (DGM) concentration was also observed in the first 20–30min of inundation (maximum of 40pg L−1). Suspended particulate matter (SPM) concentrations were inversely correlated with DGM concentrations. Dissolved Hg variation suggested that biotic DGM production in pore waters is a significant factor in addition to the photochemical reduction of Hg. Mercury volatilization (ranged from 1.1 to 3.3ngm−2h−1; average of 2.1ngm−2h−1) and DGM production exhibited the same pattern with no significant time-lag suggesting a fast release of the produced DGM. These results indicate that Hg sediment/water exchanges in the physical dominated estuaries can be underestimated when the tidal effect is not considered.

Effect on the Photo-production of Dissolved Gaseous Mercury in Post-desulfurized Seawater Discharged from a Coal-Fired Power Plant

A high concentration of dissolved gaseous mercury (DGM) was detected in post-desulfurized waste seawater, which was discharged from a coal-fired power plant equipped with a seawater desulfurization system and which was located in a coastal area. A large amount of DGM was converted from other forms of mercury during transformation processes, such as photo-reduction. The present study targeted the photo-reduction of mercury and the effects of various environmental parameters on DGM production in the post-desulfurized seawater discharged. The results suggested that the photo-reduction of mercury was significantly induced under UV radiation, especially with UVB. The particulate mercury on suspended solids was easily photo-reduced and considered as an important source of DGM. It was confirmed that the suspended solids in post-desulfurized seawater could enhance the reduction process of mercury under UV radiation. The pseudo-first-order rate constants of DGM production, which were determined through the concentration gradient and trial methods, were 1.39 × 10−3 min−1 and 1.45 × 10−3 min−1, respectively. The values showed no significant difference and were both much higher than the reported results, indicating that the photo-reduction of mercury in post-desulfurized seawater deserved more attention. In addition, the initial mercury level was observed when mixing the post-desulfurized seawater with fresh seawater, and this suggested that a significant amount of initial mercury would be produced when the post-desulfurized seawater was discharged into the adjacent sea area and thus becomes another considerable source of DGM.

Intracellular speciation and transformation of inorganic mercury in marine phytoplankton

Metal speciation is closely related to toxicity in aquatic organisms, but quantitative study of mercury transformation has rarely been reported. In this study, the ability of three marine phytoplankton species, including a green alga Chlorella autotrophica, a flagellate Isochrysis galbana and a diatom Thalassiosira weissflogii, to convert inorganic mercury were examined. We found that all algae tested were able to transform Hg(II) into dissolved gaseous mercury (DGM), phytochelatin (PC) complexes and metacinnabar (β-HgS). The most tolerant species, T. weissflogii, generally produced the highest level of PCs and β-HgS. Attributed to the highest DGM production ability, C. autotrophica accumulated the least Hg, but was the most sensitive due to low PC induction and β-HgS formation. Of the added Hg(II), less than 5% was reduced to DGM per day in all species. Of the intracellular Hg, <20% and 20–90% were chelated by PCs and transformed into β-HgS, respectively. These results suggest that intracellular biotransformation might be more important than bioavailability regulation in Hg(II) detoxification in marine phytoplankton.

Distribution and production of reactive mercury and dissolved gaseous mercury in surface waters and water/air mercury flux in reservoirs on Wujiang River, Southwest China

Transformation and distribution of mercury (Hg) species play an important role in the biogeochemical cycling of mercury in aquatic systems. Measurements of water/air exchange fluxes of Hg, reactive mercury (RHg), and dissolved gaseous mercury (DGM) concentrations were conducted at 14 sites in five reservoirs on the Wujiang River, Guizhou, Southwest China. Clear spatial and temporal variations in Hg fluxes, RHg, and DGM concentrations were observed in the study area. Hg fluxes and RHg concentrations exhibited a consistent diurnal variation in the study area, with maximum fluxes and concentrations during daytime. A typical diurnal trend of DGM with elevated concentration at night was observed in a eutrophic reservoir with elevated bacteria abundance, suggesting a bacteria‐induced production of DGM in this reservoir. For other reservoirs, a combination of sunlight‐stimulated production and loss via photo‐induced oxidation and evaporation regulated the diurnal trends of DGM. Seasonal variations with elevated Hg fluxes and RHg concentrations in warm season were noticeable in the study area, which highlighted the combined effect of interrelationships between Hg species in water and environmental parameters. Hg fluxes exhibited much more significant correlations with RHg and THg concentrations and air temperature compared to DGM concentrations and solar radiation. The measured fluxes were significantly higher than those simulated using the water/air thin film Hg0 gradient model. Aside from the potential limitations of dynamic flux chamber method, this may also suggest the thin film gas exchange model is not capable of predicting water/air Hg flux under low wind speed conditions. Additionally, it is speculated that DGM concentrations might vary significantly in surface waters with depth, and measurements of DGM at a depth of 2–4 cm below the water surface probably underestimated the DGM concentration that should be taken into account in simulations of water/air flux using the thin film gas exchange model. An empirical model of water/air Hg flux was developed, and the simulated fluxes were compared well with measurements. The model yields a mean annual Hg emission of 3.2 ± 1.0 kg in the study area.

