GLOBAL BIOGEOCHEMICAL CYCLES, VOL. 25, GBXXXX, doi:10.

1029/2010GB003956, 2011

1 The sequestration sink of soot black carbon in the Northern

2 European Shelf sediments

3 Laura Sánchez-García,1 Ingemar Cato,2,3 and Örjan Gustafsson1

4 Received 15 September 2010; revised 18 October 2011; accepted 27 October 2011; published XX Month 2011.
5 [1] To test the hypothesis that ocean margin sediments are a key final repository in
6 the large-scale biogeospheric cycling of soot black carbon (soot-BC), an extensive
7 survey was conducted along the
2,000 km stretch of the Swedish Continental Shelf
8 (SCS). The soot-BC content in the 120 spatially distributed SCS sediments was
9 0.180.13% dw (median with interquartile ranges), corresponding to
5% of total
0.26

10 organic carbon. Using side-scan sonar constraints to estimate the areal fraction of
11 postglacial clay sediments that are accumulation bottoms (15% of SCS), the soot-BC
12 inventory in the SCS mixed surface sediment was estimated at
4,000 Gg. Combining
13 this with radiochronological constraints on sediment mass accumulation fluxes, the
14 soot-BC sink on the SCS was
300 Gg/yr, which yielded an area-extrapolated
15 estimate for the Northern European Shelf (NES) of
1,100 Gg/yr. This sediment soot-BC
16 sink is
50 times larger than the river discharge fluxes of soot-BC to these coastal waters,
17 however, of similar magnitude as estimates of atmospheric soot-BC emission from the
18 upwind European continent. While large uncertainties remain regarding the large-scale to
19 global BC cycle, this study combines with two previous investigations to suggest that
20 continental shelf sediments are a major final repository of atmospheric soot-BC. Future
21 progress on the soot-BC cycle and how it interacts with the full carbon cycle is likely to
14
22 benefit from C determinations of the sedimentary soot-BC and similar extensive studies of
23 coastal sediment in complementary regimes such as off heavily soot-BC-producing areas in
24 S and E Asia and on the large pan-Arctic shelf.
25 Citation: Sánchez-García, L., I. Cato, and Ö. Gustafsson (2011), The sequestration sink of soot black carbon in the Northern
26 European Shelf sediments, Global Biogeochem. Cycles, 25, GBXXXX, doi:10.1029/2010GB003956.

