1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 A Mass Budget for Mercury and Methylmercury in the Arctic Ocean
Anne L. Soerensena,b, c,*, Daniel J. Jacobb, Amina Schartupa,b, Jenny A. Fisherd, Igor
Lehnherre,f, Vincent L. St. Louise, Lars-Eric Heimbürgergh, Jeroen E. Sonkeg, David P.
Krabbenhofti, Elsie M. Sunderlanda,b
a
Harvard T.H. Chan School of Public Health, Department of Environmental Health, Boston
MA 02215, USA
b
Harvard University, John A. Paulson School of Engineering and Applied Sciences,
Cambridge MA, 02138, USA
c
Stockholm University, Department of Environmental Science and Analytical Chemistry,
Stockholm, 11418, Sweden
d
University of Wollongong, Centre for Atmospheric Chemistry, Wollongong NSW, 2522,
Australia
e
University of Alberta, Department of Biological Sciences, Edmonton, Alberta, Canada T6G
2E9
f
University of Toronto-Mississauga, Department of Geography, Mississauga, Ontario,
Canada L5L 1C6
g
CNRS, Geoscience Environment Toulouse, Midi-Pyrenees Observatory, Toulouse, 31400,
France
h
University of Bremen, Department of Geosciences, Bremen, 28334, Germany
i
U.S. Geological Survey, Middleton, Wisconsin 53562, United States
* corresponding author: [email protected]
27 28 1 29 Key points:
30 •
31 A Hg mass budget suggest the terrestrial environment is the largest net source to the
Arctic Ocean
32 •
33 Atmospherically deposited MeHg, from oceanic Me2Hg evasion, is the largest source
to the PML
34 •
35 Geochemical box modeling shows changes in Hg loading rapidly affect Arctic PML
concentrations
2 36 Abstract
37 Elevated biological concentrations of methylmercury (MeHg), a bioaccumulative neurotoxin,
38 are observed throughout the Arctic Ocean but major sources and degradation pathways in
39 seawater are not well understood. Our mass budget calculations show that high total Hg in
40 Arctic seawater relative to other basins reflect large freshwater inputs and sea ice cover that
41 inhibits losses through evasion. We find that most net MeHg production (20 Mg a-1) occurs in
42 the subsurface ocean (20-200 m). There, it is converted to dimethylmercury (Me2Hg: 17 Mg
43 a-1), which diffuses to the polar mixed layer and evades to the atmosphere (15 Mg a-1). Me2Hg
44 has an atmospheric lifetime of only a few hours and rapidly degrades back to MeHg. We
45 postulate that most evaded Me2Hg is re-deposited as MeHg and that atmospheric deposition is
46 the largest net MeHg source (8.5 Mg a-1) to the biologically productive surface ocean.
47 Riverine MeHg accounts for an additional 15% of inputs to the surface ocean (2.5 Mg a-1).
48 MeHg concentrations in the Arctic Ocean are elevated compared to lower latitude oceans.
49 Increasing MeHg inputs from the Arctic terrestrial landscape are likely in the future given
50 increasing freshwater discharges and permafrost melt. This may offset potential declines
51 driven by increasing evasion from ice-free surface waters. Our simulations illustrate that for
52 the most biologically relevant regions of the ocean, regulatory actions that decrease
53 atmospheric Hg deposition have the capacity to rapidly affect aquatic Hg concentrations.
54 55 56 Index terms: 4805
3 57 Introduction
58 Accumulation of methylmercury (MeHg) in Arctic biota is a major concern for the
59 health of northern populations that consume large quantities of marine foods [AMAP, 2011a;
60 Riget et al., 2011b]. High MeHg concentrations in Arctic fish and marine mammals have been
61 attributed to a combination of enhanced mercury (Hg) deposition at high latitudes and
62 enhanced biomagnification due to climate-driven shifts in ocean biogeochemistry and trophic
63 structure [Braune et al., 2015; Lehnherr, 2014; Loseto et al., 2008; Stern et al., 2012]. Prior
64 work has characterized total mercury (Hg) inputs and reservoirs in the Arctic Ocean but has
65 not quantified the link to bioavailable MeHg [Fisher et al., 2013; Kirk et al., 2012; Outridge
66 et al., 2008; Zhang et al., 2015]. Here we use all available data to construct Arctic Ocean
67 mass budgets for Hg and MeHg and gain insight into processes driving MeHg bioavailability
68 for biota.
In marine ecosystems, MeHg is produced from divalent inorganic Hg (HgII) by
69 70 bacteria in benthic sediment and in the marine water column [Lehnherr, 2014]. It is also
71 produced in freshwater ecosystems and wetlands and transported by rivers into the surface
72 ocean [Nagorski et al., 2014]. Lehnherr et al. [Lehnherr et al., 2011] measured water column
73 methylation at the subsurface chlorophyll maximum and the oxycline at multiple stations in
74 the Canadian Arctic Archipelago and concluded that this is likely the major MeHg source to
75 polar marine waters. Levels of dimethylmercury (Me2Hg) measured in Arctic surface
76 seawater are unusually high compared to other oceans [Bowman et al., 2014; Horvat et al.,
77 2003]. Me2Hg is mainly produced from MeHg in the ocean as shown by incubation
78 experiments in Arctic Coastal waters [Lehnherr et al., 2011]. Recent measurements have
79 identified evaded Me2Hg from the Arctic surface ocean and subsequent atmospheric MeHg
80 deposition as a substantial source to ocean surface waters and adjacent terrestrial ecosystems
81 [Baya et al., 2015; Lin and Pehkonen, 1999; St Pierre et al., 2015].
4 82 Concentrations of total Hg are elevated in Arctic surface seawater relative to other
83 basins [Heimburger et al., 2015; Mason et al., 2012]. Sea ice cover, an extensive continental
84 shelf, large freshwater inputs, and salinity driven stratification of the surface mixed layer
85 distinguish the Arctic Ocean from the mid-latitude oceans. Springtime releases of bromine
86 result in rapid oxidation of gaseous elemental Hg (Hg0) to the water-soluble divalent species
87 (HgII) and atmospheric Hg depletion events (AMDEs) [Schroeder et al., 1998; Steffen et al.,
88 2015]. AMDEs were originally hypothesized to drive large increases in oceanic Hg inputs,
89 but subsequent work has indicated that much of the deposited HgII is reemitted back to the
90 atmosphere after photochemical reduction in the surface ocean and snowpack [AMAP, 2011a;
91 Kirk et al., 2006; Lalonde et al., 2002]. Rivers are a large source of total Hg to the Arctic
92 Ocean, but prior modeling work has not evaluated their importance for MeHg cycling [Amos
93 et al., 2014; Dastoor and Durnford, 2014; Fisher et al., 2012; Zhang et al., 2015].