Effect of Abiotic and Biotic Factors on the Photo-Induced Production of Dissolved Gaseous Mercury

This study was conducted to evaluate the contribution of environmental factors such as solar radiation and dissolved organic matter (DOM) on the photo-induced dissolved gaseous mercury (DGM) production through laboratory experiments using field water samples collected from wetlands. DGM production was more significantly influenced by UVB intensity than UVA. DGM formation was also significantly affected by DOM chemical structure/composition rather than its concentration. Increasing NO3− concentration limited DGM production, but photo-induced Hg oxidation stimulated by NO3− would possibly occur when the NO3− level is more than twice the DOC level. The addition of phosphorus into the field water samples induced a slight increase of DGM production; however, the addition of nitrogen decreased DGM formation, suggesting that an increase of limiting nutrients in water may promote biotic DGM production. Experiments using a Selenastrum capricornutum monoculture solution showed that cell density had a positive effect on DGM production. Moreover, the difference in DGM production between filtered and unfiltered samples showed that S. capricornutum significantly produced biotic DGM under UVA irradiation. Finally, our results imply that environmental factors such as light intensity, DOM sources, and site-specific microorganisms can significantly affect photo-induced Hg transformation.

Changes in the non-protein thiol pool and production of dissolved gaseous mercury in the marine diatom Thalassiosira weissflogii under mercury exposure

Two detoxification mechanisms working in the marine diatom Thalassiosira weissflogii to cope with mercury toxicity were investigated. Initially, the effect of mercury on the intracellular pool of non-protein thiols was studied in exponentially growing cultures exposed to sub-toxic HgCl 2 concentrations. T. weissflog ii cells responded by synthesizing metal-binding peptides, named phytochelatins (PCs), besides increasing the intracellular pool of glutathione and γ-glutamylcysteine (γ-EC). Intracellular Hg and PC concentrations increased with the Hg concentration in the culture medium, exhibiting a distinct dose–response relationship. However, considerations of the PCs-SH:Hg molar ratio suggest that glutathione could also be involved in the intracellular mercury sequestration. The time course of the non-protein thiol pool and Hg intracellular concentration shows that PCs, glutathione and γ-EC represent a rapid cellular response to mercury, although their role in Hg detoxification seems to lose importance at longer incubation times. The occurrence of a process of reduction of Hg(II) to Hg° and subsequent production of dissolved gaseous mercury (DGM) was also investigated at lower Hg concentrations, at which the PC synthesis doesn't seem to be involved. The significant ( P < 0.01) correlation between the cellular density in solution and the production of DGM suggests that this diatom is capable of directly producing DGM, both in light and dark conditions. This finding has been confirmed by the absence of DGM production in the culture media containing formaldehyde-killed cells. Finally, the relationship between these two different pathways of Hg detoxification is discussed.

Gaseous mercury at the air–water interface of a highly turbid estuary (Gironde Estuary, France)

The present work aims at better understanding dissolved gaseous Hg production and dynamics in surface water of highly turbid estuaries, where light penetration and photochemical processes in the maximum turbidity zone (MTZ) are very limited. Measurements of dissolved gaseous mercury (DGM) and total gaseous mercury (TGM) in surface water of the MTZ and at the mouth of the Gironde Estuary were carried out at different seasons. Diurnal cycles of DGM concentrations in surface water at both sites, showing variations by a factor of up to 60, may be attributed to photoreduction of Hg(II) by solar radiation. During low-turbidity situations at the estuary mouth, DGM concentrations paralleled the daily evolution of solar radiation. Under highly turbid conditions, DGM concentrations paralleled the daily evolution of the ratio between solar radiation and suspended particulate matter concentrations (rad/SPM) in surface water (~ 200–2000 mg L − 1 ), rather than solar radiation level alone. These results clearly suggest that high SPM levels may constitute an important factor influencing the DGM production in surface water by limiting light penetration. Despite of the generally very high SPM levels in the Gironde estuary, seasonal trends in maximum daily DGM concentrations, saturation and fluxes to the atmosphere were observed. Surface water appeared to be Hg super-saturated most of the time, especially during high radiation periods (300–1500%; May and July) resulting in Hg evasion. However, saturation levels down to 10% were observed during the night and even during the day in winter, when rad/SPM was sufficiently low. Under these conditions, Hg flux from atmosphere to the under saturated surface water may occur. Most of the year, hourly fluxes of Hg° from water to the atmosphere were positive during the day (up to 0.064 nmol m − 2 h − 1 ; 12.8 ng m − 2 h − 1 ) and were negative during the night, but in winter they were negative during the whole diurnal cycle (− 0.01 nmol m − 2 h − 1 ; − 2 ng m − 2 h − 1 ). Integration of the hourly fluxes over 24 h for the different campaigns, and extrapolation to the whole estuary scale suggest that the Gironde Estuary constitutes a Hg° net source to atmosphere during most of the year, with an annual Hg° net flux of ~ 22 mol y − 1 . However, this net Hg° flux may probably be counterbalanced by (dry + wet) Hg deposition.