27 1. Introduction et al., 1997; Gustafsson and Gschwend, 1998; Masiello and 43

Druffel, 1998; Middelburg et al., 1999; Dickens et al., 44
28 [2] Black carbon (BC), the recalcitrant carbonaceous resi-
2004; Lohmann et al., 2009]. While substantial efforts have 45
29 due of incomplete combustion, partakes in several important
been devoted to constrain the BC sources [e.g., Crutzen and 46
30 earth system processes [Goldberg, 1985]. Atmospheric BC
Andreae, 1990; Penner et al., 1993; Kuhlbusch and Crutzen, 47
31 aerosols cause substantial effects on Earth’s radiative balance
1995; Bond et al., 2004], several reviews and commentaries 48
32 through scattering and absorption of sunlight [Kaufman and
have pointed out that much less is understood of the global 49
33 Fraser, 1997; Jacobson, 2001; Chung and Seinfeld, 2002;
BC sinks [e.g., Kuhlbusch, 1998; Schmidt and Noack, 2000; 50
34 Intergovernmental Panel on Climate Change (IPCC), 2007;
Druffel, 2004; Preston and Schmidt, 2006]. We still have 51
35 Ramanathan and Carmichael, 2008]. Once washed out of the
made only limited progress toward answering the funda- 52
36 atmosphere, the recalcitrant BC may affect both the turnover mental question where on Earth does BC go? The partition- 53
37 of the soil organic carbon (OC) pool [e.g., Glaser and
ing of the BC fate between degradation, accumulation in 54
38 Amelung, 2003; Brodowski et al., 2007; Czimczik and
soils, accumulation in oceanic dissolved (DOC) and partic- 55
39 Masiello, 2007; Hammes et al., 2008; Lehmann et al., ulate (POC) OC pools [Dittmar and Paeng, 2009; Flores- 56
40 2008] and be a quantitatively important component of the
Cervantes et al., 2009] as well as burial in sediments have 57
41 sedimentary carbon burial and, thus, removal of carbon from
differential impacts on the interaction of BC with the large- 58
42 rapid cycling in the biogeosphere [Smith et al., 1973; Suman
scale carbon cycle and even on interactions between var- 59
ious carbon pools and a changing climate. For instance, 60
1
Department of Applied Environmental Science and the Bert Bolin inclusion of realistic stocks of BC in soils reduces the 61
Centre for Climate Research, Stockholm University, Stockholm, Sweden.
2
positive feedback to climate warming expected from soil 62
Geological Survey of Sweden, Uppsala, Sweden.
3
Also at Department of Earth Sciences, Göteborg University, Göteborg,
OC [Lehmann et al., 2008] and sedimentary burial of BC 63
Sweden. from biomass burning is a direct sink of CO2–C from the 64
rapidly cycling atmosphere-biosphere system [Kuhlbusch 65
Copyright 2011 by the American Geophysical Union. and Crutzen, 1995; Suman et al., 1997; Gustafsson and 66
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67 Gschwend, 1998; Masiello and Druffel, 1998; Masiello et al., BC, and thus the larger-scale BC cycle, soot-BC is 129
68 2001]. selected for this study. 130
69 [4] While the level of scientific understanding of BC [7] The present study constrains the soot-BC inventory 131
70 behavior in the large-scale system in general has been and sedimentary burial over the spatially extensive region of 132
71 defined as very low [IPCC, 2007], it has been hypothesized the Northern European margin, with the largest coverage to 133
72 that much of the emitted BC eventually is transferred to the date of BC measurements in marine sediments. Comparing 134
73 ocean either through direct atmospheric deposition or after ocean margin soot-BC fluxes with upwind soot-BC pro- 135
74 soil erosion and river runoff [Goldberg, 1985; Suman et al., duction sheds lights on the role of marine sediments in the 136
75 1997; Gustafsson and Gschwend, 1998; Kuhlbusch, 1998; larger BC cycle. The specific objectives of this study were to 137
76 Schmidt and Noack, 2000; Mitra et al., 2002; Druffel, 2004; 1) detail the sedimentary inventory and burial flux of soot- 138
77 Elmquist et al., 2008; Lohmann et al., 2009]. It has been BC on the Swedish Continental Shelf (SCS) with well- 139
78 estimated, based on sparse data, that
90% of the marine defined geophysical and geochemical constraints, 2) extrap- 140
79 BC deposition takes place on the continental margins olate the soot-BC sink flux to the larger NES scale based on 141
80 [Suman et al., 1997], yet the magnitude of the inventory and the high resolution coverage on the SCS and 3) quantitatively 142
81 burial flux of BC in marine sediments remains controversial assess shelf sediment soot-BC burial in the broader context of 143
82 [e.g., Gustafsson and Gschwend, 1998; Dickens et al., 2004; both atmospheric emissions and river discharge of soot-BC 144
83 Masiello, 2004; Elmquist et al., 2008; Lohmann et al., 2009] from the upwind European continent. 145
84 largely due to the scarcity of observations. To better under-
85 stand the life cycle of black carbon it is essential to develop 2. Materials and Methods 146
86 extensive investigations in ocean margins.
87 [5] The few existing studies of BC in ocean margin sedi- 2.1. Sediment Samples and Study Area 147
88 ments are hampered by the small number of observations. [8] Surface sediment samples were obtained from 70 cm 148
89 Previous investigations of this putatively important earth long cores retrieved by the Geological Survey of Sweden 149
90 system for the BC cycle is geographically limited to Santa from 120 locations of the SCS between 1995 and 2006 150
91 Barbara Basin [Griffin and Goldberg, 1975; Masiello and (Figure 1). A Gemini-type gravity corer [Niemistö, 1974] was 151
92 Druffel, 2001], Gulf of Panama [Suman, 1986], New used to retrieve the sediment cores [Cato and Kjellin, 2008]. 152
93 England continental shelf [Gustafsson and Gschwend, The superficial (0–2 cm) section of each extruded sediment 153
94 1998], Washington margin [Dickens et al., 2004], East- core was analyzed for BC in this study. The frozen sediments 154
95 ern [Middelburg et al., 1999] and Western [Lim and were transported in coolers to the laboratory, where they were 155
96 Cachier, 1996] Mediterranean Sea, Northwestern Black stored at 20°C until further analysis. The sedimentation rate 156
97 Sea [Middelburg et al., 1999], North Sea [Middelburg et al., at each station was determined by measuring the activity of 157
98 1999], Arctic Ocean shelves [Elmquist et al., 2008], and the 137
Cs with gamma techniques onboard the survey vessel S/V 158
99 Iberian [Middelburg et al., 1999] and Southern [Lohmann Ocean Surveyor and using the onset of the activity peak from 159
100 et al., 2009] Atlantic margins. Still, an important propor- the 1986 Chernobyl accident as a transient tracer. These 160
101 tion of the ocean sediments remain unstudied for BC in spite samples are expected to have ages of several years – few 161
102 of their key role in the global C cycle as direct sink of CO2–C. decades and are thus influenced by the anthropogenic period. 162
103 To our knowledge, there are no extensive studies conducted [9] The 120 sampling sites were distributed throughout 163
104 on the large Northern European Shelf (NES), despite that a eight marine provinces on the SCS, defined on the basis of 164
105 downwind BC impact has been predicted by models [Chung geophysical criteria such as bathymetry, sedimentology and 165
106 and Seinfeld, 2002] from one of the most densely populated seismic data [Havsområdesregister, 1993]: Bothnian Bay, 166
107 and heavily industrialized areas in the Northern Hemisphere. Bothnian Sea, Stockholm Archipelago, Gotland Sea, Born- 167
108 [6] BC comprises a continuum of carbon-rich particles holm Sea, Arcona Sea, Kattegatt and Skagerrak (Figure 1). 168
109 from incomplete combustion, spanning from large char-BC The six eastern marine provinces compose the Swedish 169
110 particles from residues of vegetation fires to nm-mm sized sector of the Baltic Sea, whereas Kattegatt and Skagerrak are 170
111 soot-BC formed from vapor-phase condensation reactions of transitional areas from the Baltic to the North Sea. Between 171
112 incomplete combustion of fossil fuel and biomass [Hedges 8 and 13 samples were collected from most marine pro- 172
113 et al., 2000; Masiello, 2004]. Char-BC may be a larger vinces. Larger number of samples/observations were taken 173
114 component than soot-BC in soils of fire-prone ecosystems, in the Bothnian (n = 27) and Gotland (n = 19) seas, because 174
115 particularly in less-industrialized regions, whereas smaller- of its greater geographical extent, and in Stockholm Archi- 175
116 sized soot-BC is likely to dominate in long-range transport pelago (n = 26), due to its stronger pollution gradient. 176
117 processes such as through the atmosphere and to the ocean [10] With a predominant SW wind direction in this region 177
118 away from major vegetation fire regions such as off [Soomere and Keevallik, 2001], the SCS is expected to be 178
119 heavily populated and industrialized northern Europe. impacted by windborne BC emissions primarily from sectors 179
120 Consequently, soot-BC is the most commonly studied closest passing over Sweden, St. Petersburg region, Poland, 180
121 form of BC in marine sediments [Elmquist et al., 2008; and Germany. Industrial activity and urban distribution in 181
122 Flores-Cervantes et al., 2009; Gélinas et al., 2001; Guo these areas is described in more detail by Sánchez-García 182
123 et al., 2004; Gustafsson et al., 1997; Lohmann et al., et al. [2010]. 183
124 2009; Louchouarn et al., 2007; Middelburg et al., 1999;
125 Persson et al., 2002; Sánchez-García et al., 2010], as 2.2. Quantification and Characterization of 184
126 well as in some rivers [e.g., Mitra et al., 2002; Mannino Sedimentary Total Organic and Soot Black Carbon 185
127 and Harvey, 2004; Elmquist et al., 2008]. Given the [11] The determination of total organic carbon (TOC) and 186
128 stronger link of the soot-BC component with atmospheric soot-BC in these 120 SCS sediments followed previously 187

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2.3. BC Inventory and Flux Calculations 208

2.3.1. Estimation of Inventories and Fluxes of Soot 209
Black Carbon for the Swedish Continental Shelf 210
[12] To estimate inventories and burial fluxes of organic 211
components in the mixed surface sediments of a given area, 212
several sediment properties must be taken into account, in 213
addition to the organic component (here soot-BC) concen- 214
tration. The soot-BC burial flux was estimated by: 215

Fburial ¼ C ⋅ r ⋅ w ⋅ ð1  fÞ ð1Þ

Where Fburial is the burial flux (mg/cm2⋅yr), C is the soot-BC 216

concentration (mg/g dw), r is the density of the dry sediment 217
particles (g/cm3), w is the sedimentation rate (cm/yr), and f 218
is the sediments porosity (dimensionless). 219
[13] This Fburial is then applied to the corresponding 220
areal extension to calculate the soot-BC inventory (I) in 221
Gg (=109 g) and sink flux (Fsink) in Gg/yr in the given 222
region, according to: 223

