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Palaeogeography, Palaeoclimatology, Palaeoecology 501 (2018) 58–69

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Palaeogeography, Palaeoclimatology, Palaeoecology


journal homepage: www.elsevier.com/locate/palaeo

Post-caldera evolution of Deception Island (Bransfield Strait, Antarctica) T


over Holocene timescales
M.C. Muniza, R.M. Anjosa, , R.P. Cardosoa, L.H. Rosab, R. Vieiraa, H. Marottaa, K. Macarioa,

A. Ayres Netoa, J.P. Felizardoa, C.D.N. Barbozaa, L.F. Rodriguesa,c, E.Q. Alvesa,d
a
Instituto de Física e Instituto de Geociências, Universidade Federal Fluminense, Av. Gal Milton Tavares de Souza, s/no, Gragoatá, 24210-346, Niterói, RJ, Brazil
b
Instituto de Ciências Biológicas, Universidade Federal de Minas Gerais, Av. Pres. Antônio Carlos, 6627, Campus UFMG, 31270-90 Belo Horizonte, MG, Brazil
c
Instituto do Petróleo e dos Recursos Naturais, Pontifícia Universidade Católica do Rio Grande do Sul., Av. Ipiranga, 6681 – 96J, 90619-900 Porto Alegre, Brazil
d
Oxford Radiocarbon Accelerator Unit, University of Oxford, Dyson Perrins Building, South Parks Road, Oxford OX1 3QY, United Kingdom

A R T I C L E I N F O A B S T R A C T
T
Keywords: The study of palaeoclimatic changes in fast warming regions can contribute to the understanding of the forcing
Cryoturbation process mechanisms responsible for the global changes that are presently happening. Deception is an active volcanic
δ13C and δ15N island in the Bransfield basin that has a complex history strongly influenced by both magmatic and tectonic
TOC:TN ratio
14
processes. However, without accurate information on the distribution of melt, depth of sediments and Holocene
C dating
timescales of its volcanic eruptions, the models for the post-caldera evolution of Deception Island are poorly
Alluvial sedimentation
constrained. Although this region has undergone severe environmental changes due to recent eruptions, hin-
dering the location of potential study areas of paleo-volcanic eruptions, it is still possible to reconstruct post-
caldera evolution at a local scale. Employing analyses such as radiocarbon dating, stable carbon and nitrogen
isotopic compositions and particle-size distributions in subsoil horizons, we have studied the coastal areas of
Whalers Bay and between Wensleydale Beacon and Cross Hill to identify the major periods of alluvial sedi-
mentation on Deception Island. Whalers Bay was influenced by a large amount of moving water generated by ice
melting. The coastal location of both sampling sites contributes to preserve the sedimentation history in their soil
profiles, despite the severe environmental changes due to recent eruptions. Our findings indicate that from
approximately 13 to 5 cal kyr BP, the accumulation of organic matter was stable and the landforms were not
altered. After that time, post-caldera eruptions occurred, melting the glacier and, consequently, flooding surficial
14
soil layers with mud. These changes are consistent with old C ages for subsoil organic matter and, therefore,
with the occurrence of intense cryogenic disturbance processes.

1. Introduction arcuate and radial faults (Martí et al., 1996; Smellie, 2001 and 2002;
Russell et al., 2014). According to the model proposed by Martí et al.
The study of palaeoclimatic changes contributes to the under- (2013), the caldera was formed during or after a single eruptive event
standing of the forcing mechanisms responsible for the global climate and numerous tectonic faults favored the downward movement of the
changes that have been happening in recent decades (Bentley et al., caldera blocks, destroying the associated magma chamber. Volcanism
2009). In this context, Deception, a Quaternary volcanic island formed then re-ascended, fed by deeper magmas and using the same fractures
on the spreading axis of the Bransfield Strait in the northern Antarctic and faults that controlled the caldera collapse as pathways, as a very
Peninsula (Vaughan et al., 2003), is considered an outdoor laboratory active geothermal system.
for volcano geophysics and phenomena such as debris-flow processes, Unfortunately, the very few published data on the subject prevent a
being the site of several multidisciplinary studies on the origin and satisfactory understanding of the post-caldera geological evolution in
morphology of the South Shetland Islands archipelago (e.g., Smellie, this region. Therefore, our knowledge about the volcanic history of
2002; Lee et al., 2007; Torrecillas et al., 2012 and 2013; Toro et al., Deception Island is incipient and usually related to the approximately
2013; Liu et al., 2016 ; Prudencio et al., 2015 ). Deception Island has 20 eruptions that have occurred in the last two centuries (Roobol, 1982;
traditionally been treated as a < 0.75 Ma collapsed caldera formed by Torrecillas et al., 2012 and 2013). The latest eruptions happened in the
the subsidence of overlapping volcanoes into a magma chamber along late 1960s and 1970s, damaging or even destroying scientific bases on


Corresponding author.
E-mail address: meigikos@if.uff.br (R.M. Anjos).

https://doi.org/10.1016/j.palaeo.2018.04.010
Received 28 June 2017; Received in revised form 6 April 2018; Accepted 15 April 2018
Received 28 June 2017; Received in revised form 6 April 2018; Accepted 15 April 2018
Available online 18 April 2018
0031-0182/ © 2018 Elsevier B.V. All rights reserved.

