Radiocarbon, 2018, p. 1–30 DOI:10.1017/RDC.2018.

62
© 2018 by the Arizona Board of Regents on behalf of the University of Arizona

MOLECULAR FINGERPRINTING OF 14C DATED SOIL ORGANIC MATTER

FRACTIONS FROM ARCHAEOLOGICAL SETTINGS IN NW SPAIN
Cruz Ferro-Vázquez1* • Joeri Kaal2,3 • Francisco Javier Santos Arévalo4 •
Felipe Criado Boado2
1
Department of Archaeology, University of York, King’s Manor, York, YO1 7EP, United Kingdom.
2
Institute for Heritage Sciences (Incipit), Spanish National Research Council (CSIC), Avenida de Vigo s/n, 15780,
Santiago de Compostela, Spain.
3
Departamento de Edafoloxía e Química Agrícola, Facultade de Bioloxía, Universidade de Santiago de Compostela,
Campus Sur, 15782, Santiago de Compostela, Spain.
4
Centro Nacional de Aceleradores, Universidad de Sevilla, Consejo Superior de Investigaciones Científicas y Junta
de Andalucía. Av. Thomas Alva Edison 7, 41092, Seville, Spain.

ABSTRACT. This paper evaluates the complexities of radiocarbon (14C) dates from soil organic matter (SOM) in
archaeological scenarios. The aqueous NaOH-insoluble residual SOM from Neolithic to medieval sites in NW Spain
produced consistently older calibrated 14C ages than NaOH-extractable SOM. Using pyrolysis-gas chromatography-
mass spectrometry (Py-GC-MS) and thermally assisted hydrolysis and methylation (THM-GC-MS), we analyzed the
molecular composition of these SOM fractions, aiming to understand the differences in 14C ages and to gain insight
on SOM dynamics in relation to age fractionation. The molecular composition of the NaOH-extractable SOM, which
accounts for roughly two-thirds of total SOM, has a larger proportion of microbial detritus than the NaOH-insoluble
SOM. This might suggest that the discrepancies between the two fractions is due to microbial rejuvenation in the
extractable fraction, leading to 14C results that are younger than the activity that is to be dated. However, archaeolo-
gical evidence presented here unambiguously shows that the 14C age of the extractable SOM provides the more accu-
rate age for the targeted activity, and that the insoluble fraction contains inherited old carbon. After statistical data
evaluation using Partial Least Squares-Regression (PLS-R), it is concluded that this inherited SOM is a mixture of
Black Carbon from wild and/or domestic fires and recalcitrant aliphatic SOM.

KEYWORDS: molecular composition, Py-GC-MS, radiocarbon dating, SOM fractions, THM-GC-MS.

INTRODUCTION
In spite of coverage in numerous papers in recent decades, radiocarbon (14C) dating of soil
organic matter (SOM) remains a difficult task. SOM consists of an inherently complex mixture
of substances from different sources as fresh organic tissues, degraded material, and old bio-
logically refractory organic components (Lehmann and Kleber 2015). These materials have
different 14C contents that may either correspond to the present atmospheric 14C, have partially
lost its initial 14C by radioactive decay, or be largely depleted in the case of old inert organic
materials. Due to the intrinsic heterogeneity of SOM, 14C ages have often been inconsistent with
the stratigraphic sequence (Wang et al. 1996; Schmidt et al. 2015). Possible causes of hetero-
geneity in the 14C activity of SOM fractions include bioturbation, leaching, incorporation of
carbonates or deposition of windblown particles containing allochtonous C (Olsson 1974;
Fowler et al. 1986; Martin and Johnson 1995; Blyth et al. 2017; Liu et al. 2017).

In an attempt to tackle these inconsistencies, SOM has traditionally been partitioned into fulvic
acid, humic acid and humin fractions, which are defined by their solubilities in alkaline and acid
solutions. Numerous studies found that fulvic acids provide younger 14C ages than humic acids,
whereas humic acids are younger than humin (e.g in Perrin et al. 1964; Balesdent 1987; Becker-
Heidmann et al. 1988; Pessenda et al. 2001; Cherkinsky and Wallace 2017; Reuther et al. 2017).
On the other hand, Tonneijck et al. (2006) demonstrated that humic acids from Andosols are
immobilized and occluded by chemisorption reactions and aggregation, giving rise to older ages
than humin, which contain more root derivatives which are relatively young. Martin and
Johnson (1995) found that there were no consistently older or younger 14C age relationships

*Corresponding author. Email: cruz.ferrovazquez@york.ac.uk.

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CC 42 3 :586 84 6 C6 CC 5 : 8 / ,
 2 C Ferro-Vázquez et al.

between total SOM (bulk SOM), humic and humin fractions in late Pleistocene loess deposits.
The causes of these divergent results are not completely understood, but several studies point to
the effects of the soil type-specific physico-chemical environment, which determines weathering
and microbial degradation pathways (Balesdent 1987; Balesdent et al. 2000; Trumbore et al
2009; Lehmann and Kleber 2015). Such decay processes have a strong effect on the composition
of the SOM (Suárez-Abelenda et al. 2011; Wang et al. 2016), particularly in the clay-size
fraction where degraded and recalcitrant SOM prevail, whereas the sand fraction has larger
proportions of fresh (particulate) organic remains (Baldock et al. 1992; Kögel-Knabner 2000).
For example, Gilet-Blein et al. (1980) found that the 14C age of the humin fraction was older
than the humic acid fraction in acidic soils, but younger in alkaline soils.

A large part of the research on 14C dating of different SOM fractions was undertaken to identify
the “oldest” fraction, representative of the beginning of soil formation of a buried layer in a
sedimentary sequence (Scharpenseel and Becker-Heidmann 1992; Pessenda et al. 2001). In these
cases, the oldest date, and therefore the oldest SOM fraction, is thought to be the most infor-
mative; the assumption here being that the younger ages of other SOM fractions are due to
rejuvenation by roots, rootlets, low molecular weight mobile constituents (including root exu-
dates), etc. (Wang et al. 1996; Puy et al. 2016). However, in cumulative sequences where soils are
formed in material developed elsewhere (upslope or upstream), the oldest date will probably not
reflect the soil formation after deposition because it includes older SOM from the pre-erosion soil
formation cycle instead, i.e. before redeposition. This applies also to samples from archaeological
sites. In archaeological dating exercises we are not seeking the oldest age of a soil or sediment
layer, but rather the age that corresponds to the human activity involved. It is thus evident that the
assessment of 14C ages requires a good comprehension of the local conditions controlling SOM
dynamics, such as the parent material, pH, and fire regime. In NW Spain, 14C dating of bulk and
alkaline extracted fractions of buried soils under terrace fills has been used to obtain archae-
ologically consistent dates for the construction of ancient agrarian terraces (e.g. Ballesteros Arias
et al. 2006; Puy and Balbo 2013; Ferro-Vázquez et al. 2014; Quirós-Castillo 2014).