I ¼ C ⋅ r ⋅ A ⋅ fab ⋅ Zmix ⋅ ð1  fÞ ð2Þ

Fsink ¼ I⋅w=Zmix ð3Þ

Where A is the area of the given region (km2 converted 224

into cm2), fab is the fraction of this total area (A) that is 225
accumulation bottom (i.e., where sediments do accumulate; 226
Aab/A), Zmix is the average bioturbated mixing depth (cm) 227
and Fsink is the area-integrated sink flux below the zone of 228
mixing in the sediments. 229
[14] The burial flux of soot-BC is first individually cal- 230
culated for the eight SCS provinces (Table 1), according to 231
Figure 1. Map showing the location of the 120 sediment equation (1). In each marine province, the arithmetic mean 232
samples in the Swedish Continental Shelf (SCS) and the soot-BC concentration is used in order to retain the influence 233
BC inventory (Gg) across the eight marine provinces studied of the highest values. For r, we chose a value of 2.5 g/cm3, 234
(delimitated by continuous lines). Yellow and blue patches commonly used as central value for sediment inventory 235
define postglacial clay areas and other types of sediments, calculations [e.g., Emerson and Hedges, 1988; Jönsson et 236
respectively. al., 2003]. Deduced values for the porosity in the sediment 237
mixed layer is frequently in the range 0.7–0.8 [e.g., Emerson 238
and Hedges, 1988; Iversen and Jørgensen, 1993; Boudreau, 239
188 described protocols [e.g., Gustafsson et al., 2001; Sánchez- 1996], with a central value of 0.75 employed for global 240
189 García et al., 2010]. Briefly, the dry and ground sediments inventories [Jönsson et al., 2003]. For Zmix, we used 9.8  241
190 were microacidified (1M HCl) in situ, followed by quanti- 4.5 cm constrained by Boudreau [1996] based on hundreds 242
191 fication of TOC with catalytic combustion elemental analy- of 234Thxs profiles, which takes into account that a fraction 243
192 sis (MicroKemi AB; Uppsala, Sweden). For the soot-BC of the shelf sediment consists of transport and/or erosion 244
193 determination, we applied the well-established chemo- bottoms with limited accumulation. 245
194 thermal oxidation method at 375°C (CTO-375) [e.g., [15] From the 137Cs measurements in the SCS (n = 63) we 246
195 Gustafsson et al., 1997, 2001; Elmquist et al., 2004]. The calculated an average w of 0.73 cm/yr, which was used for 247
196 residual carbon content was determined as soot-BC, after the whole study region. This sediment accumulation rate 248
197 in situ micro acidification as described above. The soot- compares well with an average global w estimate based on 249
198 BC content and its stable carbon isotopic composition applying the empirical relationship established between w 250
199 (d 13C) were measured with an isotope ratio mass spec- and ocean depth [Middelburg et al., 1997] for the depths of 251
200 trometer (Europa Hydra 20/20, Stable Isotope Facility, UC the SCS stations (0.41 cm/yr). The somewhat higher sedi- 252
201 Davis, USA). The limit of quantification (LOQ; defined as mentation rate in the SCS probably reflects the larger runoff 253
202 the mean blank value plus 10 times the standard deviation) and eutrophication of the Baltic Sea, and highlights the 254
203 in this study was 3.3 mg BC per capsule, and the precision importance of using a w value based on field estimations, 255
204 of the method (based on replicate analyses of the certified when available. We note that a higher w would bring a 256
205 reference material SRM-1649a) was established to range corresponding dilution of the concentration of a trace com- 257
206 from 3 to 6% [Gustafsson et al., 2001; Currie et al., ponent such as soot-BC, so that the overall Fburial would be 258
207 2002]. the same. 259

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t1:1 Table 1. Soot-BC Distribution and Fluxes in Surface Sediments Across the Eight Provinces of the Swedish Continental Shelf (SCS)
TOC Soot-BC Soot-BC Soot-BC
Shelf Areaa Medianc Mediand Mediand Meane Fburialf Fsinkf
t1:3 Marine Province (km2) fabb (% dw) (% dw) (% TOC) (% dw) (mg/cm2⋅yr) If (Gg) (Gg/yr)
t1:4 Bothnian Bay (n = 9) 17,515 0.11 3.704.00
3.00 0.100.10
0.08 2.322.47
1.97 0.090.10
0.08 415475
355 103118
88 897
t1:5 Bothnian Sea (n = 27) 35,424 0.14 3.904.60
3.19 0.130.16
0.11 3.303.78
3.06 0.140.15
0.12 631703
558 408455
361 303427
t1:6 Stockholm Archipelago (n = 26) 6,771 0.31 5.156.03
4.23 0.210.28
0.18 3.914.88
3.62 0.230.26
0.20 1,0651,194
936 298334
262 222520
t1:7 Gotland Sea (n = 19) 64,097 0.13 8.2011.8
5.61 0.340.52
0.21 4.615.41
3.63 0.470.65
0.29 2,1362,959
1,313 2,3853,304
1,466 178246109
t1:8 Bornholm Sea (n = 8) 13,139 0.10 4.605.08
4.20 0.240.33
0.21 5.407.02
4.98 0.340.53
0.14 1,5442,427
661 264415
113 20318
t1:9 Arcona Sea (n = 10) 4,183 0.12 4.335.86
2.04 0.220.34
0.18 6.616.98
5.89 0.250.33
0.18 1,1641,519
809
101
7754 648

t1:10 Kattegatt (n = 13) 7,431 0.23 2.633.65

2.37 0.170.21
0.16 6.537.02
5.73 0.180.21
0.16
960
843727 193219
166 141612
t1:11 Skagerrak (n = 8) 6,782 0.30 2.543.33
2.26 0.130.21
0.12 6.107.34
4.84 0.230.37
0.09 1,0461,963
398 284460
108 21348
t1:12 Swedish Continental Shelf (n = 120) 155,342 0.15 4.335.71
3.16 0.180.26
0.13 4.566.11
3.39 0.240.28
0.20 1,1031,281
925
g
4,0114,660
3,363
h
299348251
h

t1:13 a
Sea bottom surface covering the SCS.
t1:14 b
Accumulation bottom fraction: ratio of the accumulation area to the total continental shelf area. The areal-weighted average of the eight marine areas is
t1:15 reported as the fab for the total SCS.
t1:16 c
Total organic carbon content.
t1:17 d
Sub- and superscripts on the median refer to the first and third quartiles, respectively.
t1:18 e
Sub- and superscripts on the mean refer to the lower and upper 95% confidence intervals, respectively.
t1:19 f
Sub- and superscripts indicate the lower and upper 95% confidence intervals propagated from the BC concentration uncertainties.
t1:20 g
Total burial flux in the SCS is calculated by using the soot-BC mean of the 120 sediment samples in equation (1).
t1:21 h
Total inventory and sink flux in the SCS are calculated as the sum of the individual results in the eight marine provinces.