M.C. Muniz et al. Palaeogeography, Palaeoclimatology, Palaeoecology 501 (2018) 58–69

the island (Baker et al., 1975; Roobol, 1982; Pallas et al., 2001; Smellie, to 800 mm (Bañón et al., 2013). Vegetation on Deception Island is
2002). In terms of scientific research, these recent eruptions tend to characterized by being generally restricted to permanently moisturized
hinder the location of study areas suitable for further study of the areas of stable rock or soil (Downie et al., 2000; Bockheim, 2015). Most
landscape evolution and the soil development of Deception Island, volcanic substrata, especially those evolved from the three 1967–70
mainly during the Holocene (Liu et al., 2016). The few existing geo- eruption episodes (Fig. 1D), are characterized by being unstable, porous
chronological data are based on isochronous tephra deposits and, and arid, being devoid of broad plant communities. Deception Island's
therefore, there is only a relative chronological control for environ- flora encompasses > 70 species of mosses, seven species of liverworts,
mental changes occurred in the region (Lee et al., 2007; Liu et al., and 70 species of lichens (Downie et al., 2000 ). Terrestrial springtails
2016). Several Holocene tephra layers in ice, lake and marine sediment (Collembola: Hexapoda), mites (Acarina: Arachnida) and fresh-water
cores found in the northern Antarctic Peninsula are thought to have nematodes (Nematoda) predominates in the invertebrate fauna
originated from Deception Island's eruptions (Smellie, 2002; Kraus (Downie et al., 2000; Angulo-Precklera et al., 2017).
et al., 2013; Liu et al., 2016 ). Radiocarbon dates from tephra horizons Ice-cemented permafrost is missing on beaches and areas such as
indicate that several eruptions occurred during the last 5.0 cal kyr BP in faults and fumaroles, but occurs widely from sea level to the highest
the area (Lee et al., 2007; Liu et al., 2016 ). However, geochronological peaks (Vieira et al., 2008). Around the shores of Port Foster, the oc-
information is still needed to sustain hypotheses about post-caldera currence of stream-deposited gravelly-sandy sediment is frequent, but
volcanic history and paleo-environmental reconstructions. Fumarole Bay, Whalers Bay and between Wensleydale Beacon and
Geochemical and geochronological analyses such as the determi- Cross Hill this kind of sediment is especially abundant (Smellie, 2001).
nation of stable isotope ratios and radiocarbon dating of the organic Whalers Bay, on the east side of Port Forster (62°58′42″ S, 60°33 ′30″
matter present in sedimentary deposits can provide meaningful in- W, 9 m a.s.l), presents ice-free subpolar areas (Fig. 2). While, the 1967
formation on the complex history of Deception Island during Late volcanic eruption on Deception Island led to the deposition of a 1–5 cm
Pleistocene-Holocene times (Lee et al., 2007; Toro et al., 2013 ; Liu layer of ash over Whalers Bay, the 1969 eruption resulted in a lahar
et al., 2016). The objective of this work is to assess the data from coastal and, consequently, to the partial burial of the site (Smellie, 2001). La-
soils in ice-free subpolar areas of Whalers Bay and between Wensley- hars, also known as volcanic mudflows, are significant amounts of hot
dale Beacon and Cross Hill. These areas were deeply affected by recent or cold melt water, often carrying debris (Jakob and Hungr, 2005;
eruptions that could have promoted changes in the sequences of their Bartolini et al., 2014). Due to their high bulk density and speed, lahars
sedimentary deposits (Smellie, 2002). are very destructive. An example of their damaging power is the de-
struction of the British scientifi c station at Whalers Bay produced by the
2. Study area 1969 eruption (Baker et al., 1975; Smellie, 2002; Bartolini et al., 2014).
Although they can potentially change the sequences of sedimentary
The South Shetland Islands, located in the northern Antarctic deposits, Whalers Bay is still an ideal site for sampling soil/sediment
Peninsula region (Fig. 1A), between the Drake Passage and the Brans- depth profiles to obtain geochemical and geochronological data to as-