It is crucial to stress that even if a date does not fit with an archaeologist’s expectations, this does
not imply that it is “wrong” (Fowler et al. 1986): the calculated age will usually be analytically
correct. It would rather mean that the chosen sample or fraction is not representative for the
event or period of activity in question. In order to reduce uncertainty, the dated sample and the
extraction procedure must meet the following requirements: first, that burial has indeed pro-
duced the isolation of the soil layer from posterior organic matter additions, including illuvia-
tion and percolation processes, to such an extent that the average 14C age is not or barely
affected. Second, that the disturbance of the A horizon during or after burial (by, for example
mixing or bioturbation processes) is limited, and lastly, that the extraction process effectively
prevents older organic matter from being analyzed together with the target fraction (Gilet-Blein
et al. 1980; Matthews 1980; Geyh et al. 1983; Hetier et al. 1983; Martin and Johnson 1995;
Pessenda et al. 2001; Puy et al. 2016). Selecting a fraction that gives the most reliable 14C age on
the basis of the expectations of the researcher may be a source of bias to the interpretation
(Fowler et al. 1986), but, on the other hand, a thorough assessment of archaeological features
may also help to reject unlikely ages.

Here we combine 14C analysis of three fractions (bulk, NaOH soluble and -insoluble SOM) of
samples from archaeological settlements from different periods and spread throughout Galicia
(NW Spain). The dated extracted and residual fractions were analyzed by analytical pyrolysis
(Py-GC-MS) and thermally assisted hydrolysis and methylation (THM-GC-MS), to characterize

2565 7 CC 42 3 :586 8 4 6 0 : 6 :C 7 1: : 68 .D 2C D3 64C C C 6 ,2 3 :586 , 6 C6 7 D 6 2 2: 23 6 2C

CC 42 3 :586 84 6 C6 CC 5 : 8 / ,
 Effect of Age on Soil Organic Matter Composition 3

the macromolecular materials that compose each fraction. These molecular fingerprints are used
as input data in Partial Least Squares models for age and age differences between fractions of the
same sample, in an attempt to unravel the relationship between SOM composition and age. Then,
in the light of archaeological context of each sample, we aim to understand the processes behind
the composition of the fractions that deliver 14C ages that are most consistent with the targeted
archaeological event and elucidate the processes leading to the discrepancies between the different
fractions.

METHODS
Archaeological Sites and Sample Selection
The locations and archaeological context of the 17 samples analyzed are provided in Figure 1
and Table 1. Galicia is located in the NW of the Iberian Peninsula, and its climate is mainly mild
and humid: the sites are located within the “temperate with dry and temperate summer” (Csb)
climate area, according to the Köppen classification (Chazarra et al. 2011). Lithological setting
for each site has been assigned according to the online GEODE cartography from the Spanish
Geological Survey (GEODE-IGME).

Sample Preparation and Radiocarbon Dating

Pretreatment
Samples were dispersed in ultrapure water for 16 hr and wet sieved through a <50 µm mesh,
thereby eliminating sand- and gravel-sized minerals and macroscopic organic remains such as
rootlets. The C and N contents were measured on the <50 µm samples before and after
extraction using a LECO Truspec CHN elemental analyzer with an accuracy of 0.05‰ and
precision of 0.5% for C content, and 0.08‰ and 0.05% for N, respectively.

Figure 1 Map showing the geographic location of the archaeological sites.

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CC 42 3 :586 84 6 C6 CC 5 : 8 / ,
CC
2565 7
42 3 :586

4 C Ferro-Vázquez et al.
Table 1 Sample locations, laboratory codes, and archaeological and lithological settings. Approximate expected ages are in relation to
CC

archaeological evidence and other 14C dates from the same sites.
84

Cultural Approximate Sample

42 3 :586 8 4 6 0 : 6 :C
6 C6

Lab code Site designation expected age Location Lithology Type Structure type References
CNA.1575 Cidade da Medieval Younger than Santiago Amphibolite Agricultural Terrace Soil Ballesteros Arias et al. (2006)
CC

Cultura 1000 yr BP
CNA.1577 A Pousada Medieval Younger than Santiago Amphibolite Agricultural Wall Clay Ballesteros Arias et al. (2009)
5 : 8

1500 yr BP mortar Blanco-Rotea et al. (2010)

CNA.1579 Santa Lucia Medieval Younger than Santiago Amphibolite Agricultural Terrace Soil Ballesteros Arias (2010)
1500 yr BP
CNA.1582 Forno dos Megalithic 6000-4000 yr BP Ortigueira Schist and Funerary Mound Soil Mañana Borrazás (2005)
7 1: : 68
/ ,

Mouros slate
CNA.1583
CNA.1584
CNA.1585
CNA.1590 Punta dos Prados Iron age Around 2000 yr BP Ortigueira Greenschist Hillfort Posthole Soil Ramil González (2000)
.D

Parcero Oubiña et al. (2009)

CNA.1592 Montenegro Medieval Younger than Morrazo Granitoid Agricultural Terrace Soil Gianotti García and Cancela
1500 yr BP Cereijo (2005)
2C

CNA.1593
CNA.1594 Montealegre Iron age Around 2000 yr BP Moaña Granitoid Hillfort Hut wall Clay Aboal Fernández and Castro
mortar Hierro (2005)
D3 64C C C 6 ,2 3 :586 ,

CNA.1603 Coto do Castrelo Medieval Younger than Lalin Schist/ Agricultural Terrace Soil Ballesteros Arias and Blanco
1500 yr BP amphibolite Rotea (2009)
CNA.1604
CNA.1606 Forno dos Megalithic 5500-4000 yr BP Toques Ortogneiss Funerary Mound Soil Criado Boado et al. (1991)
Mouros Prieto Martínez et al. (2008)
CNA.1612 A Lanzada Iron Age Around 2000 yr BP Sanxenxo Granitoid Hillfort Deposit Soil Rodríguez Martínez et al.
(2011)
CNA.1614 Monte Lobeira Megalithic Younger than Vilanova de Granitoid Funerary Trench Soil López-Romero and Mañana
6 C6

4000 yr BP Arousa Borrazás (2013)

CNA.1616 Besomaño Iron age Around 2000 yr BP Ribadumia Granitoid Hillfort Hut floor Soil Aboal Fernández et al.
7 D 6 2 2: 23 6 2C

(2013); Rodríguez Martínez,

(2015)
 Effect of Age on Soil Organic Matter Composition 5

Figure 2 Diagram showing the extraction, analysis and data evaluation protocol.