260 [16] The areal extension of accumulation bottom (Aab) inventories and sink fluxes for the entire NES. The NES is 300
261 in each marine province is applied to translate the Fburial here defined to be composed of five marine systems: the 301
262 (mg/cm2⋅yr) into I (Gg) or Fsink (Gg/yr), in equations (2) Baltic Sea, Kattegat, Skagerrak, the Danish Straits (com- 302
263 and (3), respectively. The Aab is approximately propor- posed of the Belt Sea – including Mecklenburg Bay, Kiel 303
264 tional to the extension of the postglacial clay in the SCS Bay, Little Belt and Great Belt – and The Sound), and the 304
265 (Figure 1), which is where sediment accumulation and North Sea (Figure 2). As for the SCS, equations (2) and (3) 305
266 transport occurs [e.g., Håkanson and Jansson, 1983]. In are used for estimating the soot-BC inventory and sink flux 306
267 contrast, non-postglacial clay areas involve dominantly in these five systems, respectively. 307
268 sediment erosion without any sediment accumulation. The [19] For the BC estimations in the complete Baltic Sea 308
269 portion of the postglacial clay areas that are formed by (including the Gulf of Bothnia, Gulf of Finland, Gulf of Riga 309
270 accumulation bottoms was estimated on the basis of and Baltic Proper), we employ the same literature values for 310
271 seismic and hydro-acoustical mapping, using a Chirp r, f and Zmix as described above for the SCS. In the 311
272 side-scan sonar (Datasonics SIS 1000) with TritonElics- extrapolation to the entire Baltic system, we considered the 312
273 ISISA storage and processing systems [Cato et al., 2008]. mean soot-BC content of the 99 sediments sampled from the 313
274 The Stockholm Archipelago was mapped with full side- six Baltic-SCS provinces (Figure 1) as the best representa- 314
275 scan sonar coverage, whereas overview maps were used tive value. For w, we used the mean sedimentation rate 315
276 for the remaining marine provinces, based on the inter- described previously for the total SCS (i.e., 0.73 cm/yr). 316
277 polation of 1 km wide corridors separated by 10 km For A we used the total extension of the Baltic Sea 317
278 along the entire SCS [Cato et al., 2008]. On the basis of (386,700 km2) according to Fonselius [1992], and fab was 318
279 this extensive seismic surveying, it was estimated that the calculated as the ratio of the sum of the Aab in the six 319
280 sediment accumulation area is
50% of the postglacial eastern SCS provinces to the sum of their total areas (A). 320
281 clay areas in the Stockholm Archipelago and
40% in In a similar way, the inventory and flux estimations in 321
282 the other seven SCS provinces. the total Kattegatt and Skagerrak regions were obtained 322
283 [17] The overall BC burial flux in the SCS is eventually from propagating the soot-BC contents of their respective 323
284 estimated by considering the mean soot-BC content of the SCS sub-provinces to their total areas (22,090 km2 and 324
285 total 120 sediments in equation (1). The uncertainties 20,495 km2, respectively [Fonselius, 1992]). The fab cal- 325
286 reported for the total SCS Fburial (expressed as 95% Con- culated for the Kattegatt and Skagerrak sub-provinces 326
287 fidence Intervals) represent the propagated standard devia- were multiplied by their respective total areal extension to 327
288 tion of the mean soot-BC contents in the eight individual estimate the Aab values. For the other sediment properties 328
289 provinces (Table 1). In each province, I and Fsink are derived (r, f, Zmix and w), we used the same values as described 329
290 from the Fburial and the corresponding provincial area (A), above. 330
291 and general values of Zmix and w, according to equations (2) [20] Similar extrapolations are applied in the two remain- 331
292 and (3). Total SCS values of I and Fsink are then calculated ing systems. For the Danish Straits, C and fab are taken from 332
293 by summing up the values of each province. The integrated the neighboring SCS-Kattegatt, assuming a similar BC 333
294 uncertainties of both parameters (Table 1) are based on the deposition, and referred to the corresponding areal extension 334
295 propagation of the soot-BC concentration uncertainties in (21,070 km2 [Fonselius, 1992]). For the North Sea, we used 335
296 each SCS province. the mean soot-BC content (0.18% dw) of six surface sedi- 336
297 2.3.2. Extrapolation to the Northern European Shelf ments studied by Middelburg et al. [1999] in the North Sea, 337
298 [18] We consider the uniquely large observational data set as more directly representative of C in this region. This value 338
299 attained for the SCS as a baseline for estimating soot-BC is similar to the average soot-BC concentration for the SCS 339

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Figure 2. Map (GEBCO_08 grid, version 20091120, available at http://www.gebco.net) showing the BC
sink estimates (Gg/yr) in the five systems of the Northern European Shelf.

340 of 0.24% dw. An average w of 0.42 cm/yr is estimated for sediments, using the same CTO-375 technique for soot-BC 364
341 the North Sea on the basis of the empirical relationship determination, that report mean values from 0.090.12 0.07% dw 365
342 between w and the average depth of the North Sea samples for the Arctic to mean values of 0.340.47
0.21% dw for near-urban 366
343 [Middelburg et al., 1999], following the algorithm given by sediments off NE United States (Table 2). 367
344 Middelburg et al. [1997]. The effective accumulation area [22] Regarding the combustion sources of the soot-BC in 368
345 for the North Sea was obtained from the product of its total the SCS, the relative distribution of specific polycyclic aro- 369
346 continental shelf area (575,300 km2 [International Council matic hydrocarbons (PAH), co-produced with BC during 370
347 for Exploration of the Sea, 1983]) and the mean fab of the incomplete combustion, may provide useful source diagno- 371
348 entire SCS. We consider that averaging the fab values of the sis [e.g., Gustafsson et al., 1997; Elmquist et al., 2007, 2008; 372
349 heterogeneous and extensive SCS constitutes a reasonable Louchouarn et al., 2007]. In a recent study investigating the 373
350 approach, since it is a large set of observation, to use in the controls on the distribution of PAHs in these SCS sediments, 374
351 neighboring North Sea. diagnostic PAH ratios indicated overwhelming pyrogenic 375
signatures in the sediments, apparently derived from grass, 376
352 3. Results and Discussion wood and coal combustion [Sánchez-García et al., 2010]. 377
That earlier study also documented a stronger correlation 378
353 3.1. Concentration and Sources of Soot Black Carbon between PAHs and soot-BC than between PAHs and OC, 379
354 in the Swedish Continental Shelf manifesting a physical coupling in the environment of 380
355 [21] Soot-BC was detected in all 120 surface sediments of these two pyrogenic products. If charring were a problem, 381
356 the eight SCS provinces (Figure 1), at concentrations of the distribution of pyrogenic PAHs in the entire SCS 382
357 0.180.26
0.13% dw (median with interquartile ranges; Table 1). would not have been better explained by (CTO-375) soot- 383
358 Sediments in the Gotland Sea contained the highest soot-BC BC than by OC. 384
359 concentration (0.340.52
0.21% dw, n = 19) and the northernmost [23] The coupling between PAH and soot-BC (and CTO- 385
360 Bothnian Bay the lowest (0.100.10
0.08% dw, n = 9). The overall 375 method functioning in sediments) was also demon- 386
361 mean soot-BC concentrations of the 120 SCS sediments strated in a sediment core study in this region spanning the 387
362 (0.240.28
0.20% dw, mean with 95% confidence intervals) are past 700 years [Elmquist et al., 2007]. The overall parallel 388
363 broadly similar as reports for several other ocean margin distribution of the historically varying CTO375-based BC 389