field Sea (Fig. 1B), are part of a Mesozoic–Cenozoic magmatic arc that sist in the reconstruction of the post-caldera deposit (alluvial sedi-
opened in a reaction to continental back-arc extension < 1.4 Ma mentation) evolution.
(Fretzdorff and Smellie, 2002; Martí et al., 2013). According to Liu et al. Even though the coastal area between Wensleydale Beacon and
(2016), many active or recently active volcanic centres in the South Cross Hill, on the west side of Port Foster (Fig. 3; 62°56′41″ S
Shetland Islands (e.g., Deception Island, Penguin Island, Bridgeman 060°41′27″ W, 26 m a.s.l), presents heated ground and, therefore, in-
Island), many submarine seamounts and several remnant volcanic direct volcanic hazards (Bartolini et al., 2014), it is considered an area
centres on Livingston, Greenwich, and King George Islands ( Fig. 1B) that does not present extreme events of lahar, constituting an inter-
were developed due to arc magmatism and subsequent rifting. The most esting site to study.
active volcano in this region is Deception Island (62°57′ S, 60°38′ W;
Fig. 1C). It is a young (< 0.75 Ma) horseshoe-shaped stratovolcano 3. Material and methods
(submerged basal diameter ≈ 25 km and emerged diameter ≈ 15 km;
Martí et al., 1996), up to 540 m above sea level (a.s.l.) at Mount Pond 3.1. Sample collection
and 460 m at Mount Kirkwood. Glaciers account for more than half of
the island surficial area (Smellie, 2001 ; López-Martínez et al., 2012). Soil sampling was carried out in two ice free areas of Deception
The centre of the island is a depression, with ≈10 km in diameter and Island: Whalers Bay and between Wensleydale Beacon and Cross Hill,
flooded by a relative sea level change, known as Port Foster, considered during the austral summer 2013/2014. The sampling sites present the
to be the caldera (Martí et al., 2013). On the southeast coast, Port Foster following lithological and physiographic features: sand and gravel as
is connected to the sea via a shallow and narrow passage (Martí et al., bedrock type and Holocene raised beaches at 5–6 m a.s.l. (Figs. 2 and
2013). According to Smellie (2002), although the eruption responsible 3). Soil profiles were collected from pits excavated down to a depth of
for the caldera formation was a large event which may have ex- 60 cm, with a stainless-steel tool to prevent organic contamination.
pelled > 25–30 km 3 of magma, the magnitude of post-caldera eruptions Subsample sets were obtained after sectioning the soil samples at reg-
seems to have been much smaller (typically < 0.05 km 3), forming tuff ular depth increments (5 cm), due to the lack of clear soil horizon dif-
cones and maars with cinder cones and associated lavas. ferentiation. In a few situations, soil profiles displayed colour or grain
The South Shetland Islands experiences a subantarctic maritime size differences, used for sectioning the samples. In the field, soil tem-
climate according to the Köppen climate classification. Deception Island perature was measured at 45 cm depth using a digital thermometer.
has an ET (tundra climate) climate, South Hemispheric Polar Oceanic Sediment samples were kept at −20 °C to preserve the organic matter
(Köppen, 1936; Michel et al., 2014). According to López-Martínez et al. (OM) during transportation to the Fluminense Federal University in
(2012), common weather types connect with cold and dry periods Brazil.
predominant in winter, and the infl uence of the circumpolar trough of
low pressure during summer, with strong westerly wind and wet and 3.2. Sample preparation
relatively warm air masses. The mean annual air temperature at sea
level is ≈ −2.9 °C with extreme monthly temperatures ranging from Samples (200 –300 g) from each layer of the soil profiles were dried
−28 °C to +11 °C (Vieira et al., 2008). Snow cover melting and freeze- overnight in an oven at 60 °C. Dried samples were then homogenized
thaw cycles during summer are favored by such climate conditions after the removal of large rock fragments and biological remains
(López-Martínez et al., 2012). The annual precipitation ranges from 500 through a 2 mm mesh sieve. Old carbon contamination from bedrock-

