Using the INCA-Hg model of mercury cycling to simulate total and methyl mercury concentrations in forest streams and catchments.

We present a new, catchment-scale, process-based dynamic model for simulating mercury (Hg) in soils and surface waters. The Integrated Catchments Model for Mercury (INCA-Hg) simulates transport of gaseous, dissolved and solid Hg and transformations between elemental (Hg(0)), ionic (Hg(II)) and methyl (MeHg) Hg in natural and semi-natural landscapes. The mathematical description represents the model as a series of linked, first-order differential equations describing chemical and hydrological processes in catchment soils and waters which we believe control surface water Hg dynamics. The model simulates daily time series between one and 100 years long and can be applied to catchments ranging in size from <1 to ~10,000 km(2). Here we present applications of the model to two boreal forest headwater catchments in central Canada where we were able to reproduce observed patterns of stream water total mercury (THg) and MeHg fluxes and concentrations. Model performance was assessed using Monte Carlo techniques. Simulated in-stream THg and MeHg concentrations were sensitive to hydrologic controls and terrestrial and aquatic process rates.

Mercury empirical relationships in sediments from three Ontario lakes.

Total mercury (THg), methyl mercury (MeHg), total organic carbon (TOC), sediment bulk density (SBD), redox potential (Eh) and percent fines measurements were made on sediment cores collected along transects from littoral to profundal depths in Harp, Dickie, and Blue Chalk lake located on the Canadian Shield near Dorset, Ontario, Canada to determine whether empirical relationships exist among these sediment properties. MeHg was positively correlated with THg in all sediments with a MeHg:THg ratio (0.004+/-0.004) comparable to other uncontaminated profundal lakes. MeHg, MeHg:THg and TOC decreased with sediment depth within the core for all lakes, whereas THg only showed a decrease in Harp Lake. MeHg:THg ratio in surficial sediments was positively correlated with Eh and negatively correlated with TOC [MeHg:THg=-0.009 TOC (%)+0.001 Eh (mV)-1.902, p=0.026]; whereas THg was positively correlated with TOC [log THg (ppb)=0.026 TOC (%)+1.400, p<0.0001].

Assessment of thyroid system disruption in Rana pipiens tadpoles chronically exposed to UVB radiation and 4-tert-octylphenol.

Many studies have considered recent increases in ultraviolet B radiation (UVBR) and endocrine disrupting chemicals polluting the environment as possible contributing factors to the reduction in amphibian populations. It has been demonstrated that exposure of amphibians to estrogenic chemicals or UVBR can affect the timing of larval development and metamorphosis. However, amphibians in the wild are exposed to multiple environmental stressors simultaneously. Therefore, our study examines the effects of UVBR and the estrogenic chemical 4-tert-octylphenol (OP), alone and in combination, on the thyroid system of Rana pipiens tadpoles, which is the main regulator of amphibian metamorphosis. Results demonstrate that thyroid gland histomorphology measurements in Gosner stage 31 tadpoles continuously exposed to UVBR (0.21W/m(2)) were not different than those measured in animals from the control group. In a separate experiment, tadpoles exposed to environmentally relevant levels of UVBR (0.22W/m(2)) and/or OP (0.01nM or 10nM) exhibited significantly delayed development starting from Gosner stage 29, given that fewer tadpoles developed past stage 29 in these groups. In addition, significantly fewer UVBR-treated tadpoles developed past stage 34 and metamorphosed. Samples were collected from stages 29 and 34 tadpoles for gene expression analysis in tail tissue and measurements of T3 (triiodothyronine) whole body levels (minus tail). UVBR and/or OP exposure did not affect T3 levels in stages 29 and 34 tadpoles. However, a decrease in deiodinase type 2 (D2) or increase in deiodinase type 3 (D3) mRNA levels was observed in groups of tadpoles with slowed developmental rates at those developmental stages. Given that D2 activates and D3 inactivates thyroid hormones (TH), UVBR/OP mediated disruptions in development are likely caused by dysfunctions in the localized metabolism of THs through alterations in the expression of these enzymes in peripheral tissues. This is the first study to our knowledge reporting a potential thyroid-based mechanism of action for the developmental delays in amphibians exposed to UVBR and/or OP.