94 Here we develop a five-box geochemical model for the Arctic Ocean parameterized
95 using all available Hg and MeHg measurements. We force the model with changes in sea ice
96 and anthropogenic Hg deposition from 1850 to 2010. We use this analysis to gain insight into
97 critical processes affecting MeHg concentrations in Arctic Ocean biota and timescales of
98 response associated with changes in external Hg sources.
99 Model Overview
100 Our five-box geochemical model for the Arctic Ocean includes compartments
101 representing: (1) the low-salinity upper 20 m of the water column known as the polar mixed
102 layer (PML); (2) the subsurface ocean that extends to the bottom on the shelf and to 200 m
103 depth in the Central Arctic Basin and Baffin Bay; (3) the deep ocean below 200 m to the sea
104 floor in the Central Basin and Baffin Bay; (4/5) active sediment layers on the shelf (2 cm) and
105 in the Central Basin (1 cm). The active sediment layer depth characterizes benthic sediment
5 106 that interacts with the water column through bioturbation/resuspension and chemical diffusion
107 [Clough et al., 1997; Kuzyk et al., 2013; Trefry et al., 2014].
We estimate external inputs and exchanges/loss of Hg species (HgII, Hg0, MeHg,
108 109 Me2Hg) from each compartment based on a comprehensive review of all measured
110 concentrations and fluxes (Tables 1-4). Mass budgets for each species are used to derive first-
111 order rate coefficients and create a set of coupled first-order differential equations for changes
112 in chemical mass over time following Sunderland et al. [Sunderland et al., 2010]. Processes
113 in the model include: (1) external inputs from atmospheric deposition, rivers, erosion, snow
114 and ice melt, and other oceans, (2) advective transport by seawater circulation, ice transport,
115 and settling of suspended particulate matter, (3) diffusive transport through the water column
116 and at the sediment-water and air-sea interfaces, and (4) chemical transformations through
117 inorganic Hg redox reactions and methylation, and degradation of MeHg and Me2Hg. Details
118 of mass budget calculations are provided in the Tables S3-S9.
119 Hydrologic and solids budget
120 Hydrologic and solids budgets used to characterize advective transport of Hg species
121 are provided in the supplemental information (Figure S1). The hydrologic budget is based on
122 seawater inflow and outflow from the North Atlantic and North Pacific, river discharge,
123 precipitation and evapotranspiration [Beszczynska-Moller et al., 2012; Curry et al., 2011;
124 Panteleev et al., 2006; Serreze et al., 2006; Smedsrud et al., 2010]. Internal circulation is
125 based on Alfimov et al. [Alfimov et al., 2006].
126 We adapted the solids budget from Rachold et al. [Rachold et al., 2004] to include
127 enhanced productivity with reduced sea ice cover in recent years [Hill et al., 2013].
128 Productivity (550 Tg C a-1) is distributed equally between the surface layer and mid-depth Chl
129 max [Arrigo et al., 2011]. Settling of suspended particles is based on the fraction of solids
130 remaining following remineralization at each depth in the water column [Cai et al., 2010;
6 131 Moran et al., 1997; Rachold et al., 2004]. We do not estimate solids resuspension from
132 benthic sediment due to limited data. Burial rates for benthic sediment are based on shelf and
133 deep Central Arctic Basin measurements (Table 3).
134 Mercury reservoirs
135 We synthesized all data collected since 2004 on Hg species concentrations in seawater
136 (Figure 1), sediment, ice, and biota to estimate reservoirs of Hg species in the Arctic Ocean
137 (Tables 1-2). Volumes used to calculate reservoirs are provided in Table 3. Maximum
138 reservoirs of MeHg in primary producers and zooplankton occur in the Arctic summer and are
139 estimated from peak biomass, reservoirs of carbon (g C m-2) and Hg concentrations (Table 3).
140 For phytoplankton and bacteria we used Hg concentrations in seston (<200 µm) as a proxy
141 (Table 2) and for zooplankton (>200 µm) we estimate mean MeHg burden from Arctic
142 observations (Table S2).
143 Mercury fluxes
144 Atmospheric Hg fluxes include direct deposition to ice-free ocean surface waters, a
145 delayed pulse of inputs from seasonal meltwater, and evasion of Hg0 and Me2Hg from the
146 surface ocean. We adopt the recent Hg0 evasion estimate of Zhang et al. [Zhang et al., 2015]
147 that matches observational constraints from atmospheric monitoring data. Evasion of Me2Hg
148 from ice-free surface waters of 15 Mg a-1 is based on the concentration gradient between the
149 PML (Table 1) and marine boundary layer (Table 2), and mean wind speed over the Arctic
150 Ocean (Table 3). Additional details are provided in the SI (Table S9).
151 Atmospheric inputs of inorganic Hg to the ice-free surface ocean (Table 3) are taken
152 from recent modeling using the GEOS-Chem global Hg model for consistency with the
153 evasion flux [Fisher et al., 2013; Zhang et al., 2015]. Me2Hg has an atmospheric lifetime of
154 only a few hours against decomposition to MeHg [Lin and Pehkonen, 1999], while the
155 atmospheric lifetime of MeHg against photo-degradation is longer (2-5 days) [Bittrich et al.,
7 156 2011]. This allows MeHg to be scavenged in precipitation and dry deposited to the ocean and
157 adjacent terrestrial ecosystems before degradation. We base atmospheric MeHg deposition
158 (8.5 Mg a-1) on the evaded Me2Hg flux and the seasonal fraction of the surface ocean that is
159 ice-free (Table 3; Table S3). Measured MeHg concentrations in Arctic precipitation (snow,
160 rain) account for <0.5 Mg a-1 of this flux (Table 4) while the dry deposition flux, calculated
161 using the HgII dry deposition velocity for water surfaces as a proxy for MeHg [Baya et al.,
162 2015] (Table 3), accounts for between 1 and 5 Mg a-1. Fog deposition provides another
163 plausible pathway for enhanced deposition of water-soluble gases (including Hg) in the Arctic
164 summer [Evenset et al., 2004; Poulain et al., 2007; Rice and Chernyak, 1997]. Presently no
165 direct measurements of MeHg concentrations in Arctic fog droplets are available. However, at
166 lower latitudes concentrations (17±19 pM) up to two orders of magnitude higher than oceanic
167 precipitation have been observed [Weiss-Penzias et al., 2012].