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M.C. Muniz et al.

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Fig. 1. Geographic location of the study area showing (A) the location of the South Shetland Islands (SSI) relative to the Antarctic mainland; (B) the location of Deception Island; (C) Simplified geological and tectonic map
of Deception Island; and (D) the sites of the recent historical volcanic vents, observable fumarolic activity and heated ground are also indicated. Modified from Liu et al. (2016) and Bartolini et al. (2014).
Palaeogeography, Palaeoclimatology, Palaeoecology 501 (2018) 58–69
M.C. Muniz et al. Palaeogeography, Palaeoclimatology, Palaeoecology 501 (2018) 58–69

Fig. 2. Sampling site on coastal area from Whallers Bay (A-B) and its associated pedon (C-D-E).

Fig. 3. Sampling site on coastal area between Wensleydale Beacon and Cross Hill (A-B) and its associated pedon (C-D).

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M.C. Muniz et al. Palaeogeography, Palaeoclimatology, Palaeoecology 501 (2018) 58–69

Fig. 4. Granulometric distribution in versus depth in soil profiles from (A) the Whallers Bay's and (B) coastal area between Wensleydale Beacon and Cross Hill.

derived lignite and potentially large inputs of penguin guano is asso- spectrometry (AMS- 14C). Samples were prepared and analyzed at the
ciated to larger grains in the sediment (Björck et al., 1991; Zale, 1994). Radiocarbon Laboratory of the Fluminense Federal University - LACUFF
Therefore, in order to minimize this contamination, soil samples were (Anjos et al., 2013; Macario et al., 2013, 2015 ). Since macrofossils
sieved at 0.5 mm. To avoid the interference of inorganic C, carbonates (mosses, algae, and shells) were not found in sufficient amounts to
were removed with acid washing (1.0 M HCl), followed by ultrapure enable specific 14C dating, total soil organic matter (SOM) samples was
water and drying. dated (grains < 0.5 mm). Calibration was performed with OxCal soft-
ware version 4.3 (Bronk Ramsey, 2009a) using the Marine13 curve
(Reimer et al., 2013). Delta R was chosen 200 ± 600 14C yr re-
3.3. Soil analyses and AMS- 14C dating
presenting an additional uncertainty due to an unknown proportion of
organic matter from marine and terrestrial sources. For date sequences
Physical and mineralogical properties of soil were analyzed at the
showing no age inversions, a deposition model P Sequence was applied
Fluminense Federal University. General soil properties analyzed were
with the aim of evaluating the stability of such profile section (Bronk
pH, total organic carbon (TOC), total nitrogen (TN), δ 13C, δ15N, 14C Ramsey and Lee, 2013). A general outlier model with prior probability
age, and texture of the fine-earth fraction (< 2 mm). Soil moisture was
of 5% was used (Bronk Ramsey, 2009b).
determined by the gravimetric method (relative difference between
fresh and dry weights). Matrix grain size was measured by CILAS 1190
particle-size-analyzer following the methods of McCave et al. (1986). 4. Results
Bulk composition and degree of sorting were categorized following the
scheme of Folk and Ward (1957). Soil pH was measured in deionized The material in depth profiles from coastal areas of Whalers Bay
water in 1:1 soil solution ratio, using a pH electrode (Miller and Kissel, (WB) and between Wensleydale Beacon and Cross Hill (CH) are sand
2010). TOC, TN, and 13C and 15N isotope analyses were performed in and microconglomerates, including volcanic fragments and clays
the Department of Plant Sciences at the University of California, USA, at (Figs. 2 and 3). Soil surface on these raised beaches is coarse-textured,
UC Davis Stable Isotope Facility. Soils and sediments samples were being composed mainly of fine sand mixed with varying amounts of
analyzed using an Elementar Vario EL Cube or Micro Cube elemental gravels (1–5 cm diameter). However, the absence of coarse fragments
analyzer (Elementar Analysensysteme GmbH, Hanau, Germany) inter- (> 12.5 mm) at the soil surface in both soil profiles, can be related to
faced to a PDZ Europa 20–20 isotope ratio mass spectrometer (Sercon lower intensity of cryogenic processes in these areas. Along the sedi-
Ltd., Cheshire, UK). Samples were combusted at 1080 °C in a reactor mentary section, the material is essentially the same (gravelly-sandy),
packed with copper oxide and tungsten (VI) oxide. Following com- however, the amount of fine fraction varies, suggesting several sedi-
bustion, oxides were removed in a reduction reactor (reduced copper at ment layers. For instance, the sedimentary sequences observed in pro-
650 °C). The helium carrier then flowed through a water trap (magne- file WB (Fig. 2) are light gray gravelly coarse sand with fragments up to
sium perchlorate). N 2 and CO 2 were separated using a molecular sieve 1 cm (0–9 cm depth); dark gray gravelly coarse sand within muddy
adsorption trap before entering the IRMS. The following reference matrix (9–12 cm depth); light gray gravelly coarse sand with fragments
materials were used: Bovine Liver (δ 13C = −21.69 and δ 15N = −7.72), up to 1 cm (12–17 cm depth); layer composed mainly by gravel size
USGS-41 Glutamic Acid (δ 13 C = 37.626 and δ 15N = 47.6), Nylon 5 material (17–19 cm depth); dark gray gravelly coarse sand within
(δ13C = −27.72 and δ 15N = −10.31), and Peach leaves muddy matrix with millimetric muddy layers (18–26 cm depth); dark
(δ C = −26.12, %C = 46.18, δ 15N = 1.95, and %N = 2.88). Re-
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gray gravelly coarse sand within muddy matrix (26–41 cm depth); dark
plicated measurements of internal laboratory standards indicate that gray gravelly coarse sand (41–43 cm depth), and dark gray gravelly
the analytical precision of the isotopic measurements was within ± coarse sand within muddy matrix (43–50 cm depth).
0.2‰ for carbon and ± 0.3‰ for nitrogen (UC DAVIS, 2015). The contents of the fine fractions (< 2 mm) in WB are slightly
Radiocarbon dates were determined by accelerator mass variable (Fig. 4A), except in 22.5 ± 0.5 cm and 47.5 ± 0.5 cm layers.

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M.C. Muniz et al. Palaeogeography, Palaeoclimatology, Palaeoecology 501 (2018) 58–69

Fig. 5. Distributions of stable carbon and nitrogen isotopic compositions in the Whallers Bay's soil profile (WB).