Dissolved gaseous mercury production in the dark: Evidence for the fundamental role of bacteria in different types of Mediterranean water bodies

It is well established that the dissolved gaseous mercury (DGM) production in waters is mainly driven by photochemical processes. The present paper provides evidence for a significant bacteria-mediated DGM production, occurring also under dark conditions in environmentally different types of coastal water bodies of the Mediterranean basin. The DGM production was laboratory determined in sea, lagoon-brackish and lake water samples, comparing the efficiency of the DGM production processes in darkness and in the light. This latter condition was established by exposing samples at solar radiation intensity in the Photosyntetical Active Radiation region (PAR) of 200 W m − 2 . Mercury reduction rate in the dark was of the order of 2–4% of the DGM production in lightness, depending on the total mercury concentration in the water, rather than the bacterial abundance in it. Support for the active bacterial role in mercury reduction rate under dark conditions was provided by: 1) absence of significant DGM production in sterilized water samples (following filtration treatment or autoclaving), 2) restored DGM production efficiency, following re-inoculation into the same water samples of representatives of their bacterial community, previously isolated and separately cultured. Notwithstanding the low bacteria-mediated vs. the high photo-induced DGM production, whatever natural water body was considered, it is worth stressing the significant contribution of this organismal-mediated process to oceanic mercury evasion, since it occurs continuously along the entire water column throughout the 24 h of the day.

Apparent rates of production and loss of dissolved gaseous mercury (DGM) in a southern reservoir lake (Tennessee, USA)

Apparent rates of dissolved gaseous mercury (DGM) concentration changes in a southern reservoir lake (Cane Creek Lake, Cookeville, Tennessee) were investigated using the DGM data collected in a 12-month study from June 2003 to May 2004. The monthly mean apparent DGM production rates rose from January (3.2 pg L − 1 /h), peaked in the summer months (June–August: 8.9, 8.0, 8.6 pg L − 1 /h), and fell to the lowest in December (1.6 pg L − 1 /h); this trend followed the monthly insolation march for both global solar radiation and UVA radiation. The monthly apparent DGM loss rates failed to show the similar trend with no consistent pattern recognizable. The spring and summer had higher seasonal mean apparent DGM production rates than the fall and winter (6.8, 9.0, 3.9, 5.0 pg L − 1 /h, respectively), and the seasonal trend also appeared to closely follow the solar radiation variation. The seasonal apparent DGM loss featured similar rate values for the four seasons (5.5, 4.3, 3.3, and 3.9 pg L − 1 /h for spring, summer, fall, and winter, respectively). Correlation was found of the seasonal mean apparent DGM production rate with the seasonal mean morning solar radiation ( r = 0.9084, p < 0.01) and with the seasonal mean morning UVA radiation ( r = 0.9582, p < 0.01). No significant correlation was found between the seasonal apparent DGM loss rate and the corresponding afternoon solar radiation ( r = 0.5686 for global radiation and 0.6098 for UVA radiation). These results suggest that DGM production in the lake engaged certain photochemical processes, either primary or secondary, but the DGM loss was probably driven by some dark processes.