Extractions
Sieved (<50 µm) samples were chemically fractionated using the standard acid–alkali–acid
procedure for 14C samples. Prior to extraction, carbonates were removed by digestion with 1M
HCl at 75°C for 12 h, followed by washing with ultrapure water until pH > 5 and centrifugation
(3000 rpm, 10 min). The fraction that remained after this acid digestion was air dried at 50°C
and is referred to as SOMBULK.

After homogenization, subsamples of 2 g of SOMBULK were used for the isolation of alkali
soluble and alkali insoluble fractions following two protocols (Figure 2):

1. Hot extraction. After the elimination of carbonates as described above, the soil was extracted
with 0.5M NaOH (30 min, 75°C). Typically, the solution turns dark due to the presence of
humic and fulvic acids. Samples were centrifuged (4000 rpm, 10 min) and the process
repeated until the solution was clear. The supernatant was discarded and the solid residue
was demineralized by 3–5 times mild 2% HF treatment followed by washing of the residue
using several ultrapure water-resuspension-centrifugation-decantation steps until pH
exceeded 5. This treatment eliminates most of the reactive minerals that interfere with
pyrolytic reactions (Zegouagh et al. 2004). Residues obtained in this way were air dried
(50°C) and are called SOMRES, which is considered representative of humin.
2. Cold extraction. After elimination of carbonates, the soil was repeatedly extracted with 0.5M
NaOH (30 min, room temperature), until the supernatant was colorless. After centrifugation
at 3000 rpm for 20 min the extracts from the successive extraction steps were combined and
acidified with 1M HCl to pH = 1 to precipitate humic acid. The supernatant was discarded
and the precipitate was freeze-dried after repeatedly washing it to pH > 5 with ultrapure

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 6 C Ferro-Vázquez et al.

water. The obtained organic matter (SOMEX) is considered representative of the humic acid
fraction.

Because these protocols were not only applied to soil but also two mortar samples, it is noted
that these mortars are made using clay as a binder, not lime. Lime mortars would require
different pretreatment and extraction methods (Heinemeier et al. 2010; Hajdas et al. 2012;
Marzaioli et al. 2013).

Extraction yields were estimated by measuring C contents by elemental analysis of soil material
before and after extraction.

AMS Radiocarbon Dating

The AMS measurements were performed at Centro Nacional de Aceleradores (CNA) in Seville
(Spain). Samples were graphitized using an AGE system that couples an elemental analyzer (for
combustion) to the graphitization line (Wacker et al. 2010b). The amount of sample necessary
to obtain ca. 1 mg of carbon is wrapped in tin foils and combusted in the elemental analyzer and
the gas resulting from the combustion is trapped in a chromatographic column (Santos-Arévalo
et al. 2015). The reduction to graphite takes place in the presence of Fe and takes about 2 hr at
575°C. AMS measurements were done in two different facilities: SARA (Chamizo Calvo et al.
2008) which has been used until 2012, and Micadas (Wacker et al. 2010a) afterwards. Com-
parative exercises have shown statistically similar results in both facilities (Santos Arévalo et al.
2015). 14C ages were calculated using the NIST oxalic acid standard OxII, and corrected for
isotopic fractionation using the simultaneously measured 13C/12C ratio (Stuiver and Polach
1977). Typical background values correspond to ca. 45,000–50,000 yr, and modern samples can
be measured to about 2–3‰ level (Santos-Arévalo et al. 2015).

The 2σ calibrated ages for SOMBULK, SOMRES and SOMEX are given as median probability
for the purposes of the multivariate statistical exercises (AGEBULK, AGERES and AGEEX,
respectively), rounded up after Stuiver and Polach (1977). Following the recommendations on
reporting of 14C activity levels from Reimer et al. (2004), conventional 14C ages, F14C values,
calibrated age ranges and probabilities for each range are given in the Appendix. Calibrations
were made using Calib 7.0.0, with the IntCal13 calibration curve (Stuiver and Reimer 1993;
Reimer et al. 2013). AGEBULK, AGERES and AGEEX have a strong linear correlation with
F14CBULK, F14CRES and F14CEX respectively (r2 > 0.9 in all three cases, p < 0.001).

The discrepancy in F14C between SOMRES and SOMEX fractions, DISCREP(F14C) is calcu-
lated using equation 1 and reported as a percentage:
! " F 14 CRES - F 14 CEX
DISCREP F 14 C ¼ 100 ´ (1)
F 14 CEX

The discrepancy between AGEEX and AGERES (DISCREP) has been calculated, using:
AGERES - AGEEX
DISCREP ¼ 100 ´ (2)
AGEEX

The resulting values are included in Table 2. DISCREP(F14C) and DISCREP are only weakly
correlated (r2 = 0.35, p < 0.05) because F14C is a direct measure of the 14C activity of the sample,

2565 7 CC 42 3 :586 8 4 6 0 : 6 :C 7 1: : 68 .D 2C D3 64C C C 6 ,2 3 :586 , 6 C6 7 D 6 2 2: 23 6 2C

CC 42 3 :586 84 6 C6 CC 5 : 8 / ,
 Effect of Age on Soil Organic Matter Composition 7

which results from the atmospheric 14C and that has not been constant through time, while
DISCREP is calculated using calibrated values.

Molecular Composition
Conventional Analytical Pyrolysis (Py-GC-MS)
Approximately 1 mg of sample was inserted into quartz tubes with quartz wool at both ends.
Pyrolysis was performed with a CDS Pyroprobe 5250 for 20 s at 750°C (10°C/ms heating rate).
The pyrolysis products were separated on a 6890N gas chromatograph (Agilent Technologies)
under He flow (1 mL/min), using a HP-5MS polysiloxane-based column (temperature program
50–325°C at 20°C/min), and identified using an Agilent 5975 mass selective detector operating
in 70 eV electron impact mode (m/z 50–500). The relative proportions of each pyrolysis product
were calculated as the percentage of the sum of all peak areas (% of total quantified peak area,
% TQPA). Replicate analyses were performed for the extracts only. Average values of the
replicates were used to calculate coefficients of determination (r2) and for evaluation by means
of multivariate statistics.