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t2:1 Table 2. Comparison of BC Concentration and Burial Flux in the Swedish Continental Shelf With Other Marine Systems
BC (% dw) BC (% TOC) Fburial (mg/cm2⋅yr)
t2:3
t2:4 Marine Regime na Range Meanb Range Meanb Range Meanb
t2:5 Swedish Continental Shelfc 120 0.06–1.77 0.240.28
0.20 2–47 564 267–8,067 1,1031,281
925
t2:6 Continental Shelf Regimesd 40 (12) 0.01–0.82 0.150.21
0.09 1–44 162012 2–300 97147
47
t2:7 Pelagic Regimese 44 (23) 0.04–0.82 0.170.23
0.10 3–56 192215 0.5–7.8 3.0
2.31.5
t2:8 Near-Urban Sitesf 10 (4) 0.12–0.69 0.340.47
0.21 3–13 684 470–2,300 1,1301,937
323
t2:9 Subarctic Fjord Systemg 16 0.04–0.73 0.310.39
0.23 4–16 9711
– –
t2:10 Near-Coastal Arctich 20 0.02–0.25 0.090.12
0.07 1–17 810
6 – –
t2:11 a
Numbers in brackets refer to available data for burial fluxes.
t2:12 b
Sub- and superscripts refer to the lower and upper 95% confidence intervals, respectively.
t2:13 c
This study (CTO-375 method).
t2:14 d
According to Griffin and Goldberg [1975] and Suman [1986] (chemical digestion + infrared spectrometric detection), Gustafsson and Gschwend [1998]
t2:15 (CTO-375 method), and Dickens et al. [2004] (CTO-375 method with chemical pre-treatment). These data include also values from Lim and Cachier [1996]
t2:16 (chemical oxidation with K2Cr2O7/H2SO4 + thermal treatment) and Middelburg et al. [1999] (CTO-375 method) for BC concentration, but not for burial
t2:17 fluxes.
t2:18 e
According to Masiello and Druffel [1998] (chemical oxidation with Cr2O7/H2SO4), Middelburg et al. [1999] and Lohmann et al. [2009] (CTO-375
t2:19 method). Burial flux data correspond only to Lohmann et al. [2009].
t2:20 f
According to Gustafsson and Gschwend [1998] and Sundelin et al. [2004] (CTO-375 method).
t2:21 g
According to Persson et al. [2002] (CTO-375 method). This system is heavily impacted by an Al smelter point source.
t2:22 h
According to Guo et al. [2004] and Elmquist et al. [2008] (CTO-375 method).

390 and PAH mirrored the historical energy consumption pat- Table 1). The soot-BC fraction is lowest in the Bothnian Bay 428
391 terns and presumed combustion emission during the last (2.32.5
2.0% TOC) and highest in the southern provinces 429
392 centuries. Historically varying energy consumption and (Arcona Sea, Kattegatt, Skagerrak, Bornholm, Gotland), 430
393 shifts in combustion technology taking place in recent dec- with median soot-BC fractions spanning 4.6–6.6% TOC 431
394 ades in the northern European region, such as decrease in oil (Table 1), consistent with distances to presumed source 432
395 consumption, stricter controls on particle emission, regions on continental Europe [Sánchez-García et al., 2010]. 433
396 improved combustion technologies and a growing replace- The soot-BC fraction of TOC in the SCS is also in the range 434
397 ment of oil-burners with softwood pellet-burners as an of those of other shelf sediments determined with similar 435
398 alternative domestic heating fuel, were consistent with the methods (Table 2). Comparing these results with other 436
399 radiochronologically constrained variations in PAH and soot-BC data generated with the same CTO-375 method 437
400 soot-BC signatures in the sediment core [Elmquist et al., (Table 2), sediments in the marine environment of Gren- 438
401 2007]. Taken together, the spatial distribution and correla- landsfjords (Norway) contained soot-BC at 4–16% of TOC 439
402 tion with co-produced PAHs indicate quality of the obtained [Persson et al., 2002], and Middelburg et al. [1999] 440
403 sediment soot-BC data and suggest that long-range atmo- determined soot-BC fractions ranging from 14% to 51% 441
404 spheric transport of soot-BC from densely populated and of TOC in marine sediments north of the European con- 442
405 industrialized parts of Northern Europe is responsible for the tinent (coastal Atlantic Ocean and North Sea). Amid those, 443
406 obtained patterns. the North Sea sediments contained soot-BC fractions of 444
407 [24] The soot-BC d 13C values varied between 27.8 and 15–51% of TOC [Middelburg et al., 1999]. In summary, 445
408 17.0‰ (23.122.3 24.5‰; Table S1 in the auxiliary there appears to be comparable ranges of soot-BC:TOC in 446
409 material).1 Overall, these heterogeneous isotopic signatures several coastal regimes around Europe. 447
410 are in the range of that of other combustion products (e.g.,
411 PAHs) in aerosols (29 to 21‰ [Norman et al., 1999; 3.2. Burial Flux of Soot Black Carbon in the Swedish 448
412 Okuda et al., 2002; Mandalakis et al., 2004; Sheesley et al., Continental Shelf 449
413 2009]). However, source apportionment based on soot-BC [26] BC burial flux informs about the sequestration of BC 450
414 d13C values is difficult due to (i) overlapping d13C-BC sig- in the sediments. In the SCS, the soot-BC burial flux ranged 451
415 natures of different combustion sources; (ii) the variability of from 267 to 8,067 mg/cm2⋅yr (Table 2) in the eight marine 452
416 the d 13C values depending on both the isotopic signature of provinces. The highest mean fluxes were calculated for the 453
417 the parent fuels [O’Malley et al., 1997; McRae et al., 1999] southeastern provinces of Gotland Sea (2,136 mg/cm2⋅yr) 454
418 and the combustion temperature [McRae et al., 1999]; and and Bornholm Sea (1,544 mg/cm2⋅yr), and the lowest in the 455
419 (iii) the possibility of fractionation during incomplete com- northern Bothnian Sea (631 mg/cm2⋅yr) and Bothnian Bay 456
420 bustion. Therefore, the use of d13C is limited for source (415 mg/cm2⋅yr) (Table 1). These values are, as expected, 457
421 apportionment of environmental soot-BC. substantially higher than reported soot-BC fluxes for 458
422 [25] BC may constitute a significant fraction of the sedi- pelagic/deep-sea sediments (Table 2). The soot-BC burial 459
423 ment TOC due to its recalcitrant character that makes it more fluxes in the SCS are in the high range of results generated 460
424 resistant to degradation than other OC forms. In the SCS, the with the same method in other continental shelf regimes 461
425 TOC content represented 4.335.71 3.16% of the sediment dry worldwide (Gulf of Maine Proper, Santa Barbara Basin, 462
426 weight (median with interquartile ranges; Table 1), from Washington coasts, Gulf of Panama and Saanich Inlet in 463
427 which soot-BC contributed 2–47% of TOC (4.66.1 3.4% TOC; British Columbia; n = 12) (Table 2). The mean Fburial in the 464
SCS (1,103 mg/cm2⋅yr) is similar to that of sediments near 465
1
Auxiliary materials are available in the HTML. doi:10.1029/ metropolitan centers in the NE United States (1,130 mg/cm2⋅yr) 466
2010GB003956. (Table 2), indicating the strength of the heavy influx of 467

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t3:1 Table 3. Estimation of the Soot-BC Sedimentary Inventory and Sink Flux in the Northern European Shelf (NES)
t3:3 System Shelf Areaa (km2) Cb (% dw) fabc Id (Gg) Fsinkd (Gg/yr)
t3:4 Baltic Sea 386,700 0.25 0.13 7,9089,357
6,459 590698
482
t3:5 Kattegatt 22,090 0.18 0.23 573652
494 4349
37
t3:6 Danish Straits 21,070 0.18 0.23 546622
471 4146
35
t3:7 Skagerrak 31,530 0.23 0.30 1,3202,137
503 98159
38
t3:8 North Sea 575,300 0.18 0.15 9,11014,749
3,471 387626
147
t3:9 Northern European Shelf 1,015,620 – – 19,45722,603
16,312 1,1591,346
971

t3:10 a
Total areal extension of the continental shelf in each system.
t3:11 b
Soot-BC concentration in equation (2): for the Danish Straits is considered to be that of Kattegat, for the North Sea is taken from Middelburg et al.
t3:12 [1999], for the rest systems values of this study are considered (Table 1).
t3:13 c
Accumulation bottom fraction: for the Danish Straits is considered to be that of Kattegatt, and for the North Sea the mean value of the eight SCS
t3:14 provinces (Table 1).
t3:15 d
Lower and upper 95% confidence intervals are presented as sub- and superscripts, respectively. In both columns, total values are calculated as the sum of
t3:16 the individual results in the five NES systems.