For most soil layers, the clay content varies between 1.3% and 1.7%, (Fig. 6A-B). The same goes for the distributions of δ 13C and δ 15N,
while the content of sand varies between 71.3% and 77.9% and, silt ranging from −27.4‰ to −21.1‰ and 0.7‰ to 4.9‰ (Fig. 6D-E).
from 20.5% to 27.2%. The clay content is 1.8% and 2.9%, sand is 65.3% TOC:N, in turn, varies gently to 40 cm depth, where there is an abrupt
and 51.7%, and silt is 32.9% and 45.4% for the layers of 22.5 ± 0.5 cm increase. It ranges from 12.2 to 22.9 (Fig. 6C). The chronology of soil
and 47.5 ± 0.5 cm, respectively. The contents of the fine fractions deposition in raised beaches of Whalers Bay and between Wensleydale
(< 2 mm) in the profile CH are also slightly variable (Fig. 4B), showing Beacon and Cross Hill is shown in Tables 1 and 2, respectively.
a similar behavior of profile WB. However, there is an intermediary
subsoil layer enriched in mud (clay contents ranging from 7.3–11.3%).
5. Discussion
In general, in the soils of the Holocene beaches, from upper land-
scape positions downwards, silt and clay contents decrease and sandy
5.1. Soil properties
textures dominate (Navas et al., 2008). Profile WB has muddy-sand
texture throughout the profile, while CH has a muddy texture in its
Since soil formation in the Antarctic environment is largely influ-
central layer. The soil temperature varied between 4.0 and 4.5 °C in
enced by physical processes and rock disintegration (Campbell and
both soil profi les. They had pH ranging from neutral to slightly alkaline
Claridge, 1987), analyses of grain size distribution may help to un-
(6.8 to 7.6), with small depth-related variability, showing no signi ficate
derstand how such processes act on the process of soil development on
difference between the sandy and muddy layers along both soil profiles
different bedrocks (Navas et al., 2008). Soils from ice-free areas of
(Fig. 4A-B). Low values of organic matter were observed, and TOC
Whalers Bay and between Wensleydale Beacon and Cross Hill are eu-
contents had similar depth profile distributions. The depth distribution
tric, with low ornithogenic influence. Low cryoturbic activity is sug-
of TN also exhibits similar patterns in parallel with organic matter.
gested by the absence of coarse fragments at soil surface and angular/
Fig. 5A-B shows the contents of total organic carbon and total ni-
unstained fragments in subsoil. Soils grayish colour indicates low de-
trogen in the profile WB, reported as weight %TOC and %TN of the dry
gree of oxidation (Campbell and Claridge, 1987) and the very low
matter, respectively. The TOC and TN amounts present low values
contents of organic matter suggest they are poorly developed, with
(%TOC < 0.04 and %TN < 0.004). There are small changes in the
physical, chemical and morphological characteristics possibly strongly
compositions of the layers, with no significant statistical variability.
related to their parent materials (Simas et al., 2008). The alluvium and
From very low values (%TOC ~ 0.02) in the bottom samples, the or-
scree deposits in the Whalers Bay are probably originated from the
ganic content increases smoothly up to the 27.5 ± 0.5 cm sediment
Pendulum Cove Formation as indicated by the erosional slopes built up
layer, but then it goes down again to around 0.01 up to the surface.
of volcanoclastic material and fissure-erupted Strombolian scoria and
Similar behavior occurs for the total nitrogen content, increasing at the
gray lavas, where their landforms can have been modified by subglacial
27.5 ± 2.5 cm and 22.5 ± 0.5 cm layers, where it doubles its amount.
eruptions during the Holocene (Smellie, 2001). Since muddy-sand soil
The TN content then drops sharply and rises smoothly up to the surface,
presents reduced water-holding capacity, poor ability to store plant
reaching ~0.003%. According to Fig. 5C, the TOC:TN ratio shows an
nutrients, quick decomposition of OM, and considerable risk of pollu-
inverse behavior to that of TN and organic matter distributions, with a
tant leaching, the coastal area of Whalers Bay is currently highly sus-
minimum value around the depth of 27.5 cm and ranging from 5.1 to
ceptible to wind and water erosion (Haynes, 1998).
8.6. The same goes for the δ 13C distribution, ranging from −24.8‰ to
On the other hand, the amounts of TOC and TN in the profile CH are
−23.0‰ (Fig. 5D). On the other hand, δ 15N behaves similarly to TN
significantly greater than in the WB horizons and the TOC:TN ratio is
and organic matter distributions, with a maximum value around
also significantly higher, showing mud textures in the intermediary
27.5 cm and ranging from 1.3‰ to 6.6‰ (Fig. 5E).
layers of its soil profile. This is because nutrients can have been leached
Although the amount of organic material and total nitrogen are low
from higher parts of the terrestrial ecosystem and accumulated in lower
in both soil profiles, they are more pronounced in the profile CH. Fig. 6
landscape positions. Therefore, the coastal area between Wensleydale
shows the distributions of %TOC, %TN, TOC:N, δ 13C, and δ 15N in this
Beacon and Cross Hill can be related to the mudstone outcrops from the
soil profile. The lowest values of %TOC and %TN are observed in the
White Ash Member of the Pendulum Cove Formation (Smellie, 2001).
soil surface, with a maximum around the layer of 20 cm depth. They
The obtained values of δ 13C in the WB and CH profiles are discussed
range from 0.05% to 0.13% and 0.003% to 0.010%, respectively
from Fig. 9A-C, which are compared with typical ranges for organic

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M.C. Muniz et al. Palaeogeography, Palaeoclimatology, Palaeoecology 501 (2018) 58–69

Fig. 6. Distributions of stable carbon and nitrogen isotopic compositions in the soil profile CH from coastal area between Wensleydale Beacon and Cross Hill.