Thermally Assisted Hydrolysis and Methylation (THM-GC-MS)

The THM-GC-MS analyses were performed under the same conditions as for Py-GC-MS, but
with prior addition of an aliquot of tetramethylammonium hydroxide (TMAH, 25% in water,
Sigma Aldrich), and a pyrolysis set point temperature of 600°C instead of 750°C (Challinor
2001). The SOMEX fractions of all samples were analyzed but only two of the SOMRES samples
were analyzed due to the poor signal obtained.

Data Evaluation
The data were evaluated using ANOVA (SPSS 24) for identification of differences in a con-
tinuous variable in relation to the values of an independent discrete variable. Correlations are
presented in the text as r2, and significance reported as p values. Partial Least Squares
Regression (PLS-R) was done using the PLS package of R statistical environment R3.2.1
(R Core Team 2014) to generate models that explain the relationship between molecular
composition and age, and between molecular composition and the discrepancy between frac-
tions (DISCREP) for both SOMEX and SOMRES. Further details on this technique can be
found in (Abdi 2010). Given the strong correlation between calibrated ages and F14C values of
each fraction (r2 > 0.9, p < 0.001), the models built for AGERES and AGEEX are also valid for
F14CRES and F14CEX. On the contrary, the models built targeting DISCREP cannot be extra-
polated to DISCREP(F14C) because they do not covariate.

RESULTS AND DISCUSSION

Radiocarbon Data, Extraction Yields, and Age Discrepancy
The ages obtained for SOMBULK and SOMEX were similar (r2 = 0.98, p < 0.001, Table 2) with a
difference of only 6% (average) ± 15% (SD). The medians of the calibration intervals for the
residues and the extracts are correlated (r2 = 0.82, p < 0.001), AGERES being 70 ± 65% older
than AGEEX (ANOVA significance p < 0.001). DISCREP is not correlated to the age of any of
the fractions.

The estimated yields show that SOMEX corresponds to 63 ± 9% of the SOM (measured as C %)
of the samples, whereas SOMRES accounts for 26 ± 9% of the SOM (Table 2). Hence, SOMEX

2565 7 CC 42 3 :586 8 4 6 0 : 6 :C 7 1: : 68 .D 2C D3 64C C C 6 ,2 3 :586 , 6 C6 7 D 6 2 2: 23 6 2C

CC 42 3 :586 84 6 C6 CC 5 : 8 / ,
CC
2565 7
42 3 :586

8 C Ferro-Vázquez et al.
CC
84

Table 2 Sample codes, median age of the probability distribution of bulk, residual and extracted fractions (AGEBULK, AGERES, AGEEX),
42 3 :586 8 4 6 0 : 6 :C
6 C6

difference between AGERES and AGEEX in years (Dif.), age discrepancy (according to equation 1), F14C discrepancy (according to equation 2),
elemental composition (% C and C/N [wt/wt] ratio), sample clusters based on the relation of AGEBULK and C content (Group, see text) and yields
for the extractable and residual fraction (as % of total SOM).
CC 5 : 8

YIELDEX YIELDRES
DISCREP C (C in extract (C in residue
DISCREP (F14C) (<50 μm) C/N after cold after hot
Lab code AGEBULK AGERES AGEEX Dif. (%) (%) (%) (<50 μm) Group extraction) (%) extraction) (%)
7 1: : 68
/ ,

CNA.1575 950 1944 730 1216 165 –13.7 3.6 9.5 B 67 20

CNA.1577 2790 5810 2620 3205 122 –26.8 1.5 10.7 B 58 28
CNA.1579 1130 2570 1020 1560 153 –15.5 2.7 9.7 B 58 23
CNA.1582 7530 12930 6490 6445 99 –48.7 1.7 12.4 C 59 26
.D

CNA.1583 4410 9120 4670 4447 95 –39.7 3.6 13.7 C 66 15

CNA.1584 5820 9610 5810 3785 65 –36.0 3.4 13.6 C 69 15
CNA.1585 7080 9950 6280 3634 58 2.9 12.5 C 63 17
2C

–34.1
CNA.1590 2360 5450 1850 3619 195 –29.6 1.0 11.0 B 39 36
CNA.1592 1160 1330 1240 87 8 –1.7 10.3 12.2 A 71 32
CNA.1593 1250 1330 1270 56 5 –1.2 10.0 12.4 A 70 46
D3 64C C C 6 ,2 3 :586 ,

CNA.1594 1490 2620 1480 1139 77 –10.9 2.2 10.7 B 70 20

CNA.1603 1260 1790 1120 655 60 –7.7 2.8 9.0 B 65 22
CNA.1604 1440 2620 1330 1300 97 –13.0 1.6 10.3 B 58 28
CNA.1606 6240 6470 6100 336 6 –4.1 7.6 17.1 C 69 28
CNA.1612 2100 2410 2030 358 19 –3.7 10.4 19.4 A 76 17
CNA.1614 2770 2800 2800 18 0 –0.3 12.7 22.2 A 74 34
CNA.1616 1930 1250 1880 –628 –34 8.0 11.9 21.9 A 62 34
6 C6
7 D 6 2 2: 23 6 2C
 Effect of Age on Soil Organic Matter Composition 9

Figure 3 Sample groups according to age and soil organic matter content: (A) calibrated age of bulk (<50 µm
fraction) samples plotted against carbon content of the same bulk fraction; (B) the discrepancy between the calibrated
age of the NaOH-soluble and -insoluble fractions (DISCREP, Eq. 1) plotted against carbon content of the bulk
fraction.
represents a larger proportion of the SOM than SOMRES, which is in agreement with the fact
that AGEEX is more similar to AGEBULK than is AGERES (Table 2).

If age (AGEBULK, for illustration) is plotted against SOM content, the samples group in three
clusters (Figure 3a). The relatively young samples (<4000 cal BP) split in two groups, one with
high C content (10–15%; Group A) and one with low C content (<4%; Group B). The relatively
old samples (>4000 cal BP) have low C content as well (2–8%; Group C). There is a clear
negative correlation (r2 = 0.68; p < 0.001) between SOM content and the discrepancy between
fractions (DISCREP, Figure 3b), and DISCREP is significantly different (p < 0.001) for the
samples of Group A (0 ± 20%), Group B (124 ± 49%) and Group C (65 ± 37%). SOM content is
negatively affected by the intensity of mineralization, which is reflected by a positive correlation
between %C and C/N (r2 = 0.64, p < 0.005). The negative correlations between DISCREP and
%C (r2 = 0.68, p < 0.001) and DISCREP and C/N (r2 = 0.50, p < 0.001) indicate that SOM
degradation degree may affect DISCREP values. Indeed, the C/N ratio is higher (p < 0.001) for
samples from Group A (18 ± 5) than Group B (10 ± 1) and Group C (14 ± 2) (Table 2). This
suggests that differences in SOM content between samples of Group A and Group B (which
have a similar age) are due to a better SOM preservation in Group A (from a different point of
view, accelerated SOM decay in Group B samples). There are no correlations between
DISCREP and the yields of SOMEX and SOMRES, and there are no significant differences for
the SOMEX and SOMRES yields of the three clusters. The value of DISCREP is thus indepen-
dent from the extractability of the samples (i.e. relative proportions of humic acid and humin).