468 soot-BC to these Northern European coasts. The extensive ranged from 6 to 14 Gg/yr in the Arcona Sea, Bothnian Sea 512
469 coverage of this study allows us to extrapolate the con- and Kattegatt to 178 Gg/yr in the Gotland Sea. The total SCS 513
470 strained burial fluxes determined for the eight SCS pro- soot-BC sink-flux was
300 Gg/yr (Table 1). The extensive 514
471 vinces to even larger scales in this region. soot-BC inventorying of this study provides an opportunity 515
to estimate the magnitude of the soot-BC sink to the total 516
472 3.3. Inventories of Soot Black Carbon in the Swedish NES and to interpret the sedimentary BC fluxes from a 517
473 and Northern European Continental Shelves broader biogeochemical perspective. Because soot-BC is 518
474 [27] The SCS inventory of soot-BC was determined by relatively inert to degradation, its accumulation in marine 519
475 accounting for the fraction of the continental shelf area that sediments represents a sequestration sink of C from the 520
476 is involved in effective sediment accumulation. The inven- global atmosphere-biogeosphere C cycle and the BC sedi- 521
477 tories in the SCS provinces ranged from 77 to 2,385 Gg ment fluxes may provide an independent constraint on 522
478 (Figure 1), with a total SCS stock of
4,000 Gg of soot-BC model estimates of the atmospheric BC emissions. To obtain 523
479 (Table 1). About 87% of the estimated SCS soot-BC stock as accurate estimate as possible, the extrapolations accoun- 524
480 resides in the southern provinces, with Gotland Sea alone ted for the average soot-BC content and the area-weighted 525
481 holding 59% (Figure 1). This is consistent with the location average fab of the eight neighboring SCS provinces 526
482 of this region and expected impact by source regions such as (Table 3). For the North Sea, an average observed soot-BC 527
483 Stockholm and south Sweden, St. Petersburg region, Poland concentration of 0.18% dw by Middelburg et al. [1999] was 528
484 and northern Germany. In addition to proximity to anthro- used for estimating the BC sink flux. We note that this value 529
485 pogenic soot-BC sources, the fraction of sediments that are is quite similar to the mean soot-BC concentration observed 530
486 accumulation bottoms in a SCS province affects its soot-BC for the 120 locations in the SCS of 0.24% dw (Table 2). 531
487 inventory. For instance, the small province of Skagerrak Accordingly, the area-integrated sediment sink fluxes of 532
488 contains a relatively large soot-BC stock (284 Gg), despite soot-BC were calculated to be 590 Gg/yr in the complete 533
489 also a relatively low soot-BC content (mean of 0.23% dw), (SCS + rest of the) Baltic Sea, 43 Gg/yr in Kattegatt, 41 Gg/yr 534
490 which is due to its large fraction of effective accumulation in the Danish Straits, 98 Gg/yr in Skagerrak and 387 Gg/yr in 535
491 (fab = 0.30) (Table 1). In contrast, Arcona Sea (mean BC the North Sea (Table 3 and Figure 2). The total sink flux of 536
492 content of 0.25% dw) yielded a lower soot-BC inventory due soot-BC in the sediments of the NES was thus estimated at 537
493 to its smaller accumulation area (fab = 0.12).
1,100 Gg/yr. This is comparable in magnitude to estimates 538
494 [28] The extensive coverage of this study, encompassing of soot-BC sediment sink fluxes for other marine regimes 539
495 nearly an order of magnitude more spatially distributed such as 400–800 Gg/yr in the extensive New England con- 540
496 observations than any previous shelf sediment study, con- tinental shelf off NE United States [Gustafsson and 541
497 stitutes a useful baseline to extrapolate soot-BC inventories Gschwend, 1998] and 480–700 Gg/yr in the entire South 542
498 to a larger scale. On the basis of these and additional pub- Atlantic shelves and basin [Lohmann et al., 2009] (Table 4). 543
499 lished soot-BC data for the North Sea [Middelburg et al., [30] Based on extrapolations from limited data, there are 544
500 1999], the sedimentary soot-BC inventory in the entire also published estimates of the BC sink flux in the total 545
501 NES was estimated (Table 3). The soot-BC inventories were continental shelf sediments of the entire world of 9,500 Gg/yr 546
502 7,908 Gg (Baltic Sea), 573 Gg (Kattegatt), 546 Gg (Danish of BC (chemical digestion plus infrared spectrometry [Suman 547
503 Straits), 1,320 Gg (Skagerrak) and 9,110 Gg (North Sea). In et al., 1997]) and 16,000–275,000 Gg/yr of soot-BC [Flores- 548
504 total, the five NES marine regimes account for a total soot- Cervantes et al., 2009]. Based on one BC sediment flux data 549
505 BC stock of
19,500 Gg. from the open ocean and six data points from the Washington 550
continental shelf, Dickens et al. [2004] estimated a pre- 551
506 3.4. Sink Fluxes of Soot Black Carbon in the Swedish industrial sink flux of graphitic soot-BC to the world ocean 552
507 and Northern European Continental Shelves sediments of 700 Gg/yr. Their Fsink estimate is based on a 553
508 [29] Accounting for the province-varying accumulation soot-BC determination generated from a variant of the CTO- 554
509 areas, the area-integrated sediment sink fluxes of soot-BC 375 method, where an extra washing step destined to remove 555
510 were computed for each of the eight marine provinces labile organic matter [Gélinas et al., 2001] has been repor- 556
511 composing the SCS (Table 1). The soot-BC sink fluxes ted to be susceptible to lose hydrophobic soot-BC [Elmquist 557

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t4:1 Table 4. Comparison of Soot-BC Sink Fluxes in Surface Sediments With Riverine Export Fluxes and Emission
t4:2 Estimates
t4:4 BC Interface n Fsink (Gg/yr) Source
t4:5 Sediment Sink Fluxes
t4:6 Northern European Shelf 126
1,100 this study
t4:7 New England Shelf 15 400–800 Gustafsson and Gschwend [1998]
t4:8 South Atlantic Shelves + Basin 23 480–700 Lohmann et al. [2009]
t4:9 World continental margins 38 9,500 Suman et al. [1997]
t4:10 World continental margins – 16,000–275,000 Flores-Cervantes et al. [2009]
t4:11 World Ocean 7 700 Dickens et al. [2004]
t4:12
t4:13 River Export Fluxes
t4:14 Mississippi River – 500 Mitra et al. [2002]
t4:15 Chesapeake Bay Rivers – 24 Mannino and Harvey [2004]
t4:16 Pan-Arctic Rivers – 200 Elmquist et al. [2008]
t4:17 Global fluvial export – 12,000 Suman et al. [1997]
t4:18 Global fluvial export – 26,000 Elmquist et al. [2008]
t4:19
t4:20 Atmospheric Emissions
t4:21 Europe (anthropogenic and natural) – 368–1,070 Bond et al. [2004]
t4:22 World (only natural emissions) – 4,700–270,000 Kuhlbusch and Crutzen [1995]
t4:23 World (anthropogenic and natural) – 4,746–19,926 Bond et al. [2004]