168 We use a mid-point estimate of inorganic Hg releases from snowmelt from various
169 models that range between 20 and 50 Mg a-1 [Dastoor and Durnford, 2014; Fisher et al.,
170 2012]. For MeHg, the snowmelt flux is based on the volume of snow deposited to the ice-
171 covered surface ocean and mean concentrations in aged snow and snow melt (Table 4). Hg
172 and MeHg inputs from melting of multi-year sea ice are taken from Beattie et al. [Beattie et
173 al., 2014].
174 We use inputs of inorganic Hg from Arctic rivers based on terrestrial dissolved
175 organic carbon (DOC) inputs to the ocean from the modeling work of Dastoor and Durnford
176 [Dastoor and Durnford, 2014]. This estimate agrees well with the upper bound from a
177 compilation of empirical measurements from Amos et al. [Amos et al., 2014] and recent work
178 by Zhang et al. [Zhang et al., 2015]. Inputs of MeHg from rivers are calculated from the
179 observed fraction of total Hg (1-10%, Table 4). Coastal erosion of inorganic Hg is based on
180 the solids budget (Figure S1A) and Hg concentrations in eroding material (61-114 ng g-1)
8 181 from Leitch et al. [Leitch, 2006]. MeHg concentrations are assumed to be negligible in
182 eroding material.
183 Advective transport of Hg species with inflowing/outflowing seawater and ice is based
184 on flow volumes and measured concentrations at the appropriate flow depths (Figure S1B).
185 Internal transport of Hg species associated with seawater flow among boxes is based on the
186 hydrologic budget (Figure S1A). The surface ocean is strongly stratified [Macdonald et al.,
187 2005], so we only consider vertical Hg fluxes in the PML associated with settling of
188 suspended particles and diffusive transport. We estimate settling rates and burial of Hg
189 species based on the solids budget and Hg concentration data from Table 2.
190 Within the water column, the eddy diffusion flux is based on concentration gradients
191 between the surface ocean (10 m), the average mid-depth peak (140 m) and the deep ocean
192 (300 m) [Heimburger et al., 2015], and a mean diffusivity of 1 x 10-4 m2 s-1(range 0.5 -2.3 x
193 10-4) [Joos et al., 1997; Shaw and Stanton, 2014; Strode et al., 2010]. For benthic sediment
194 we use data from North Atlantic estuarine and shelf regions to estimate partitioning of HgII
195 and MeHg between the dissolved and solid phases (log Kd: Hg = 3.5; MeHg = 2.7) [Hollweg
196 et al., 2010; Schartup et al., 2015a; Sunderland et al., 2006]. Dissolved concentrations are
197 used to calculate upper and lower bounds for diffusion of Hg species at the sediment-water
198 interface [Sunderland et al., 2010] (Table S6).
199 Chemical transformations
200 We specify the seawater oxidation rate following the parameterization of Soerensen et
201 al. [Soerensen et al., 2010] and constrain the reduction rate using the measured Hg0:HgII
202 fraction in PML and subsurface seawater along with Hg0 evasion loss. Internal production and
203 decomposition of MeHg and Me2Hg in the water column is based on a compilation of rate
204 constants measured in seawater (Table S1). We calculate a base methylation rate in the deep
205 ocean using experimental measurements from dark filtered seawater [Monperrus et al., 2007].
9 206 To account for the influence of enhanced microbial activity in the subsurface ocean (20-200
207 meters) on methylation, we scale the base rate by monthly primary production. Our average
208 methylation rate correspond to the upper range of experimentally measured values in summer
209 at mid-latitudes (0.017 d-1) [Monperrus et al., 2007], and our calculated fall value (0.007 d-1)
210 agrees with rates measured in the Canadian Arctic Archipelago [Lehnherr et al., 2011] (Table
211 S1). No methylation rates have been measured in the Arctic Ocean PML and we therefore
212 estimate the net biotic methylation needed to close the PML budget for MeHg. This is
213 reasonable given significant, but low, net methylation recently reported in oxic marine waters
214 of the sub-Arctic [Schartup et al., 2015b] and detectable methylation measured at the base of
215 the PML in the Canadian Arctic Archipelago [Lehnherr et al., 2011].
216 Production of Me2Hg from MeHg in seawater is taken from direct rate
217 measurements [Lehnherr et al., 2011]. Photolytic MeHg degradation to HgII in seawater is
218 based on the mean of published rates (Table S1) and averaged summer photosynthetically
219 active radiation (PAR) within the photic zone of ice free surface waters and melt ponds
220 [Porter et al., 2011; Serreze and Barry, 2005] (Table 3). Parsing the photodemethylation rate
221 into specific UV-A, UV-B and PAR fractions based on Arctic freshwater studies results in a
222 lower degradation flux [Lehnherr and St Louis, 2009]. Biotic degradation/decomposition of
223 Me2Hg to MeHg is based on data from the deep Pacific Ocean [Mason et al., 1995]. We
224 neglect photodegradation of Me2Hg in the PML as Me2Hg is not readily photodegraded in the
225 ocean [Black et al., 2009]. We constrain the pool of MeHg available for demethylation using
226 the measured ratio of MeHg:HgII in seawater.
227 Methylation in benthic sediment (0.03 d-1) is based on measurements from the North
228 Atlantic shelf and estuaries [Heyes et al., 2006; Hollweg et al., 2010]. The benthic sediment
229 demethylation rate is constrained using the dissolved fraction of total Hg as MeHg in
230 porewater (Table S6).