Table 1 sediment and thus decrease TOC:TN ratios. According to Liu et al.
14
C ages of the bulk sediment samples from soil profile from Whalers Bay. (2006), penguin droppings make the nitrogen concentration of soils
LACUFF Depth (cm) 14
C Calibrated/modelled age (cal yr BP) much higher, whereas carbon content is lowered, especially when
Code conventional compared with black humus of plant origin. Therefore, according to our
age (yr BP) 2σ μ ±σ findings, the main source of organic matter in Whalers Bay is penguin
guano. However, TOC:TN results in the profile CH (Fig. 9D) suggest the
150,250 2.5 ± 2.5 4761 ± 53 6140–3190 4690 ± 750
150,288 12.5 ± 2.5 11,620 ± 200 14,300–10,930 12,760 ± 820
opposite scenario, in which the main source of organic matter in the
150,125 22.5 ± 2.5 10,381 ± 64 12,750–9660 11,290 ± 800 coastal area between Wensleydale Beacon and Cross Hill would be
150,034 27.5 ± 2.5 4622 ± 41 5940–2990* 4520 ± 750 mosses and lichens.
150,035 32.5 ± 2.5 7249 ± 47 8800–6160* 7490 ± 650 Typical values of δ 15N of seabird excrement and soil under its in-
150,126 37.5 ± 2.5 10,215 ± 64 12,630–9510* 11,080 ± 820
fluence range between 6‰ and 26‰ (Wada et al., 1981; Mizutani and
150,127 42.5 ± 2.5 11,019 ± 67 13,420–10,480* 12,010 ± 760
Wada, 1988; Cocks et al., 1998; Liu et al., 2006; Cipro et al., 2011; Nie
Note: *modelled ages obtained from deposition model. For samples 6 to 9, the et al., 2014). For plant samples not significantly influenced by marine
calibrated ages were obtained from a depositional model in the OxCal software animal activity, δ 15N values are in the range from −3.5‰ to 6.6‰ (Liu
while the results for the other samples are independent calibration intervals et al., 2006; Nie et al., 2014). Therefore, Fig. 5E suggests that the
since no assumptions could be made. 2.5 ± 0.5 cm and 27.5 ± 0.5 cm sediment layers in the profile WB
received the highest amount of penguin droppings. On the other hand,
Table 2 the organic matter present in the lowest layers would be mostly com-
14
C ages of the bulk sediment samples of the soil profile from costal area be- posed by plant not signi ficantly influenced by marine animal activity.
tween Wensleydale Beacon and Cross Hill. These hypotheses can be explained by post-depositional processes oc-
LACUFF Depth (cm) 14
C conventional Calibrated age (cal yr BP) curring in ornithogenic soils, which may significantly influence δ 15N
Code age (yr BP) through the decomposition of guano and ammonia volatilization (Nie
2σ μ ±σ
et al., 2014). Moreover, low δ 15N values may indicate that these layers
150,233 7.5 ± 2.5 13,510 ± 130 17,360–13,800 15,590 ± 920 are from places that are not greatly influenced by seabird excrements.
150,234 17.5 ± 2.5 9460 ± 110 12,030 –8700 10,360 ± 810 Relatively large changes of nitrogen isotopic values are possibly re-
150,254 22.5 ± 2.5 10,021 ± 53 12,520–9300 10,820 ± 820 flecting the expected hypothesis of the nitrogen pool being more sen-
150,255 27.5 ± 2.5 11,440 ± 56 13,920–10,910 12,510 ± 770
sitive to isotope changes than the carbon one.
150,235 32.5 ± 2.5 6496 ± 90 8040–5450 6790 ± 650
150,289 37.5 ± 2.5 11,900 ± 95 14,800–11,350 13,150 ± 800
Regarding nitrogen isotopes, Heaton (1986) and Cipro et al. (2011)
150,256 42.5 ± 2.5 10,400 ± 190 12,810–9620 11,320 ± 830 suggest that after deposition, urea and uric acid hydrolysis (producing a
temporary rise in pH) contribute to the formation of ammonia that is
easily volatilized to the atmosphere. Kinetic fractionation resulting
inputs in coastal environments. Their δ 13C values overlap with those of from these procedures leads to strongly 15N-depleted ammonia, while
Antarctic C3 plants (such as lichens, mosses, marine algae, and fresh- the remaining ammonium is 15N-enriched. These fractionations make
water aquatic plants) and fresh Antarctic animal excrements. Organic plants nearby the excrement zone assimilate 15N enriched in inorganic
material in coastal sediments is derived from autochthonous sources (in nitrogen whereas species at upland sites present δ 15N signatures re-
situ sources, such as plants growing on the sediment surface) and al- flecting the δ 15N of the isotopically depleted ammonia source. That
lochthonous sources (organic material transported to the sediment from explains why animal-derived nitrogen uptake is associated with large
elsewhere, such as with the tide, meltwater or a river; Lamb et al., δ15N ranges (Cipro et al., 2011 ). Finally, the δ 15N values observed in
2006). Our sampling sites are predominantly vegetated by lichens and Fig. 6E confirm that the coastal area between Wensleydale Beacon and
mosses. Tree-type C4 plants and terrestrial C3 plants are not found in Cross Hill is enriched by nutrients from mosses and lichens.
Antarctic lands. Additionally, freshwater and marine plants were not
observed on the coastal lands. Therefore, the δ 13C values from the two 5.2. 14
C ages
soil profiles indicate that the organic matter in their sediments are
predominantly composed of remains of terrestrial vegetation (such as Due to the nature of SOM in subsoils, 14 C ages usually increase with
mosses and lichens) and possibly with mixture of fresh Antarctic animal soil depth (e.g. Scharpenseel and Becker-Heidmann, 1989; Paul et al.,
excrements. On the other hand, our TOC:N values in the profi le WB 1997; Krull and Skjemstad, 2003; Eusterhues et al., 2003; Trumbore,
(Fig. 9B) are close to those of fresh animal excrements, but considerably 2009; Schmidt et al., 2011). According to Rumpel and Kogel-Knabner
lower than those of plants. Seabird guano can introduce nitrogen to the (2011), apparent 14C ages of SOM in subsoils may be observed because