Molecular Characterization of SOM Fractions

Pyrolysis-GC-MS
The SOMEX and SOMRES produced the same set of pyrolysis products (Supplementary
Information 1), albeit in considerably different relative proportions. The monocyclic aromatic
hydrocarbons (MAHs) are the most abundant group of compounds in both SOMEX
(53.0 ± 15.0% of TQPA) and SOMRES (58.0 ± 5.9%). In both fractions, benzene and toluene
dominate. In SOM admixtures, MAHs originate predominantly from degraded and microbial
SOM (particularly toluene) and pyrogenic SOM (PySOM) from fire residues (particularly
benzene; Buurman et al. 2006; Kaal et al. 2008a; Buurman and Roscoe 2011).

Polycyclic aromatic hydrocarbons (PAHs) such as indenes, naphthalenes, and biphenyls,

account for 2.5 ± 1.0% of TQPA in SOMEX and 12.0 ± 2.3% in SOMRES. Even though these

2565 7 CC 42 3 :586 8 4 6 0 : 6 :C 7 1: : 68 .D 2C D3 64C C C 6 ,2 3 :586 , 6 C6 7 D 6 2 2: 23 6 2C

CC 42 3 :586 84 6 C6 CC 5 : 8 / ,
 10 C Ferro-Vázquez et al.

compounds can be formed as secondary reaction products of non-pyrogenic SOM components

(Saiz-Jimenez 1994), they are also known as typical PySOM products (González-Vila et al.
2001; Ross et al. 2005; Rumpel et al. 2007). The very high abundance of PAHs in the SOMRES
fraction is an especially strong indication of a major proportion of PySOM.

Methylene chain compounds (MCC; n-alkanes, n-alkenes and n-alkanoic acids) account for
15.5 ± 3.4% of TQPA in SOMRES. They are dominated by C10-C33 n-alkanes and C12-C31
n-alkenes (95 ± 9% of total MCC). In Py-GC-MS fingerprints, the long chain n-alkanes (C27 and
higher) often originate from vegetal epicuticular waxes whereas the shorter products originate
from aliphatic biopolymers such as cutin, suberin, cutan and suberan (Nip et al. 1986; Tegelaar
et al. 1989; Kolattukudy 2001). The variation in the proportion of MCC is much larger for
SOMEX, i.e. 13.2 ± 17.5% of TQPA, as most extracts have a low MCC proportion (n = 12,
3.5 ± 2.9% of TQPA) except a few samples that have very high proportions (samples from
Group C, n = 5, 22–58%). Contrary to SOMRES, in SOMEX the n-alkanoic acids (mostly C16
and C18 fatty acid), from free or esterified vegetal or bacterial fatty acids, are more abundant
than n-alkanes and n-alkenes (56 ± 20% of total MCC). Hence, SOMEX contains few aliphatic
SOM structures with the exception of samples from Group C that are prolific of fatty acids,
whereas SOMRES stores primarily aliphatic biopolymers.

Pyrolysis products with at least one nitrogen atom are more abundant in SOMEX (15.4 ± 8.2%)
than in SOMRES (8.0 ± 2.2%). The majority of the N-compounds originate predominantly
(e.g. pyrroles, pyridines and indoles) or exclusively (e.g. acetamide) from proteins and chitin
(a microbial polysaccharide) from microbial SOM components (Van der Kaaden et al. 1984;
Tsuge and Matsubara 1985). In addition, benzonitriles and isoquinoline are products of
N-containing groups in PySOM (Kaal et al. 2008b). In the pyrolysates of SOMEX, the sum
of N-containing products is negatively correlated to the C/N ratio of the bulk samples (r2 = 0.52,
p < 0.005). This negative correlation is also significant for all N-compounds individually
except for benzonitrile, which has a weak positive correlation with C/N (r2 = 0.23, p < 0.05).
These results show that the pyrolysis fingerprints are coherent with the elemental composition,
and suggest that microbial SOM is represented by the N-compounds except for benzonitrile,
which is related to PySOM and therefore to a larger abundance of C-rich charcoal-
derived SOM.

Products that can be traced to carbohydrate precursors such as acetic acid, furans and fur-
aldehydes (Pouwels et al. 1989) are concentrated in SOMEX (13.3 ± 8.3%, against 2.1 ± 1.3% in
SOMRES). The lack of products of (intact) plant-derived polysaccharides such as pyrans or
anhydrosugars suggests that the carbohydrate products should be attributed to degraded and
microbial material (Schellekens et al. 2009), in addition perhaps to weakly charred poly-
saccharides in PySOM (Pastorova et al. 1994). Finally, phenolic compounds (phenol, alkyl-
phenols and acetophenone) account for 2.6 ± 1.2% in SOMEX and 4.4 ± 2.1% in SOMRES. The
phenols probably originate from strongly altered lignin and/or microbial products (Tsuge and
Matsubara 1985; Kracht 2001). Lignin markers from Py-GC-MS (guaiacols and syringols)
were below the detection limit, but their unambiguous detection by THM-GC-MS (see below)
suggests that the phenols are mostly pyrolytic alteration products of degraded lignin.

In summary, SOMEX is composed primarily of microbial SOM, whereas PySOM and aliphatic
SOM are scarce (although clearly recognizable) with the exception of several samples with a
significant fatty acid content. The pyrolysates of SOMRES, on the other hand, originate pre-
dominantly from aliphatic biopolymers and PySOM, whereas microbial SOM is a relatively
small constituent. These results are in agreement with previous research that studied the

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 Effect of Age on Soil Organic Matter Composition 11

molecular composition of NaOH-soluble and NaOH-insoluble SOM fractions (Verde et al.

2008; Suárez-Abelenda et al. 2011; Schellekens et al. 2017).