10 231 232 Results and discussion
233 Total Hg Budget
234 Figure 2 shows that more than half of the Hg reservoir in the Arctic Ocean is
235 contained in the active layers of benthic and shelf sediment (3900 Mg) followed by an
236 additional 35% in the deep ocean and only 7% in the upper ocean. We estimate the total Hg
237 reservoir in Arctic seawater at 2870 Mg, with a lifetime against losses of 13 years. Although
238 the age of total Hg in the deep water (>200 m) is longer (45 years) it is still less than central
239 Arctic basin tracer ages, that can exceed several hundred years, because the reservoir also
240 includes Baffin Bay and upper intermediate waters. Evasion of Hg0 and Me2Hg (100 Mg a-1)
241 are the major removal pathways from the water column, accounting for 44% of total losses
242 (Figure 3). Seawater outflow to the North Atlantic accounts for an additional 86 Mg a-1
243 removal of total Hg (38%) and sedimentation of suspended solids is relatively smaller at 38
244 Mg a-1 (17% total losses).
245 Figure 3 shows that the terrestrial environment accounts for more than a third of total
246 Hg inputs to the water column (erosion and rivers: 83 Mg a-1), as does the atmosphere (direct
247 deposition and meltwater: 76 Mg a-1). Ocean inflow from the North Atlantic and North
248 Pacific account for an additional 53 Mg a-1 (24%), and sediment diffusion makes up the
249 remaining 5% of total inputs (11 Mg a-1). Substantial inputs of total Hg from rivers and
250 coastal erosion to the Arctic Ocean and declining sea ice cover drive high evasion (100 Mg a-
251 1
252 meltwater and direct atmospheric deposition of total Hg in our budget (-23 Mg a-1) suggests
253 the Arctic Ocean is a net source to the atmosphere, which is consistent with previous work
254 [Fisher et al., 2012; Sonke and Heimburger, 2012; Zhang et al., 2015].
) [Chen et al., 2015; Zhang et al., 2015]. The difference between evasion and inputs from
11 255 Figure 4 shows Arctic seawater is enriched in total Hg relative to inflowing waters
256 from the North Atlantic and North Pacific Oceans at all depths resulting in a 26 Mg a-1 net
257 loss from the Arctic. We infer from our mass budget that the observed enrichment in total Hg
258 in Arctic seawater relative to mid-latitude basins is caused by higher relative freshwater
259 inputs and ice-cover that inhibits losses through evasion. Future increases in mobilization of
260 Hg from thawing permafrost [Leitch, 2006; Rydberg et al., 2010] could increase Hg inputs to
261 the Arctic Ocean, offsetting the current declining trend due to enhanced losses from Hg0
262 evasion with sea ice retreat suggested by Chen et al. [Chen et al., 2015].
263 Methylated Hg Species Budget
264 The stability of MeHg and Me2Hg is enhanced under the dark, cold conditions with
265 low biological activity found in the deep ocean that contains almost 80% of the methylated
266 species reservoir (450 Mg) (Figure 2). However, the PML and subsurface ocean are the most
267 important reservoirs for MeHg accumulation at the base of the food web due to the
268 concentration of algal production and biological foraging in these regions. Summer peak
269 concentrations of MeHg in phytoplankton and zooplankton indicate a reservoir of only 0.7
270 Mg or about 2% of the MeHg reservoir in the upper ocean (0-200 m).
271 Unlike total Hg, only a small fraction of methylated Hg species are found in benthic
272 sediment (2.2%) (Figure 2), and we do not calculate a substantial diffusive flux from benthic
273 sediments to the overlying water column (<1 Mg a-1). Data on Arctic-wide solids
274 resuspension are needed to further elucidate on the importance of sediments as a MeHg
275 source to the shelf water column.
276 Similar to total Hg, the Arctic Ocean is enriched in methylated Hg species at all
277 depths relative to inflowing seawater from the North Atlantic and North Pacific Oceans
278 (Figure 4). For methylated Hg species, peak concentrations in excess of 200 fM are found in
279 subsurface seawater (20-200 m). Subsurface peaks of methylated Hg species in seawater are
12 280 observable across the global oceans [Bowman et al., 2014; Cossa et al., 2011; Sunderland et
281 al., 2009] but occur at much shallower depths in the Arctic [Heimburger et al., 2015;
282 Lehnherr et al., 2011]. Due to rapid Me2Hg evasion, a smaller fraction of methylated Hg is
283 found as Me2Hg in the PML than subsurface water while concentrations of bioavailable
284 MeHg are similar in the two layers (Table 1). This indicates that the subsurface peak is at
285 least partly driven by the evasion of Me2Hg in the PML. The subsurface peak of methylated
286 Hg species may also be enhanced by the pronounced halocline structure in the Arctic
287 [Heimburger et al., 2015; Schartup et al., 2015b]. Schartup et al. [Schartup et al., 2015b]
288 showed that salinity driven stratification can concentrate terrestrial dissolved organic matter
289 (DOM) in a relatively restricted vertical zone, which in turn may stimulate the activity of
290 methylating bacteria and increase methylated Hg production. Climate driven increases in
291 stratification of Arctic seawater and declining sea ice cover may thus have a large impact on
292 future levels of methylated Hg production and loss.
293 Figure 5 shows net production of MeHg from HgII only occurs in the water column of
294 the subsurface (20-200 m depth) ocean (20 Mg a-1). A large fraction of MeHg produced in the
295 subsurface ocean is converted to Me2Hg (17 Mg a-1), much of which diffuses to the PML
296 (~12 Mg a-1) and is evaded to the atmosphere (15 Mg a-1). Our budget suggests the major net
297 source of MeHg to the PML is atmospheric redeposition of this evaded Me2Hg (~8.5 Mg a-1)
298 originally produced in the subsurface ocean.
In addition to deposition, MeHg sources to the PML include rivers (2.5 Mg a-1),
299 300 diffusion from the subsurface ocean (1.6 Mg a-1), biotic degradation of Me2Hg in the water
301 column (0.5 Mg a-1) and inflow from the North Atlantic and Pacific (0.3 Mg a-1). The
302 reservoir of MeHg in the PML is small (3.8 Mg) and turnover is relatively fast (Figure 5).
303 Thus, we assume on an annual basis the MeHg budget must balance and infer based on this
304 assumption that a small net biotic production of MeHg in the range of other inputs occurs in
13 305 the PML water column (5 Mg a-1). Lehnherr et al. [Lehnherr et al., 2011] observed significant
306 methylation at the base of the PML in the Canadian Arctic Archipelago and Schartup et al.