Global increases in ultraviolet B radiation: potential impacts on amphibian development and metamorphosis.

Levels of ultraviolet B radiation (UVBR) reaching the Earth's surface have increased since the 1970s as a result of stratospheric ozone depletion caused by the emission of ozone-depleting substances (ODSs) such as chlorofluorocarbons. Despite international agreements to phase out harmful ODSs, these substances are persistent, and even under the most optimistic scenarios, stratospheric ozone levels will not return to pre-1980 levels for several decades. Furthermore, climate change may enhance chemical stratospheric ozone depletion. Global phenomena such as climate change, ozone depletion, and acidification of aquatic ecosystems interact to modify dissolved organic carbon levels in aquatic systems, thereby increasing the penetration of UVBR. Since amphibians inhabit both aquatic and terrestrial habitats and have unshelled eggs and permeable skin, they are vulnerable to changes in environmental conditions and habitat quality. Increased exposure of amphibians to UVBR can produce lethal and sublethal effects, especially in individuals that do not possess adequate defense mechanisms to protect themselves. In this article, we discuss worldwide increases in UVBR and the adverse effects of UVBR exposure on amphibians. Specifically, studies on the effects of UVBR on amphibian development and metamorphosis are summarized, and possible mechanisms of thyroid system disruption caused by UVBR exposure are considered.

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.

Factors affecting methylmercury distribution in surficial, acidic, base-metal mine tailings.

The most toxic form of Hg commonly of concern in the environment is methylmercury (MeHg), as it accumulates in living tissues and bioconcentrates in food webs. Sulfide-rich metal ores are often enriched in Hg, but little is known regarding the potential for Hg methylation in acidic tailings produced from these ores. This study examined acidic tailings from four mines in northern Ontario, Canada, to determine whether they could be an important source of MeHg to downstream environments. Where sulfate reducing bacteria (SRB) were abundant and active in pH-circumneutral, unoxidized layers (Potter mine), negligible MeHg was detected. By contrast, a zone of active sulfate reduction found in the acidic, oxidizing, surficial layers of tailings from the Kidd Metsite contained the highest concentrations of MeHg in bulk tailings (12.1 nmol kg(-1) dry wt. of sediment) and porewaters (88 pM) measured in this study. Cell count estimates of SRB by the "most-probable-number" (MPN) method were low in these surficial tailings, suggesting that sulfate reducers from this environment were acidophilic and did not thrive under the pH-neutral conditions of the MPN incubations. A later study of bacterial DNA from these tailings produced evidence of a novel Deltaproteobacterium which has only previously been detected in acid mine drainage environments. Further research will be necessary to determine whether this Deltaproteobacterium is a sulfate reducer and/or an efficient Hg methylator. Surface water concentrations of MeHg did not exceed Canadian water quality guidelines at any of the sites sampled, but one site (Broulan) featured total Hg (HgT) concentrations of 838 pM in filtered samples, far in excess of recommended levels. Trends in surface water MeHg and HgT reflected corresponding values in porewaters from the same sites, indicating that concentrations of these substances in tailings influence surface water concentrations.

Temporal trends and spatial variability of mercury in four fish species in the Ontario segment of the St. Lawrence River, Canada.

The Massena (New York) and Cornwall (Ontario) region has a long history of Hg discharge into the St. Lawrence River. The objectives of this study were to evaluate if Hg levels have declined in this portion of the river since 1975 and to compare Hg level in fish species upstream and downstream of this area in order to evaluate the anthropogenic contribution to Hg levels in fish. Mercury levels in four fish species were monitored over a 20-year period (1975-1995). A general linear model and an analysis of covariance were used to extract temporal trends and spatial variability, respectively, while correcting the data for fish length. Over time, Hg levels declined in most fish species. In the four regions studied, Hg levels in fish were similar, which suggests that other sources like atmospheric deposition and Hg loading from the Great Lakes may also contribute to the Hg burden in fish in the St. Lawrence River. This indicates that fish, with large home range, are good biomonitors of temporal Hg releases but their ability to avoid point sources makes them less appealing as biomonitors to address spatial variability in Hg releases.