64
M.C. Muniz et al. Palaeogeography, Palaeoclimatology, Palaeoecology 501 (2018) 58–69

of continuous microbial recycling of labile material. Components such


as low-density C and microbial phospholipid fatty acids get older while
decomposition rates decrease with depth (Trumbore, 2009). Usually,
mean residence times of up to several thousand years characterize
carbon in deep soil horizons (Rumpel and Kogel-Knabner, 2011;
Schmidt et al., 2011). With few exceptions, the SOM content and its
carbon-to‑nitrogen ratio (TOC:TN) decrease with soil depth, while the
stable C and N isotope ratios (δ 13C and δ 15N) of SOM increases, in-
dicating that OM in deep soil horizons is highly processed (Rumpel and
Kogel-Knabner, 2011). The presence of charred material in volcanic
islands, may explain increases in TOC:TN with depth in a few soils
(Rumpel and Kogel-Knabner, 2011). Additionally, in such context,
topsoil may be affected by modern carbon originated from plants and
droppings from birds that currently inhabit the island. The surface layer
may also have been contaminated by bomb 14 C ( 14C produced by at-
mospheric nuclear weapons testing; Trumbore et al., 1989; Hua et al.,
2013).
According to Tables 1 and 2, a few bulk 14 C ages disclosed dis-
continuities or inversions of the soil layers. This e ffect may be related to
cryoturbation processes in these maritime periglacial environments
with several freeze-thaw cycles. Therefore, 14C dates from SOM are still
important, since they can help to reconstruct the past environments
(Pessenda et al., 2001).
Considering the specific context of the Antarctic region, where the
marine reservoir effect (MRE) is more pronounced than the global
average (Björck et al., 1991 ; Berkman and Forman, 1996; Peck and
Brey, 1996), and the fact that part of the organic matter from soil may
have its origin in penguin guano, the need for considering such effect
when calibrating radiocarbon ages is evident.
According to the 14Chrono Marine Reservoir Database (calib.org/
marine), the mean of the five available values for local marine reservoir
correction is 880 ± 130 14C yr (Björck et al., 1991; Berkman and
Fig. 7. Calibrated radiocarbon ages (gray squares represent 95.4% ranges and
Forman, 1996; Peck and Brey, 1996) for the Antarctic Peninsula region.
circles represent mean values with 1 sigma uncertainties shown) and deposition
Since the relative contributions of marine and terrestrial sources have model versus depth (P sequence parameters are shown; the yellow square
not been established, it is reasonable to consider both possibilities and comprises modelled dates and envelopes 95.4% ranges in light blue). (For in-
to consider an extra uncertainty within the calibration process, that is a terpretation of the references to colour in this figure legend, the reader is re-
Delta R = 200 ± 600, comprising both atmospheric values ferred to the web version of this article.)
(ΔR = −400 14 C yr) and characteristic marine values including the
mean delta R from literature for such region (ΔR = 800 14C yr). rate of 1.95 ± 0.12 cm kyr −1.
From Table 1, one can observe that the 0–5 cm section from the
Contrary to the 14 C age behavior observed in subsoil horizons from
Whalers Bay profile shows an apparent 14C age significantly lower than Whalers Bay, one can see from Table 2 and Fig. 8 that there is no
the 5–10 cm and 10–15 cm sections, suggesting that the organic matter
correlation between the apparent 14C ages and stratigraphic order in
near the surface may have been relocated by physical and chemical the coastal area between Wensleydale Beacon and Cross Hill. 14C ages
processes (Kristiansen et al., 2003). The sections or layers between 5.0 of bulk SOM range randomly from 17 to 7 cal kyr BP, suggesting that its
and 25 cm (7.5 ± 2.5 cm to 22.5 ± 2.5 cm) depth have the highest
subsoil horizons may have been strongly influenced by lateral move-
values of apparent 14C ages, ranging from 14 to 12 cal kyr BP. These ment of material.
findings disclose typical problems associated with 14C dating of SOM in
From Table 1, Figs. 5 A and 7, one can note that the behavior ex-
burial mounds. Besides the occurrence of physical and chemical pro- pected for the vertical distribution of TOC and 14C, respectively, is
cesses near the surface, certain SOM fractions may decompose slowly observed below 27.5 ± 2.5 cm depth in the Whalers Bay's soil profile.
and the SOC, which originates from above and below ground plant There is a positive correlation between the burial depth and the ap-
parts, can be recycled by soil biota. The sum of these processes will parent 14C age of bulk SOM. TOC and TN are decreasing with soil depth,
make organic C in buried soil surfaces appear older than the actual time
while TOC:TN (Fig. 5C), δ 13C (Fig. 5D), and δ 15N (Fig. 5E) of SOM are
of burial (Kristiansen et al., 2003). increasing. Therefore, the accumulation of organic matter is stable from
On the other hand, the organic matter in subsoil horizons below approximately 13 to 5 cal kyr BP and the Whalers Bay landforms were
27.5 ± 2.5 cm depth is characterized by very long turnover times that
not altered (or perturbed) by volcanic eruptions during this period.
increase with depth. This behaviour in the deeper soil horizons is in These findings suggest therefore that the volcanic eruptions on De-
accordance with the representation of soil carbon in ecosystem models ception Island began at about 5 cal kyr BP and are consistent with
(considering stabilized C pools), such as no change in processes or previous results from tephra layer analysis from the South Shetland
constant rates with depth of soil or carbon are expected (Schmidt et al.,
Islands. Previous studies reveal that the primary source of Quaternary
2011). Therefore, the obtained 14C ages below 27.5 ± 2.5 cm depth
tephra deposits to the SSI is the Deception Island volcano, whereas the
were used to build a deposition model using the OxCal software, where island's geomorphic evolution has been controlled by different volcanic
the ages were modelled considering a time/depth sequence (Bronk
eruptions from 5 cal kyr BP to 1970 CE ( Pallas et al., 2001; Smellie,
Ramsey and Lee, 2013 ). Fig. 7 illustrates the relationship between the 2001 and 2002; Lee et al., 2007; Torrecillas et al., 2012; Prudencio
14
C age and burial depth in Whalers Bay profile. The model has an et al., 2015; Liu et al., 2016).
agreement of 100%, which reveals that the accumulation of organic Coastal changes occurred in Whalers Bay can also be understood
matter was stable below 27.5 ± 2.5 cm depth with a mean deposition

65
M.C. Muniz et al. Palaeogeography, Palaeoclimatology, Palaeoecology 501 (2018) 58–69

time of deposition (e.g. about 160% modern at the time of the 1969
eruption, presently 105% modern or lower values before 1950 CE; Hua
et al., 2013) would have produced such results. From the results for the
section below 25 cm, on the other hand, it is possible to state that the
coastal area on Deception Island was disturbed only since the last
5 cal kyr BP. Although this interpretation is based on a single deposi-
tional sequence and more data would be desirable to confirm such
findings, this is the first study to provide subsidies that allow us to
correlate Deception Island's eruptions with the tephra records from the
northern Antarctic Peninsula (Lee et al., 2007; Liu et al., 2016).
Examining the behavior of TOC, TN, TOC:N, δ 13C, δ15N, and 14C
ages in the profile CH (Figs. 6, 8 and Table 2), the findings suggest that
the accumulation of organic matter was not stable and, consequently,
the subsoil layers may have been subjected to mixing processes over
time. Besides the fact that 14 C ages of bulk soil organic matter do not
show a linear relationship with depth, old 14C ages are observed
throughout the soil profile. Both information suggests, therefore, that
this coastal area may have been subjected to more than one reworking/
resedimentation event during the Holocene and it is consistent with the
occurrence of permafrost thaw/glacier melting phenomena from higher
parts and/or subglacial eruptions. Therefore, the profile CH cannot be
used to extract information about the Deception Island evolution over
Holocene timescales.