307 [Schartup et al., 2015b] measured net dark methylation in oxic estuarine seawater from the
308 sub-Arctic. Both studies indicate that net biotic methylation in the PML is plausible.
309 Response to global change and anthropogenic emissions
310 Biogeochemical cycling of Hg in the Arctic Ocean is highly sensitive to ongoing
311 climate variability [Fisher et al., 2013; Krabbenhoft and Sunderland, 2013; Stern et al.,
312 2012]. Mean air temperature is increasing rapidly driving decreases in the extent and
313 thickness of sea ice cover [Bintanja et al., 2011; Kwok and Rothrock, 2009]. In addition,
314 global shifts in emissions of anthropogenic Hg will affect atmospheric inputs of Hg to the
315 Arctic ocean, either directly through atmospheric inputs or indirectly through terrestrial runoff
316 [Stern et al., 2012].
317 Figure 6 shows modeled changes in total Hg in Arctic Ocean seawater forced by
318 differences in atmospheric inputs and changes in sea ice cover. Atmospheric inputs since
319 1850 are estimated by scaling current inputs using historical deposition scenarios from
320 Horowitz et al. (2014). A 20% decrease of sea ice since 1975 is based on data from AMAP
321 [AMAP, 2011b]. Modeled external inputs to the PML increased by 50% between 1850 and
322 2010 and has an almost linear effect on total Hg concentrations in the PML (44%) and
323 subsurface water (33%) (Figure 6) reflecting the short turnover time of the total Hg reservoir
324 in the upper ocean (~3 year for 0-200 meter; Figure 5). Outridge et al. [Outridge et al., 2008]
325 hypothesized that MeHg concentrations in the Arctic Ocean are unlikely to be affected by
326 changes in external Hg inputs due to the large inorganic Hg reservoir, which they suggested
327 provides inertia against changes in loading over time. Our simulations illustrate that for the
328 most biologically relevant parts of the water column (0-200 meters), regulatory actions that
14 329 decrease Hg emission and associated atmospheric deposition have the capacity to rapidly
330 affect aquatic Hg concentrations.
331 Concentrations of methylated Hg can be expected to rapidly follow shifts in inorganic
332 Hg given rapid exchange between species shown in Figure 5. The impacts of changes in Hg
333 loading may be obscured or enhanced by other biogeochemical shifts in the ecosystem
334 affecting the lifetime of Hg species through evasion, methylation and degradation. Separating
335 these processes allows us to diagnose the impacts of Hg emissions reductions. For example,
336 Figure 6 shows the rapid decline in ocean Hg concentrations in recent years is for a large part
337 attributable to increased evasion as sea ice cover disappears [Chen et al., 2015].
338 We are unable to simulate the counteracting influence of changes in terrestrial
339 discharges due to lack of data, which represents a critical uncertainty in scenarios for MeHg
340 accumulation in the changing Arctic. The relative importance of external MeHg sources to the
341 Arctic Ocean depends in large part on the stability of MeHg complexes in seawater. Ongoing
342 changes in the terrestrial landscape such as permafrost melt and increases in freshwater
343 discharges of DOM are likely to increase MeHg inputs from Arctic rivers to the ocean in the
344 future [Krabbenhoft and Sunderland, 2013; Rydberg et al., 2010]. Recent work by Jonsson et
345 al. [Jonsson et al., 2014] suggests riverine MeHg bound to terrestrial DOM is both resistant to
346 degradation and biologically available. Thus, the overall lifetime of MeHg in the ocean is
347 likely to be enhanced in the future with increasing terrestrial DOM discharges, which would
348 lead to increases in the bioavailable MeHg reservoir.
349 Summary and Conclusion
350 We have developed a five-box biogeochemical model for the Arctic Ocean to gain
351 insight into processes and timescales driving changes in MeHg concentrations in the Arctic
352 Ocean. The model includes compartments representing three ocean and two sediment
15 353 reservoirs: the PML, subsurface and deep ocean water, and active sediment layers on the shelf
354 and in the Central Basin.
355 Results from the total Hg mass budget calculations suggest that exchange with both
356 the atmosphere (direct deposition and snowmelt) and lower latitude ocean results in net loss
357 of total Hg from the Arctic Ocean. The terrestrial landscape is the only net Hg source. We use
358 the box-model simulation to demonstrate the importance of the sea ice cover in controlling
359 surface ocean evasion loss. From this we infer that the observed enrichment in total Hg in
360 Arctic seawater relative to mid-latitude basins is caused by higher relative freshwater Hg
361 inputs and ice cover that inhibits losses through evasion.
The methylated Hg budget suggests that most net MeHg production (20 Mg a-1)
362 363 occurs in the subsurface ocean (20-200 m). There, it is subsequently converted to Me2Hg (17
364 Mg a-1), which readily diffuses to the PML and is evaded to the atmosphere (15 Mg a-1).
365 Me2Hg has an atmospheric lifetime of only a few hours and rapidly photochemically degrades
366 back to MeHg. We postulate that most evaded Me2Hg is re-deposited to the ocean and
367 surrounding landscape as MeHg and that atmospheric MeHg deposition is the largest net
368 source (8.5 Mg a-1) to the biologically productive surface ocean (0-20 m). We find that other
369 important MeHg sources to the PML are river input (2.5 Mg a-1) and postulated net biotic
370 methylation (5 Mg a-1). Rivers are likely to be disproportionately important for biological
371 uptake in marine food webs since binding to terrestrial DOM extends the MeHg lifetime in
372 the water column. We suggest that the overall lifetime of MeHg in the Arctic ocean is likely
373 to be enhanced in the future with increasing terrestrial DOM discharges.
374 We forced our box model of the Arctic Ocean with changes in sea ice and
375 anthropogenic Hg deposition from 1850-2010. Our results show that because of the short
376 lifetime (3 years) of total Hg in the most biologically relevant parts of the water column (0-
16 377 200 meters), regulatory actions that decrease Hg emission and associated atmospheric
378 deposition have the capacity to rapidly affect aquatic Hg concentrations.
17 379 Acknowledgements
380 We acknowledge financial support from the U.S. National Science Foundation (OCE
381 1130549, PLR 1023213). ALS acknowledges financial support from the Carlsberg
382 Foundation (2012_01_0860). JAF acknowledges financial support from a University of
383 Wollongong Vice Chancellor’s Postdoctoral Fellowship. JES acknowledges financial support
384 from the European Research Council (ERC-2010-StG_20091028). IL and VSL acknowledge
385 financial support from the Northern Contaminants Program and ArcticNet.