558 et al., 2004; Hammes et al., 2007]. This may have resulted impact. The existing broad surveys of extensive regional 597
559 in an underestimation of the global Fsink. In contrast to the shelf systems [Gustafsson and Gschwend, 1998; Flores- 598
560 present study, none of these previous studies have in their Cervantes et al., 2009; Lohmann et al., 2009; this study] 599
561 areal extrapolations accounted for the fact that only a minor are useful building blocks toward a revised and more robust 600
562 fraction of the shelf sediments are net accumulating (i.e., the global estimate. Future investigations should focus on the 601
563 fab factor) and this likely have resulted in the overestimation soot-BC sediment fluxes in coastal sediments of less studied 602
564 of some Fsink estimates, such as the higher range by Flores- regions, such as S and E Asia (enveloping major BC source 603
565 Cervantes et al. [2009]. The existing estimates of the soot- regions) and the Arctic (the world’s largest continental shelf 604
566 BC sink on the entire world continental shelf thus span over system). 605
567 a very broad range from <700 to 275,000 Gg/yr. Based on
568 small data sets, these estimations are furthermore not con- 3.5. The Soot-BC Sink of the Northern European Shelf 606
569 sidering variations in Fburial of the many shelf regimes dif- in a Context of the Soot-BC Biogeospheric Cycle 607
570 fering in regional characteristics such as wind directions, [32] To better understand the global soot-BC cycle it is 608
571 fluvial releases and strongly varying soot-BC source useful to contrast estimates of the soot-BC sediment sink 609
572 strengths from both vegetation fires and anthropogenic with other large-scale soot-BC fluxes across different inter- 610
573 combustion processes. On the basis of the above-described faces in the biogeosphere. For example, soot-BC sediment 611
574 limitations, these existing estimates of the soot-BC sink flux sink fluxes may be compared with soot-BC riverine export 612
575 to the global continental shelf sediments should thus be fluxes to shed light on the relative importance of rivers 613
576 regarded as uncertain. versus atmospheric deposition in delivering soot-BC to the 614
577 [31] Nevertheless, the growing set of observations com- sea. Also based on the CTO-375 method, some important 615
578 bine to suggest that shelf sediments are likely to be a sig- river systems have been found to export coastally 500 Gg of 616
579 nificant final repository in the soot-BC life cycle. Several soot-BC/yr (Mississippi River [Mitra et al., 2002]), 200 Gg 617
580 investigations have documented strongly declining fluxes of soot-BC/yr (the combined seven largest Arctic rivers 618
581 away from the continental sources of BC [e.g., Smith et al., [Elmquist et al., 2008]) and 24 Gg of soot-BC/yr (the rivers 619
582 1973; Suman et al., 1997; Lohmann et al., 2009; Flores- draining into the Chesapeake Bay in the NW Atlantic Ocean 620
583 Cervantes et al., 2009; this study] and combustion marker [Mannino and Harvey, 2004]) (Table 4). Two independent 621
584 PAHs [Gustafsson et al., 1997b], with one synthesis esti- estimates place the global worldwide export of BC by rivers 622
585 mating that 90% of BC burial in marine sediments occur on to the ocean at 12,000 Gg of BC/yr [Suman et al., 1997] and 623
586 the continental shelf, covering just 10% of the World Ocean 26,000 Gg of soot-BC/yr [Elmquist et al., 2008]. Noticeable 624
587 [Suman et al., 1997]. The soot-BC sink fluxes estimated by discrepancies are observed when comparing these global 625
588 the now three extensive regional studies of (i) the New fluvial fluxes with the uncertain estimates of the global 626
589 England continental shelf [Gustafsson and Gschwend, 1998], sedimentary soot-BC sink (Table 4). Given an annual world 627
590 (ii) South Atlantic shelves and basin [Lohmann et al., 2009] river BC discharge between 12,000 and 26,000 Gg of BC, 628
591 and (iii) NES continental shelf (this study) are of similar with an unknown additional input from direct atmospheric 629
592 magnitude and illustrate the potential importance of ocean deposition, the world continental margin sediments are 630
593 margins in accumulating atmospheric soot-BC. More reliable likely burying soot-BC amounts larger than the data-lean 631
594 estimates of the soot-BC shelf sink are likely to develop from global estimate of 9,500 Gg/yr [Suman et al., 1997] but 632
595 such exhaustive studies of key regional continental shelf lower than the upper estimate of 275,000 Gg/yr [Flores- 633
596 regimes, selected to represent distinctly different soot-BC Cervantes et al., 2009], which was also based on a very 634