Relationship between the loading rate of inorganic mercury to aquatic ecosystems and dissolved gaseous mercury production and evasion

The purpose of our study was to test the hypothesis that dissolved gaseous mercury (DGM) production and evasion is directly proportional to the loading rate of inorganic mercury [Hg(II)] to aquatic ecosystems. We simulated different rates of atmospheric mercury deposition in 10-m diameter mesocosms in a boreal lake by adding multiple additions of Hg(II) enriched with a stable mercury isotope ( 202Hg). We measured DGM concentrations in surface waters and estimated evasion rates using the thin-film gas exchange model and mass transfer coefficients derived from sulfur hexafluoride (SF 6) additions. The additions of Hg(II) stimulated DGM production, indicating that newly added Hg(II) was highly reactive. Concentrations of DGM derived from the experimental Hg(II) additions (“spike DGM”) were directly proportional to the rate of Hg(II) loading to the mesocosms. Spike DGM concentrations averaged 0.15, 0.48 and 0.94 ng l −1 in mesocosms loaded at 7.1, 14.2, and 35.5 μg Hg m −2 yr −1, respectively. The evasion rates of spike DGM from these mesocosms averaged 4.2, 17.2, and 22.3 ng m −2 h −1, respectively. The percentage of Hg(II) added to the mesocosms that was lost to the atmosphere was substantial (33–59% over 8 weeks) and was unrelated to the rate of Hg(II) loading. We conclude that changes in atmospheric mercury deposition to aquatic ecosystems will not change the relative proportion of mercury recycled to the atmosphere.

Formation of dissolved gaseous mercury in a tropical lake (Petit-Saut reservoir, French Guiana)

Formation of dissolved gaseous mercury (DGM) and its volatilization from aquatic systems can be considered as a natural attenuation process, which limits the methylation of mercury (Hg) and Hg accumulation in fish. Although gold-mining activity and erosion of tropical soils lead to increased Hg concentration in aquatic systems, little is known about DGM production and distribution in tropical aqueous systems. Our work explores the vertical distribution and principal sources of DGM in a meromictic Amazonian reservoir. Dissolved gaseous mercury measurements carried out in Petit-Saut reservoir (French Guiana, South America) revealed DGM increase in the surface waters and at the bottom layers of the reservoir during the dry season. As in arctic and temperate lakes, high DGM concentrations in surface waters were attributed to sunlight-mediated photochemical processes. Dissolved gaseous mercury concentrations in the anaerobic hypolimnion were larger than in temperate or arctic lakes. In order to elucidate Hg(II) reduction pathways in the bottom layer of tropical reservoir, laboratory Hg(II) reduction experiments were performed with anoxic aqueous suspensions of surface sediments either untreated or treated by γ-ray and NaN 3. Our results indicated that DGM production at the bottom layer of Petit-Saut reservoir was biologically mediated. Dissolved gaseous mercury formation rates in the surface sediment suspensions were of the same order of magnitude as formation rates in freshwater lakes reported in literature.

Relationship between DOC photochemistry and mercury redox transformations in temperate lakes and wetlands

We compared diurnal variations in dissolved gaseous mercury (DGM) concentration and in losses of dissolved organic carbon fluorescence (DOCF) in four boreal Canadian Shield lakes, in one beaver pond, and in filtered and unfiltered water from a wetland in Lake St. Pierre, a fluvial lake of the St. Lawrence River. These systems were chosen to represent a spectrum of DOC. We also determined the contribution of UVB, UVA and visible light on DGM photo-induced production in the four lakes. Our results showed a strong relationship between DGM concentrations and light intensity and between DGM production and losses in DOCF, in all study sites. We also observed higher rates of DGM formation and of DOCF bleaching in the presence of UV radiation. Under UVB light, production of DGM was higher in clear lakes than in the humic ones. Inversely, in the UVA range, DGM production tended to be higher in humic lakes. We suggest that DOCF bleaching can be used as a proxy for the rate of formation of reactive species that may alter the redox state of mercury in surface waters. We also have indications that DGM production is more important in clear than in humic waters.

Biological and photochemical production of dissolved gaseous mercury in a boreal lake

We used in situ experiments and measured depth profiles of dissolved gaseous mercury (DGM) to investigate the relative contribution of photochemical versus biological processes on the production of DGM in an oligomesotrophic lake of the Canadian Shield. At the surface, DGM production was mainly photomediated, with reduction rates being twice as high in the wetland than in the lake. In the water column, the distribution of DGM concentrations was not strictly related to light but followed a multimodal distribution, with peaks encountered below the epilimnion at depths receiving &lt;5% of the incident light. Those peaks were recorded in the middle and at the bottom of the metalimnion during the ice‐free season, as well as under ice cover and at the bottom of an anoxic hypolimnion. Rather than being a consequence of the bacterial mercuric reductase activity, metalimnetic DGM peaks were associated with the intensity and duration of phytoplankton blooms. In situ incubation experiments also showed that DGM production ceased when samples were kept in the dark, filtered, or when an inhibitor of photosynthesis was added. Our results illustrate the important role of phytoplankton on Hg redox dynamics in the water column of lakes.

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.