386 18 387 388 389 390 391 392 393 394 395 396 397 398 399 400 401 402 403 404 405 Table 1. Measured concentrations of Hg species in Arctic Ocean seawater. Cruise tracks for observations are
shown in Figure 1. Averages used in our budget are based on raw data from the cruises presented here.
Region
Total Hg (pM)
Methylated Hg Fraction
Me2Hg (fM)
Hg0 (fM)
(fM)
Methylated
(%)
a
a
Polar Mixed
1.56 ± 0.32
64 ± 43
4.5±3.4a
60±70c
126±51c,
c
c
c
j
Layer (<20 m)
2.92 ± 2.88
141±79
5
55±20
220±110d
b
j
j
f
2.09 ± 1.85
474±70
45.2
37
643±179j
e
k
k
g
0.55–1.40
284, 454, 364
30-40
50
30f
j
f
f
h
0.70 - 1.20
102
5.5
168
89g
f
g
g
l
2.29 ± 2.00
105±61
4.4
34±30
127h
g
h
h
m
1.91 ± 9.24
250
13.7
17±10
1.82 ± 0.45h
122l
146m
Best Estimate
2.0±1.8
130±110
7%
50±40
180±90
90±70 (MeHg)
Subsurface
1.10 ± 0.20a
216±95a
19.3±7.3a
362±184c
171±149c
c
c
c
f
Ocean (20-shelf 1.43±1.11
445±180
31
277
82f
f
f
f
g
bottom or
2.02±0.52
407
20 ,
331
48g
g
g
g
h
200m)
1.92±0.32
627
33
427
103h
h
h
h
l
1.57±0.31
517
33
138
1.1±0.45i
200±150i
18±14i
65m
l
248
212m
Best Estimate
1.29±0.53
320±220
25%
220±150
110±70
110±70 (MeHg)
Deep Central
1.00±0.25a
201±86a
20.6±9.5a
Basin and
Baffin Bay
(>200 m)
Best Estimate
1.00±0.25
200±90
20%
n/a = not available. Best Estimate is used in mass budget calculations. The Hg0 reservoir in the PML is estimated
by subtracting Me2Hg concentrations from measured dissolved gaseous mercury (DGM). The best estimate of
MeHg concentrations in the upper ocean is based on the ratio of MeHg:Me2Hg (PML: 2:1 and subsurface: 0.7:1)
[Lehnherr et al., 2011].
a
[Heimbürger et al., 2015] Aug-Sep 2011 Cruise in the Central Basin. See Figure 1.
b
[Zdanowicz et al., 2013], Baffin Bay July 2008
c
[Kirk et al., 2008], Canadian Arctic Archipelago/border to Baffin Bay August-October 2005 (station 1-11).
d
[Andersson et al., 2008] July-September measurements in Baffin Bay, Shelf and Central Arctic Basin reported
as dissolved gaseous Hg (Hg0+Me2Hg).
e
[Chaulk et al., 2011], Canadian Arctic Archipelago, March-May 2008
f
[Lehnherr et al., 2011], Canadian Arctic Archipelago, October 2007
g
[Lehnherr, 2015], Canadian Arctic Archipelago, September 2006.
h
[Lehnherr, 2015], Canadian Arctic Archipelago, August 2010.
i
[Wang et al., 2012], Beaufort Sea, March – July 2008
j
[St Louis et al., 2007], Canadian Arctic Archipelago May 2004 and May 2005k
l
[Baya et al. 2014], Canadian Arctic Archipelago July-August 2010 and 2011m
19 406 407 408 Table 2. Measured concentrations of Hg species in ice, suspended particles in the water column, benthic
sediment and air from the Arctic Ocean.
Medium
Total Hg
MeHg
Fraction MeHg (%)
Ice (pM)
4.0, 5.6, 12,7 (0.65-61)a
0.5-4.0, max 20b
3.9±1.0c
7.4 (2.8-10.0)
33±26 (4-88)d
36±27f
74± 27 (45-98)g
0.2, 1.35 (<.10-2.64)a
3.5-10a
0.75 (0.15-1.3)
1.4±1.1 (0.15-3.51)d
1.1e
<0.15f
3.7±1.0 (2.6-4.4)g
2 (0.15-3.51)
0.15±0.07 (0.03-0.29)h
0.05-0.37i
0.37±0.36 (<0.01-1.41)j
10%
<4d
<0.5f
Best Estimate
Suspended solids
(ng g-1 dry weight)
Best Estimate
Shelf sediment
(ng g-1 dry weight)
409 410 411 412 413 414 415 416 417 418 419 420 421 422 423 424 425 426 50 (30-70)
31±10 (5-55)h
50-100i
23 (8-40)k
41±29l
54±23m
47±18
<50-70n
4%
0.43±0.17h
~0.05-0.20i
0.70±0.40j
Best Estimate
0.19±0.12
0.4%
Central Basin/Baffin Bay
<0.05-0.10n
~0.05n
sediment
(ng g-1 dry weight)
Best Estimate
47±18
0.05 (0.01-0.10)
0.1%
Marine Boundary Layer
1.7±0.4 (ng Hg0 m-3)o
3.8±3.1 (pg Me2Hg m-3)p
Best Estimate
1.7
3.8
Best estimate for each medium is used in mass budget calculations.
a
[Beattie et al., 2014], Multitear sea ice from three cores in the Beaufort Sea in May, August and September
b
[Chaulk et al., 2011], Multiyear sea ice from the Canadian Arctic Archipelago in May
c
[Poulain et al., 2007], multiyear sea ice from the Canadian Arctic Archipelago in June
d
[Burt, 2012], total suspended solids from the Canadian Arctic Archipelago.