Investigation of pathogenic Escherichia coli and microbial pathogens in pulp and paper mill biosolids.

Biosolids produced from pulp and paper mill wastewater treatment have excellent properties as soil conditioners, but often contain high levels of Escherichia coli. E. coli are commonly used as indicators of fecal contamination and health hazard; therefore, their presence in biosolids causes concern and has lead to restrictions in land-spreading. The objectives of this study were to determine the following: (1) if E. coli from the biosolids of a wastewater-free pulp and paper mill were enteric pathogens, and (2) if other waterborne microbial pathogens were present. E. coli were screened for heat-labile and heat-stable enterotoxin and verocytotoxin virulence genes using a polymerase chain reaction. Ten isolates were also screened for invasion-associated locus and invasion plasmid antigen H genes. None of the 120 isolates carried these genes. Tests for seven other microbial pathogens were negative. Effluents and biosolids from this mill do not contain common microbial pathogens and are unlikely to pose a health hazard.

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.

Health of tree swallow (Tachycineta bicolor) nestlings exposed to chlorinated hydrocarbons in the St Lawrence River basin. Part I. Renal and hepatic vitamin A concentrations.

Sixteen-day-old tree swallows (Tachycineta bicolor), near fledging, were collected in 1999 and 2000 from nine sites representing a gradient of dioxin concentrations, within the vicinity of the St. Lawrence River in Canada and the United States, to determine if organochlorine contaminants correlated with vitamin A levels measured as retinol and retinyl palmitate. Mean concentrations of hepatic retinol ranged from 3 mg /kg to 13 mg /kg, and from 0.35 mg /kg to 1.5 mg /kg for renal retinol. Mean concentrations of hepatic retinyl palmitate ranged from 18 mg /kg to 146 mg /kg, and 1mg /kg to 6 mg/kg for renal retinyl palmitate. In 1999, molar ratio of renal retinol: retinyl palmitate was significantly and positively correlated with total polychlorinated dibenzodioxin (PCDD) concentration. Among sites, total PCDDs ranged from 5.4 ng /kg wet weight to 79.5 ng /kg wet weight in tree swallows. These results suggest that current levels of organochlorine contaminants in the St. Lawrence River and surrounding tributaries may be interacting with the vitamin A pathway. Lower circulating levels and higher tissue concentrations of retinoids may result in compromised immune function and reduced reproductive success in adult birds.

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.

Microbial reduction and oxidation of mercury in freshwater lakes.

The evasion of elemental mercury represents a significant pathway for reducing the level of this potentially toxic material in aquatic ecosystems. The evasion rate is controlled by the concentration of dissolved gaseous mercury (DGM) across the air-water interface, water, and air temperature as well as wind speed. Here we investigate the role of microbial mercury oxidation and reduction in regulating DGM diel patterns in two freshwater lakes, Jack's Lake and Lake Ontario. Three replicate diurnal cycles of DGM in Brookes Bay, Jack's Lake peaked at 313 fM between 9:00 to 10:30 and decreased to 79.6 fM by 16:00. Microbial mercury reductase activity (converts Hg2+ to Hg0) increased with DGM concentrations and mercury oxidase activity (converts Hg0 to Hg2+) increased as DGM concentrations decreased in the mid-afternoon. This illustrates that mercury oxidase activity was linked to hydrogen peroxide (H2O2) diurnal patterns. Thirty minutes after spiking Lake Ontario water with H2O2, mercury oxidase activity increased by 250% and by 60 min, DGM decreased to 28% of its initial value. Two hours after the H2O2 spike, mercury oxidase activity had declined, but mercury reductase activity and DGM both increased. Four hours after the spike, mercury reductase and DGM levels had returned to original levels. Our results are consistent with the following sequence of events. In the morning, microbial activity produces DGM (in addition to any DGM formed through photoreduction of Hg2+). As photochemically produced H2O2 increases in concentration it induces the biologically mediated decrease in DGM concentrations throughout the afternoon. To predict concentration of DGM in surface waters and flux rates to the atmosphere, the contribution of photoreduction and photooxidation must be placed in context with reduction and oxidation rates due to microbial activity.