6. Conclusions

From the analysis of the persistence of soil organic matter as an


ecosystem property, it was possible to predict how the coastal area of
Deception Island responded to landform changes over time by glacial
erosion processes and/or subglacial volcanic eruptions. Deep soil hor-
izons from Whalers Bay indicated that the upper part of the coastal area
Fig. 8. Calibrated radiocarbon ages (squares represent 95.4% ranges and circles
have originated from elsewhere and resedimented there, forming a
represent mean values with 1 sigma uncertainties shown) versus depth. continuous sandy-gravelly beach. The presence of old carbon indicates
that this upper layer may be from glacier melting or permafrost thaw
processes. Because Deception is a volcanic island and previous studies
from data in Table 1 and Fig. 7. They show that the oldest 14C ages of
report the occurrence of subglacial eruptions in Whalers Bay, these
subsoil OM (between 13.5 and 11 cal kyr BP) are observed in upper soil
intense debris flows are consistent with water flow coming from west-
horizons (above 25 cm depth). Considering the complex history of De-
facing slopes of Mount Pound. Unfortunately, the data do not allow us
ception Island during the Holocene, this result suggests that the upper
to know how many post-caldera eruptions occurred for the formation of
part of the section may have originated from elsewhere and re-
the upper layers (above 25 cm deep) of these plains of stream-deposited
sedimented on Whalers Bay. Old OM forms the bulk of the glacier
gravelly-sandy sediment. However, it is possible to indicate that the
carbon pool that accumulated over thousands of years. Glacier melting
accumulation of organic matter was stable on this area from
(or permafrost thaw) stimulates the release of old carbon that will
13 cal kyr BP to 5 cal kyr BP and the Whalers Bay landforms were not
contribute to the occurrence of old 14 C ages in both aquatic and ter-
altered (or perturbed) during this period. Therefore, post-caldera
restrial communities, including SOM (Schuur et al., 2009 ; Schmidt
eruptions began after this time. This result agrees with previous tephra
et al., 2011; Hagvar and Ohlson, 2013). Therefore, the upper soil hor-
layer measurements from solitary beds in lake sedimentary sequences
izons could be associated to processes of cryoturbation in these mar-
on the South Shetland Islands. This is important information that can
itime periglacial environments with several freeze-thaw cycles
help the understanding of landscape changes on Deception Island.
(Chesworth, 2008). Sedimentological processes, such as alluvial sedi-
Moreover, this kind of study can also assist in the understanding of
mentation, can also be originated from lahars (Kataoka et al., 2009).
conditions for cryogenic soil processes that are predicted to dramati-
Comparing the behavior of the TOC, TOC:TN, δ 13C, and δ 15N
cally change in response to the ongoing climate changes.
(Fig. 5A-C-D-E, respectively) of the upper soil horizons with deep soil
horizons (below 25 cm deep) in the profile WB, one can see that they do
Acknowledgments
not exhibit similar patterns. Upper soil horizons show fluctuations,
suggesting that above the 25 cm depth, the physical and chemical
The authors would like to thank the Brazilian funding agencies for
properties of the soil as well as its biogeochemical reactions are un-
their financial support: CNPq (Conselho Nacional de Desenvolvimento
stable and, consequently, this soil layer may have been subjected to
Científico e Tecnológico: 302066/2015-2, 402309/2013-8, 305079/
mixing processes over time.
2014-0 and INCT-FNA, 464898/2014-5), FAPERJ (Fundação Carlos
Considering the soil characteristics observed for the Whalers Bay
Chagas Filho de Amparo à Pesquisa do Estado do Rio de Janeiro: E-26/
(Fig. 4A) and that the subsoil discloses very little horizon differentia-
202.794/2017, E-26/010.001512/2014, E-26/201.413/2014, E-26/
tion, it is not possible to state whether the material reworked/re-
010.003023/2014), and CAPES (Coordenação de Aperfeiçoamento de
sedimented in the upper part of the section (above 25 cm deep) is ori-
Pessoal de Nível Superior: 23038.001227/2014-54). We also thank the
ginated from one single deposition event or if the depositional pattern
INCT-Criosfera (Brazilian National Institute for Cryospheric Science and
has not changed over time. Variable contributions from old material
Technology) and PROANTAR (Brazilian Antarctic Program), and the
(e.g. about 20% modern for the oldest samples dated in the present
team of the 32nd Antarctic Operation of the Brazilian Antarctic
work) transported and material in equilibrium with atmosphere at the
Program (OPERANTAR XXXII) that assisted us at several steps of this

66
M.C. Muniz et al. Palaeogeography, Palaeoclimatology, Palaeoecology 501 (2018) 58–69

13
Fig. 9. Typical δ C and TOC:TN ranges for organic inputs to coastal environments (data compiled from: Prahl et al., 1980; Björck et al., 1993; Meyers, 1994; Tyson,
1995; Galimov, 2000; Gleixner et al., 2002; Gordon and Goñi, 2003; Killops and Killops, 2004; Lamb et al., 2006; Liu et al., 2005 and 2006; Cipro et al., 2011 ; and
13
references therein). The bands in gray represent the range of δ C and TOC:TN values obtained from soil horizons of the Whalers Bay ((A) and (B), respectively) and
between Wensleydale Beacon and Cross Hill ((C) and (D), respectively).

work. region. The Holocene 19, 51 –69.


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