e
[Lehnherr, 2015], total suspended solids from the Canadian Arctic Archipelago
f
[Pucko et al., 2014], particulate organic matter from the Canadian Arctic Archipelago
g
[Graydon et al., 2009], total suspended solids in the Beaufort Sea
h
[Fox et al., 2013], benthic sediment Chukchi Sea
i
[Kading and Andersson, 2011], benthic sediment Chukchi Sea and Yermak Plateau
j
[Fox et al., 2013], benthic sediment Beaufort Sea
k
[ICES], Bering Sea upper 1-2 cm benthic sediment from 2004, 2006, 2009
l
[Trefry et al., 2003], upper 2 cm Beaufort Sea benthic sediment
m
[Canario et al., 2013], Canadian Arctic Archipelago >65N benthic surface sediment
n
[Kading and Andersson, 2011], Central Basin surface sediment
o
[Sommar et al., 2010]
p
[Baya et al., 2014]
20 427 428 429 Table 3. Physical characteristics of Arctic Ocean basin used to develop mass budgets for Hg species
Parameter
Value
Reference
Volume of Arctic Ocean (m3)
136×1014
[Jakobsson, 2002]
Volume of polar mixed layer (0-20 m) (m3)
2.22×1014
[Jakobsson, 2002]
Volume of mid-depth water (shelf: 20-bottom;
16.1×1014
[Jakobsson, 2002]
Central Basin and Baffin Bay: 20-200 m) (m3)
Volume of water below 200 meters (m3)
118×1014
[Jakobsson, 2002]
3
Volume of sea ice (m )
0.1×1014
[Serreze et al., 2006]
Volume of active shelf sediment (m3) (0.02 m depth) 18×1010
Volume of active deep sediment (m3) (0.01 m depth) 5×1010
Surface area of shelf regions (m2)
608×1010
[Jakobsson, 2002]
Surface area of the Central Basin and Baffin Bay
500×1010
[Jakobsson, 2002]
(m2)
Total Arctic surface area (m2)
1109×1010
[Jakobsson, 2002]
-2
Bacterial biomass (g C m )
0.34
[Kirchman et al., 2009]
Phytoplankton shelf biomass (g C m-2)
1.75 (1.00[Kirchman et al., 2009]
2.50)
Phytoplankton Central Basin biomass (g C m-2)
0.50
[Kirchman et al., 2009]
Zooplankton shelf biomass (<82oN) (g dw m-2)
6.9±4.1
[Kosobokova and Hirche, 2009]
Zooplankton Central Basin biomass (>82oN) (g dw
2.5±0.5
[Kosobokova and Hirche, 2009]
m-2)
Zooplankton [MeHg], best estimate (ng g-1 dw)
11 (5-35)
Table S2
Carbon to dry weight plankton
2
[Hedges et al., 2002; Redfield et al.,
1963]
Average precipitation (mm)
340
[Serreze et al., 2006]
Fraction of summer precipitation
0.6
[Serreze and Barry, 2005]
Fraction of ice-free water in summer (Apr-Sept.,
0.65
[Macdonald et al., 2005; NSIDC, 2013]
average)
Fraction of ice-free water in winter (Oct.-March,
0.10
[Macdonald et al., 2005; NSIDC, 2013]
average)
Shelf sediment burial rate (m a-1)
30×10-5
[Kuzyk et al., 2013; Pirtle-Levy et al.,
2009; Polyak et al., 2009]
MeHg (HgII) deposition velocity
1 cm s-1
[Zhang et al., 2009]
Deep sediment burial rate (m a-1)
3×10-5
[Polyak et al., 2009]
Average concentration of Chl a in mixed layer
0.6×10-3
[Galand et al., 2008; Jin et al., 2012]
(mg/L)
Average summer shortwave radiation (W m-2)
160
[Hatzianastassiou et al., 2005]
Concentration of DOC in water column (mg L-1)
0.8
[Dittmar and Kattner, 2003; Hansell et
al., 2012]
Net primary production
0.28
[Arrigo and van Dijken, 2011; Hill et
al., 2013]
Average wind speed at 10 m above sea surface
5.6 (4-6)
[Nummelin et al., 2015; Serreze and
Barry, 2005]
21 430 431 Table 4. External inputs of Hg species to the Arctic Ocean. SI Figure S2 and S3 report uncertainty ranges on
reservoirs and fluxes not given here.
Medium
Total Hg
MeHg
Fraction MeHg (%)
Rain and fresh snow (pM)
Best Estimate for wet
deposition (pM)
Surface snow (pM)
Snowpack (pM)
Runoff (pM)
Best Estimate for melt
water (pM)
Rivers and rivulets (pM)
432 433 434 435 436 437 438 439 440 441 442 443 444 445 446 447 448 449 450 451 452 453 454 455 456 457 458 Best Estimate for rivers
(pM)
Erosion (ng g-1)
Best Estimate for erosion
(ng g-1)
2.6±0.75a
0.13±0.05b
0.80±0.35a
0.50c
0.50 (0.15-0.80)
30a
15.8±15.5d
35.7e
3.5±2.8f
10.2±3.5g
39i
2.6-8.8j
6.7-19.4k
10-250l
170m
3.6±0.8n
5.8±4.8o
10.1±3.2o
15 (2.5-30)
0.25±0.95d
0.1e
0.35±0.15f
1.6d
0.2e
10f
0.37±0.10h
0.35-0.43j
<0.08-0.10k
21-31j
0.77±0.41n
0.31±0.19p
19.9n
3.2p
0.3 (0.1-0.7)
5 (2-20)
45.7±27.5q
61.3±8.2r
35.8s
33.5-67.7t
73v
31, 39, 24, 18, 14x
~0.35q
0.35±0.05r
0.10±0.10u
1.1 (5.2 shelf)q
0.2-1.5r
1.3u
5 (1-10)
114, 61, 67y
81 (61-114)
0
a
[Zdanowicz et al., 2013], fresh snow from Baffin Bay collected in April.