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635 small observational database with limited geographical is remarkable that all the three, geographically separated, 696
636 coverage (the New England shelf). Given both the river and extensive regional studies of the sedimentary soot-BC sink 697
637 atmospheric input to the ocean, the world ocean should report integrated ocean margin BC sinks that are broadly in 698
638 definitely bury a much larger amount than the estimate of agreement with estimates of upwind atmospheric emissions 699
639 700 Gg of graphitic soot-BC/yr proposed by Dickens et al. and/or deposition of soot-BC [Gustafsson and Gschwend, 700
640 [2004] with a method known to be prone to under- 1998; Lohmann et al., 2009; this study]. 701
641 estimations. These discrepancies illustrate the need to scru- [35] Estimates of global atmospheric BC emissions span 702
642 tinize and revise several of the existing global BC flux over nearly two order of magnitudes from
4,700 to 703
643 estimates. The degradability of BC in natural matrices is 270,000 Gg-BC/yr [Penner et al., 1993; Liousse et al., 704
644 certainly an aspect to take into account [e.g., Middelburg 1996; Cooke et al., 1999; Kuhlbusch and Crutzen, 1995; 705
645 et al., 1999; Hockaday et al., 2006], yet considering that Bond et al., 2004], with the higher end diverging from 706
646 the degradation of up to 50% of sedimentary soot-BC may
19,900 Gg/yr [Bond et al., 2004] to 270,000 Gg/yr 707
647 take a timescale of
10,000 years [Middelburg et al., [Kuhlbusch and Crutzen, 1995] (Table 4). The latter study 708
648 1999], degradation of soot-BC in surface sediments (sev- considers only emissions derived from vegetation fires, 709
649 eral years – few decades) is likely to be minimal. Clearly, whereas the more recent assessment by Bond et al. [2004] 710
650 the revision of the existing global flux estimates requires includes both natural and anthropogenic sources. Key 711
651 particular emphasis on improving the estimate of the shelf aspects to consider in this interpretation are the large 712
652 sediment sequestration. uncertainties in the emission models and potential differ- 713
653 [33] The NES regional shelf sink estimate of
1,100 Gg ences in employed BC analytical techniques. For instance, 714
654 of soot-BC/yr, as well as the two other extensive regional the BC emitted from biomass burning, such as in forest 715
655 shelf studies with similar sink estimates [Gustafsson and fires and wood-fuel combustion, is associated with large 716
656 Gschwend, 1998; Lohmann et al., 2009] are roughly on par uncertainties due to highly variable emission factors [e.g., 717
657 with the magnitude of the soot-BC fluvial discharges. Using Boström et al., 2002; Bond et al., 2004]. These dis- 718
658 the same approach as the two estimates of the global river crepancies put into manifest the need to revise the global 719
659 BC flux [Suman et al., 1997; Elmquist et al., 2008], we BC emission, and call to interpret the existing ones with 720
660 scaled the soot-BC estimates to the North Sea drainage caution. Given existing emission inventories, the soot-BC 721
661 basin by considering the discharge of total suspended sink in the NES represents 0.4–23% of those estimates for 722
662 matter (gdw/yr) via the two major rivers Rhine (2.9⋅1012 the global BC emissions (Table 4). Comparing foremost 723
663 gdw/yr) and Elbe (0.84⋅1012 gdw/yr) [Meybeck and Ragu, with Bond et al. [2004], the NES sediment sink flux is 724
664 1995] and the average soot-BC content in the North Sea about the same as their estimate of BC emissions to the 725
665 surface sediment (0.18% gdw; Table 3). This yields a rough European atmosphere. Despite the large uncertainties 726
666 estimate of soot-BC river discharge of 7 Gg/yr to the North regarding several vectors of the large-scale BC cycle, the 727
667 Sea, which is
2% of its annual sediment sink (Table 3). It shelf sediment sink is clearly an important removal process 728
668 thus appears that direct atmospheric deposition of soot-BC is of soot-BC from active cycling in the global biogeosphere. 729
669 the most important input to the NES system. This soot-BC sediment sink may in systems such as for the 730
670 [34] The sedimentary soot-BC sink estimate for the NES northern European continent serve as an inverse approach 731
671 was consequently also contrasted with atmospheric BC or check on reasonableness of BC emission estimates. 732
672 emissions. Atmospheric BC emissions in Europe, including
673 both contained combustion and open burning are estimated
674 to range 368–1,070 Gg/yr [Bond et al., 2004] (Table 4). This 4. Summary and Conclusions 733
675 is of the same magnitude as the estimated soot-BC sink on [36] The present study contributes to assess the role of 734
676 the extensive NES. However, a direct comparison is com- marine sediments in removing soot-BC from the atmosphere 735
677 plicated for several reasons, including differences in the and large-scale biogeospheric cycling, by constraining the 736
678 analytical methodologies and the potential for additional inventory and sediment flux of soot-BC for both the Swedish 737
679 fluvial input of soil soot-BC that remained on the ground, Continental Shelf (SCS) and the entire Northern European 738
680 formed from lower-temperature biocharring processes. The Shelf (NES). The soot-BC concentrations and burial fluxes 739
681 dominance of southwesterly wind-patterns in the Baltic and were toward the high end of reports for other shelf surface 740
682 the entire NES area [Soomere and Keevallik, 2001] suggests sediments and attests to the substantial soot-BC influx from 741
683 a potential for downwind transport of significant amounts of the highly industrialized and densely populated regions 742
684 soot-BC from the most populated and industrialized regions upwind of NES. 743
685 in Northern Europe (e.g., St. Petersburg area, Poland and [37] The large and geographically distributed sediment 744
686 Northern Germany). Long-range transport from other soot-BC data set allowed estimating the inventories and 745
687 important industrial areas in Europe, such as the United area-extrapolated sink fluxes for the entire region. In contrast 746
688 Kingdom, may also contribute to explain a high soot-BC to earlier studies, this areal extrapolation was attenuated by 747
689 atmospheric deposition in the North Sea. Interestingly, taking into consideration that only
15% of the total SCS 748
690 Chung and Seinfeld [2002] predicted some of the highest and NES area is estimated to host net accumulating sedi- 749
691 atmospheric soot-BC loadings worldwide over Central and ments. Thus, taking into consideration geochemical and 750
692 Northern Europe. This supports the idea that the NES con- geophysical characteristics of sub regimes, well-constrained 751
693 stitutes an important depository of soot-BC at the European estimates were determined for the NES for both the mixed 752
694 scale and, thus, contributes to remove a large amount of BC- surface sediment soot-BC inventory of
19,500 Gg and 753
695 carbon from the atmosphere and the biogeospheric cycle. It shelf sediment soot-BC sink flux of
1,100 GgBC/yr. 754

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755 [38] The current state of our understanding of the soot-BC Cato, I., and B. Kjellin (2008), The National Swedish Status and Trend 819
756 biogeospheric life cycle was assessed by contrasting existing Monitoring Programme based on chemical Contamination in offshore 820
sediment—An overview of the results from 2003. An updated version 821
757 estimates of marine sediment fluxes, river fluxes and atmo- 2008, SGU Rapp. 2008:19, 31 pp., Geol. Surv. of Swed., Uppsala. 822
758 spheric emission fluxes. There are large uncertainties in the Cato, I., B. Håkansson, O. Hallberg, B. Kjellin, P. Andersson, C. Erlandsson, 823
759 current view of the global soot-BC cycle with several of J. Nyberg, and P. Axe (2008), A new approach to state the areas of oxygen 824
760 the previous estimates internally inconsistent. For the deficits in the Baltic Sea, SGU Rapp. Medd., 2008:40, 18 pp., Geol. Surv. 825
of Swed., Uppsala. 826
761 NES, it appears that river soot-BC fluxes account for only Chung, S. H., and J. H. Seinfeld (2002), Global distribution and climate 827
762 a few percent of the sediment soot-BC sink, whereas a forcing of carbonaceous aerosols, J. Geophys. Res., 107(D19), 4407, 828
763 dominant portion of European atmospheric soot-BC emis- doi:10.1029/2001JD001397. 829
Cooke, W. F., C. Liousse, H. Cachier, and J. Feichter (1999), Construction 830
764 sion is matched by the shelf sediment fluxes. Atmospheric of a 1°  1° fossil fuel emission data set for carbonaceous aerosol and 831
765 delivery from industrial regions in Northern Europe (e.g., implementation and radiative impact in the ECHAM4 model, J. Geophys. 832
766 Scandinavia, Poland, Germany, St. Petersburg and United Res., 104(D18), 22,137–22,162, doi:10.1029/1999JD900187. 833
767 Kingdom) is suggested to play a key role in the input of Crutzen, P. J., and M. O. Andreae (1990), Biomass burning in the tropics: 834
Impact on atmospheric chemistry and biogeochemical cycles, Science, 835
768 soot-BC into the NES. This may be similar to the situation 250, 1669–1678, doi:10.1126/science.250.4988.1669. 836
769 on the New England continental shelf, where atmospheric Currie, L. A., et al. (2002), A critical evaluation of interlaboratory data 837
770 emissions from NE United States and shelf soot-BC sink on total, elemental, and isotopic carbon in the carbonaceous particle 838
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790 cycle would likely result from studies involving (i) radio- EMEP air monitoring station in Aspvreten, Sweden, Environ. Sci. Technol., 864
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