From ANOVA analysis, the SOMEX of Group B samples is enriched (p < 0.05), relative to
Group A and Group C, in the products of microbial SOM (polysaccharide products,
N-compounds except benzonitrile). This implies that the relatively young samples with low
SOM content and high DISCREP are enriched in microbial products in SOMEX. The SOMEX
of samples in Group C is enriched in products of PySOM (benzene, PAHs, benzonitrile) and
aliphatic SOM (detected as fatty acids). The large proportion of fatty acids in the oldest samples
was not expected, as they tend to be less abundant in pyrolysates of “evolved” SOM due to
degradation (Buurman et al. 2006). We do not have a definite explanation for this observation,
but we cannot exclude the possibility that these compounds had remained trapped in or bound
to charcoal particles and thereby survived long-term storage. For the SOMRES fraction, the
differences between the three clusters were less informative. Suffice it to mention that the
SOMRES of Group B is enriched in pyrolysates of aliphatic biopolymers (represented by
n-alkanes/n-alkenes), whereas samples in Group A are enriched in phenols, probably from lignin.

THM-GC-MS
Among the THM-GC-MS products of SOMEX, the C12-C32 fatty acid methyl esters (FAMEs)
and C10-C30 ω-methoxy FAMEs are the most abundant group of compounds (45.3 ± 17.2%,
Supplementary Information 2). The ubiquitous C16 and C18 FAMEs are the most abundant
(74 ± 17% of total FAMEs). They probably originate from free or esterified fatty acids (similar
to the fatty acids from Py-GC-MS) but cannot be related to a specific source. The long-chain
FAMEs and ω-methoxy FAMEs are probably products of the aliphatic biopolymer suberin,
which is abundant in vegetable bark and root materials (Kolattukudy 2001). The compounds
identified as N-containing products (23.8 ± 11.8%) are probably related to microbial sources
(Chiavari and Galletti 1992), even though a PySOM contribution to some of the unidentified
products (e.g. compound N8; Supplementary Information 2) cannot be ruled out. There are no
significant correlations between the relative proportions of the N-containing THM products
and the C/N ratio of the bulk sample.

The benzene carboxylic acids (BCA, detected as methyl esters) account for 16.4 ± 8.9% of
TQPA. The BCAs are major products of degraded polyphenolic materials such as lignin.
Furthermore, oxidized PySOM produces BCAs upon THM (Kaal et al. 2008a), especially BCA
with more than two carboxylic groups (Kaal and Filley 2016). The only PAH that was quan-
tified is naphthalene (0.4 ± 0.3%) and probably originates from PySOM.

The products of plant-derived polyphenolic SOM account for 7.4 ± 4.1%. The polyphenolic
products include traces of the methylated product of ferulic acid (compound PP12; Supple-
mentary Information 2) and larger proportions of mono-, di- and trimethoxybenzoic acid
methyl esters (PP6, PP9 and PP11) which shows that lignin is detectable in all samples but that it
is strongly altered by degradation, which supports the interpretation of the phenols and
guaiacols from Py-GC-MS.

Finally, carbohydrate products are scarce (2.5 ± 2.2%), likely due to the relatively poor obser-
vability of microbial polysaccharides by THM-GC-MS, in comparison with Py-GC-MS (Weiss
2017). The fatty diacid dimethyl esters (DAMEs), of unknown source (e.g. suberin or degraded
aliphatic materials), account for 3.9 ± 2.3% of TQPA.

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 12 C Ferro-Vázquez et al.

The ANOVA analysis of the THM-GC-MS fingerprints of SOMEX show that Group B samples
are enriched (p < 0.05) in trimethylpyrimidone (a marker of microbial tissue), whereas samples
from Group A show relatively large proportions of long-chain FAMEs (C24-C26) and
ω-methoxy-FAMEs (C22-C27) from suberin in root (and possibly bark) detritus. Samples from
Group C are enriched in C16 and C18 FAMEs, which is in agreement with high abundance of
fatty acids presented by Py-GC-MS, but we have no explanation for this effect.

Only two sample residues were analyzed by THM-GC-MS, which curtails a detailed discussion
comparing the extracts and residues. The extracts seemed to contain larger proportions of
lignin, microbial SOM (carbohydrates, N-containing compounds) and aliphatic biopolymers
(long-chain FAMEs and ω-methoxy-FAMEs), whereas the residues were enriched in C16- and
C18-FAMEs. The benzene tri- and tetracarboxylic acid products, allegedly from oxidized
PySOM (Kaal and Filley, 2016), are more abundant in the extracts.

Composition in Relation to 14C Ages

Pyrolysis-GC-MS
Function 1 (F1) of the PLS model for AGEEX from Py-GC-MS explains 80.4% of calibrated age
variance (Figure 4a), implying that there are clear trends in pyrolysis fingerprints of SOMEX related
to age. Positive loadings in this vector are found for the n-alkanes, n-alkenes and recalcitrant PySOM
products (benzene, benzonitrile, unsubstituted PAHs from condensed PySOM (Kaal et al. 2008a),
whereas negative loadings correspond to microbial products (N-compounds and carbohydrate
products) as well as the phenols and some of the alkyl-substituted MAHs and PAHs (Figure 4c,
x-axis; Supplementary Information 1). Hence, it appears that the recalcitrant PySOM and aliphatic
biopolymers in SOMEX increase with age, whereas microbial SOM, lignin detritus and weakly
condensed PySOM tend to decrease. These observations are in agreement with expected suscept-
ibilities to degradation, as the chemical recalcitrance of aliphatic SOM and PySOM usually exceeds
that of lignin, polysaccharides and proteins (Buurman et al. 2006). However, inevitably the older
samples correspond to different archaeological settings (megalithic) than the younger samples (ter-
races and hillforts). Hence, an additional, non-exclusive, explanation for this effect would be that the
uphill megalithic tomb environments (oldest samples and thus positive scores in F1, Supplementary
Information 1) were more frequently subjected to fire, whereas in the more recent hillforts and terrace
environments (negative in F1) larger inputs of vegetal remains and agricultural waste would generate
higher metabolic activity and subsequent formation of microbial SOM.

As mentioned before (section 3.1), there is no significant correlation between AGEEX and
DISCREP. Nevertheless, the F1 loadings for DISCREP (33.9% of DISCREP variance) are
inversely correlated (r2 = 0.90, p < 0.001) with those of AGEEX (Figure 4c). This means that a
higher proportion of NaOH-soluble PySOM and aliphatic biopolymers in SOMEX contributes
to reduce DISCREP values (Figure 4b, samples from Group C), while the preponderance of
microbial SOM increases them (Figure 4b, mainly samples from Group B). Furthermore, in the
case of F2 (not shown) for DISCREP (36.6% of the variance), the MCC have positive loadings
and the other compounds have negative loadings (Supplementary Information 1). Loadings
and scores in this vector are positive for Group C and negative for Group A samples (Supple-
mentary Information 1). If F1 and F2 are considered together (F1 + F2 = 70.5%), these results
suggest that the presence of a pool of well-preserved NaOH-extractable SOM is linked to low
DISCREP in samples from Group A (which have also high C contents), while a higher
degradation (noted by microbial enrichment in SOMEX) produces high DISCREP in samples of
Group B. Finally, accumulation of PySOM and aliphatic biopolymers leads to intermediately
high DISCREP in Group C samples.