[Hammerschmidt et al., 2006], rain collected from the Canadian Arctic Archipelago collected in June
c
[Lehnherr et al., 2012], rain collected from the Canadian Arctic Archipelago collected in July
d
[St Louis et al., 2005], surface snow from the Canadian Arctic Archipelago collected in April and May
e
[St Louis et al., 2007], surface snow from the Canadian Arctic Archipelago collected In May (median)
f
[Zdanowicz et al., 2013], surface snow from Baffin Bay collected in April.
g
[Poulain et al., 2007], surface snow from the Canadian Arctic Archipelago collected in June
h
[St Louis et al., 2005], fall-winter snowpack from the Canadian Arctic Archipelago
i
[Lu et al., 2001], fall-winter snowpack from the Central Basin collected in November-January
j
[St Louis et al., 2005], spring snowpack from the Canadian Arctic Archipelago in April-May (means), first & second year
snow
k
[St Louis et al., 2007], spring snowpack from the Canadian Arctic Archipelago in May (medians), first and second year
snow
l
[Poulain et al., 2007], spring snowpack from the Canadian Arctic Archipelago in June
m
[Lu et al., 2001], spring snowpack from the Central Basin collected in February to May
n
[St Louis et al., 2005], supraglacial runoff from the Canadian Arctic Archipelago collected in June and July
o
[Zdanowicz et al., 2013], supraglacial runoff from Baffin Bay collected in June
p
[St Louis et al., 2005], subglacial runoff from the Canadian Arctic Archipelago collected in June and July
q
[Graydon et al., 2009], Mackenzie River Canada in June to August
r
[Emmerton et al., 2013], Mackenzie River Canada ice free season
s
[Leitch et al., 2007], Mackenzie River Canada
t
[Wang et al., 2012], Mackenzie River and Horton River, Canada in open water (means)
u
[Zdanowicz et al., 2013], Baffin Bay, Canada in June
v
[Riget et al., 2011a], Zackenberg, Greenland in May to October
x
[Amos et al., 2014], Mackenzie, Lena, Ob, Yenisei, and Kolyma rivers
y
[Leitch, 2006], coastal erosion along the Beaufort Sea coast
b
22 459 Figure captions
460 Figure 1. Recent cruises in the Arctic Ocean that collected samples for Hg species
461 measurements and Arctic Ocean boundaries as specified in this work. Light brown to dark
462 blue toning represents increasing depth. 463 464 Figure 2. Relative distribution of Hg species reservoirs (Mg) in different components of the
465 Arctic Ocean.
466 467 Figure 3. Inputs and losses (Mg a-1) including uncertainty ranges for total Hg. Each ocean
468 depth is indicated by a different color on the plot.
469 470 Figure 4. Total Hg and methylated Hg concentrations in seawater flowing into (red) and out
471 of (blue) the Arctic Ocean. Atlantic Ocean concentrations for each depth interval are based on
472 2013 measurements in the North Atlantic (50°N - 62°N) (Text S1). Pacific Ocean
473 concentrations are from the upper 50 m of the water column close to the shallow sill at the
474 Bering Strait [Sunderland et al., 2009]. We use Hg species concentrations in seawater and ice
475 leaving the Arctic through the Barents Sea, Fram Strait, and Davis Strait (Table 1).
476 477 Figure 5. Reservoirs (Mg) and mass flows (Mg a-1) in the Arctic Polar Mixed Layer and
478 subsurface ocean. Red arrows indicate external sources, blue arrow losses out of the system,
479 black arrows internal fluxes, and white arrows indicate net fluxes. Figure 3 shows fluxes for
480 the deep ocean, which cannot be resolved on species specific basis due to lack of data.
481 482 Figure 6. Simulated impact of atmospheric mercury loading and sea-ice cover on total Hg
483 concentrations in Arctic Ocean seawater. Atmospheric inputs are calculated by scaling current
23 484 Arctic atmospheric inputs by the historical trajectory simulated by Horowitz et al. [2014]
485 based on shifts in global emissions. The trend in sea-ice cover is based on AMAP [2011]. No
486 data are presently available to simultaneously consider changing inputs from the terrestrial
487 landscape and the Pacific and Atlantic Oceans.
488 24 489 Figure 1
90 W
4
Chukchi
Sea
5
East Siberian
Beaufort
Sea
Sea
3
Laptev Sea
Central
Canadian Basin
Archipelago
(CAA)
Kara Sea 2
Lincoln
Sea 85˚N
Baffin
1
Bay
Barents Sea
90 E
180 W
White
Sea
65˚N
Ocean Data View
75˚N
0˚
Arctic Ocean boundary
Marine MeHg obs.
Kirk et al. 2008
Lehnherr et al. 2011 &
Lehnherr et al. 2015
Wang et al. 2012
Heimburger et al. 2015
St. Louis et al. 2007
Zdanowicz et al. 2013
1
2
3
4
5
River locations
Ob River
Yenisei River
Lena River
Kolyma River
Mackenzie River
490 491 25 492 493 Figure 2
Total Hg distribution (Mg)
Ice (15)
Deep sediment
1150
PML (87)
6%
Sub-surface ocean
Methylated Hg distribution (Mg)
Deep sediment (<2)
Shelf sediment (11)
Plankton (<1)
Ice (<2)
420
104
PML (6)
Sub-surface ocean
2360
2750
494 495 Shelf sediment
Deep ocean
Deep ocean
475
26 496 497 Figure 3
498 499 27 500 501 Figure 4
502 503 28 504 505 Figure 5
Polar Mixed Layer (0-20 m depth)
direct deposition
rivers
evasion
8.0
Hg: 1.9
net 90
8390
HgII
73
37
settling
MeHg: 0.1
5.0
2.5
8.5
0.5
photo
12
MeHg
4.0
3.8
0.5
5
net biotic (?)
1.5
20
settling
Hg0
North Atlantic
8300
snow
ice
meltwater
30
50
30
37
Hg: 2.5
MeHg: 0.2
85
coastal erosion
North Atlantic
15
evasion
1.6
Hg: 10
MeHg: 0.8
Me2Hg
2.1
11.5
Subsurface Ocean (20-200 m depth)
HgII
950
MeHg
203
280
930
35
25
Hg: 18
MeHg: 5.0
Me2Hg
70
8
3+
-5*
6+
30*
7.0+
settling
34
net 3
circulation
Hg: 12
MeHg: 0.8
Hg0
settling
North Atlantic
200
North Atlantic
0.1+
1.3*
3.0+
0.9*
circulation
Hg: 3.0
MeHg: 0.3
3.8+
Settling/diffusion/circulation associated with the deep ocean
*Settling/diffusion associated with shelf sediment
+
reservoirs (Mg)
506 507 29 508 509 Figure 6
1.6
External
inputs
relative change
1.5
1.4
PML
1.3
1.2
Historic trends in:
Atmospheric deposition
Atmospheric deposition
& sea-ice cover
1.1
relative change
1.0
1.3
1.2
Deep
water
1.1
1.0
1850
510 Subsurface
water
1890
1930
year
1970
2010
30 511 References
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