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 Effect of Age on Soil Organic Matter Composition 13

From the PLS model for AGERES, the negative loadings on F1 (64.8%; Figure 5a) correspond
to phenols, carbohydrates, N-compounds, alkyl-MAHs and alkyl-PAHs, whereas unsub-
stituted MAHs and PAHs have positive loadings (Figure 5c, x-axis). Furthermore, the MCC
are divided according to chain length, with positive loadings for C10 to C27 (from aliphatic
biopolymers) and negative loadings for >C27 n-alkanes and n-alkenes (probably from waxes).
Again, these results can be explained largely by accumulation in the residual fraction of recal-
citrant PySOM and aliphatic biopolymers with age, even though differences in archaeological
setting cannot be discarded. To the contrary, lignin, microbial SOM and waxes are pre-
ferentially depleted with age. Hence, the PLS models are consistent in that SOM composition of
extracts as well as residues tend to change from microbial/lignin/intact lipids towards PySOM/
degraded lipids with increasing age. Note that F1 only explains 65% of the AGERES variance
which implies that others mechanisms may be involved (but we could not provide a meaningful
interpretation of F2 or other functions).

The F1 of the PLS model for DISCREP using SOMRES (74.7%; Figure 5c, y-axis) displays a
clear separation between phenols (predominantly from lignin) and long-chain n-alkanes/
n-alkenes with negative loadings, and short-chain n-alkanes/n-alkenes with positive loadings.
This suggests that DISCREP is relatively high in samples with abundant NaOH-insoluble
aliphatic biopolymers and is low when lignin remains and plant waxes are preserved. Typical
PySOM and microbial SOM products have neutral loadings on F1. However, F2 (Supple-
mentary Information 1) of the DISCREP model (F1 + F2 = 93.6%) has negative loadings for
phenols, microbial products and long-chain MCC and positive loadings for PySOM and short-
chain MCC (Supplementary Information S1). This shows the positive effect of recalcitrant
PySOM (and again aliphatic biopolymers) on DISCREP, similar to F1 of the PLS model of
SOMEX for DISCREP. However, the relation of molecular composition with age and DIS-
CREP is less explicit for SOMRES than for SOMEX.

THM-GC-MS
The F1 extracted by the PLS model for SOMEX based on THM fingerprints accounts for 41.9%,
of variance in AGEEX (Figure 6a). The short-chain FAMEs (C16, C18) and BCA have high
positive loadings on F1, while long-chain FAMEs, products of lignin/tannin and microbial
SOM load negatively (Figure 6c, x-axis; Supplementary Information 2). Hence, similar as for
SOMEX, the C16 and C18 fatty acids and PySOM are abundant in the samples of Group C
(Figure 6b), whereas Group A samples contain more relatively intact lignin and aliphatic
biopolymers (mainly suberin, recognized as long-chain FAMEs and methoxyl FAMEs), and
samples from Group B are enriched in microbial SOM.

The same clear distinction between these SOM components is made for PLS targeting DIS-
CREP (Figure 6c, y-axis), components, with positive loadings on F1 (44.6% of variance) for
microbial SOM, oxidized lignin products and short-chain FAMEs, and negative effects of the
markers of suberin and intact lignin. Indeed, there is a significant positive correlation between
loadings of F1 of AGEEX and DISCREP (n = 98 compounds, r2 = 0.38, p < 0.001), which was
also observed for Py-GC-MS of SOMEX.

14
C Ages and Molecular Fingerprints in the Light of Archaeological Setting
The existing archaeological information on the sites and samples largely shows that the 14C
dates obtained for the SOMEX fraction are more accurate than the dates from SOMRES.
Moreover, whereas AGEEX significantly groups samples (ANOVA p < 0.005) in three cultural

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 14 C Ferro-Vázquez et al.

Figure 4 Results from PLS models of the molecular composition of the NaOH-soluble SOM as determined by
Py-GC-MS. (A) F1 sample scores of the model using the measured age of the soluble SOM as the target variable.
The linear regression coefficient shows that this F1 explains 80% of the variation of age. (B) Sample scores in F1 of
the PLS model targeting the measured age of the SOMEX (AGEEX, x-axis), plotted against the scores in the F1 of the
PLS model targeting the age discrepancy (DISCREP, y-axis). (C) Composition behind the distribution of samples
shown in graph B: loadings of the pyrolysis products on F1 of the PLS model targeting the measured age of the SOM

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 Effect of Age on Soil Organic Matter Composition 15

periods (agricultural terraces: 1120 ± 220 cal BP, corresponding to Medieval Period; hillforts:
1810 ± 230 cal BP, corresponding to Iron Age; and burial mounds: 5870 ± 640 cal BP, belonging
to Megalithic period), the difference in AGERES for these different periods is not significant,
which points towards the limitations of the SOMRES fraction for dating samples from
NW Spain.

The molecular composition of the samples is consistent with the archaeologically defined
typologies for the sites listed in Table 1, and with earlier findings on ancient forms of land
management. In particular, the abundance of PySOM was expected, as colluvial soils from
Galicia have displayed large amounts of PySOM resulting from an intense fire regime (wild or
intentional, for clearance) over the last >6500 years that has contributed to shape the Galician
landscape (Kaal et al. 2008b). The larger abundance of microbial SOM in the extracts of
samples from agricultural and hillfort settings is consistent with the addition of vegetal remains
and agricultural wastes to the soil as argued by Bouhier (1979) for traditional agricultural
management in NW Spain and by Ferro-Vázquez et al. (2014, 2015) for terraced soils built
during the Medieval Period.

Hillfort Samples
Four samples originate from hillfort settings, corresponding to the Iron Age (roughly 1900–
2800 cal BP, (Parcero-Oubiña and Ayán Vila 2009; Jordá Pardo et al. 2009). These samples
correspond to Group A and Group B and their AGEEX ranges between 1500 and 2030 cal BP,
whereas AGERES varies between 1300 and 5400 cal BP. The sample from Besomaño (Riba-
dumia) is the only sample where AGERES (1240 cal BP) is lower than AGEEX (1880 cal BP;
DISCREP = −34%). This sample corresponds to sediment from a domestic structure (house)
which, according to archaeological evidence, corresponds to Roman period (Aboal Fernández
et al. 2013; Rodríguez Martínez 2015). It has high C content (11.9%) and high C/N (21.9,
Table 2) and corresponds to Group A. The sample from A Lanzada (Sanxenxo) also belongs to
Group A, with high C content (10.4%) and C/N (19.4). AGEEX (2030 cal BP) and AGERES
(2410cal BP) are similar and, on the basis of what is known of this hillfort, both ages are within
the plausible range of habitation (Suarez Otero and Fariña Busto 1990; Rodríguez Martínez
et al. 2011; Franco and Rodríguez Martínez 2015). Both Besomaño and A Lanzada samples
have low microbial SOM content, in both SOMEX and SOMRES fractions, which is interpreted
as evidence of good SOM preservation. In contrast, the posthole sample from Punta dos Prados
(Ortigueira) belongs to Group B. It has a low C content (1.0%) and C/N ratio (11.0) and a high
DISCREP (195%). The AGEEX of 1850 cal BP is archaeologically more accurate than AGERES
(5450 cal BP). This sample has a high microbial SOM content, especially in the extract. It is
suggested that a more intense SOM reworking caused the enrichment of microbial SOM and
depletion of other SOM components except for PySOM, which is more recalcitrant. The
SOMRES from these samples would contain inherited old C, probably from fire residues, the
signal of which would be amplified by a stronger degradation, thus exacerbating the inheritance

(x-axis), plotted against the loadings of the same products on the F1 of the PLS model targeting the age discrepancy
(y-axis). The compounds that tend to be more abundant in older samples (positive F1 on x-axis) tend to have a negative
effect on DISCREP, and vice versa. MAHs = monocyclic aromatic hydrocarbons, PAHs = polycyclic aromatic
hydrocarbons, MCC = methylene chain compounds (n-alkanes, n-alkenes and n-alkanoic acids), N-comp = products
with nitrogen, PHE = phenolic compounds, PS = polysaccharide products. Loadings of individual products are
provided in Supplementary Information 1. Groups A, B, and C are defined on the basis of age and SOM content
(Figure 3).

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 16 C Ferro-Vázquez et al.

Figure 5 Relationship of the molecular composition (Py-GC-MS) of the SOMRES with age: graph A shows the relation of
the molecular composition of the residual fraction (F1 sample scores of the PLS model from Py-GC-MS results, which
represents 65% of the variance) with AGERES. Graphs B and C plot the scores (B) and loadings (C) of the PLS models from
Py-GC-MS of the residues after NaOH-extraction in relation to DISCREP; where x-axis is F1 of the PLS model for
AGERES and y-axis is F1 of the PLS model for DISCREP. MAHs = monocyclic aromatic hydrocarbons, PAHs = polycyclic
aromatic hydrocarbons, MCC = methylene chain compounds (n-alkanes, n-alkenes and n-alkanoic acids), N-comp = products
with nitrogen, PHE = phenolic compounds, PS = polysaccharide products. Loadings of individual products are provided in
Supplementary Information 1. Groups A, B, and C defined according to the ANOVA analysis represented in Figure 3.

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 Effect of Age on Soil Organic Matter Composition 17

Figure 6 Relationship of the molecular composition (THM-GC-MS) of the SOMEX with age. (A) The F1 of the
model of AGEEX using the results of THM-GC-MS explains only a 42% of the AGEEX variance. Graphs B and C
display scores (B) and loadings (C) for the PLS models from THM-GC-MS of the soluble fraction. x-axis: F1 of the
PLS model for AGEEX. y-axis: F1 of the PLS model for DISCREP. FAMEs = fatty acid methyl esters,
N-comp = products with nitrogen, BCA = benzene carboxylic acids, PAH = polycyclic aromatic hydrocarbons,
PHE = phenolic derivatives, PS = polysaccharide products, DAMEs = diacid dimethyl esters, OTHER = not identified
products. Loadings of individual products are provided in Supplementary Information 2. Groups A, B, and C
defined according to the ANOVA analysis represented in Figure 3.

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 18 C Ferro-Vázquez et al.

effect in the Group B samples but not in the better preserved Group A samples, where root and
lignin detritus are preserved.

The stronger impact of degradation on the samples from Group B in comparison with those of
Group A, cannot be explained in terms of climatic variability, as some of the samples showing
evidence of less degraded SOM correspond to locations with higher mean annual temperatures
and lower thermal amplitude (Martínez-Cortizas and Pérez-Alberti 1999). It is, in turn, more
plausible that the more acidic, granitic parent material in samples from Group A (GEODE-
IGME) has an effect on the SOM degradation rates. These rocks naturally release, upon
weathering under temperate and wet conditions, large amounts of Al, which readily forms
organometallic SOM-Al complexes under acidic pH (Shoji and Fujiwara 1984; Kaiser and
Guggenberger 2000; Kaiser and Zech 2000). This complexation reaction provides protection
against microbial SOM degradation through sorptive preservation and associated occlusion in
micro-aggregates (Schwesig et al. 2003; Kalbitz et al. 2005; Grand and Lavkulich 2011). In fact,
complexation with Al has been reported to decrease the biodegradability of labile SOM con-
siderably, while the half-life of the more recalcitrant pool can increase up to 4 times as well
(Schwesig et al. 2003). Other mechanisms than sorptive preservation may occur simultaneously,
such as toxicity of free Al to microorganisms in acidic soils (Tokashiki and Wada 1975; Ton-
neijck et al. 2010). Unlike Group A samples, Punta dos Prados lithological setting (as well as for
the rest of the samples from Group B) is more alkaline, i.e. greenschist parent material
(GEODE-IGME; Castroviejo et al. 2004), which is more easily altered than granite and pro-
vides larger amounts of basic cations and much less Al to the soil solution. It is concluded that
the soil mineralogical and chemical environment, in particular the role of free or organically
bound Al, influences the degradation-preservation dynamics of the SOM—and thereby
DISCREP, as also found for other soils in Galicia by (Suárez-Abelenda et al. 2011).

The last sample from a hillfort setting, from a house wall from Montealegre, showed an AGEEX
that is considered too recent compared with existing archaeological information (1480 cal BP,
Table 2), and an AGERES that is too old (2620 cal BP), since the cultural material from this site
corresponds to the first to second centuries AD (Aboal Fernández and Castro Hierro 2005;
González-Ruibal et al. 2007). Despite the low C content (2.2%) and C/N (10.7), and high
DISCREP (77%) and microbial SOM content (especially in SOMEX), this sample from Group
B comes from a site where granitic material dominates. However, this sample is anomalous in
that it is not from a soil but instead has been sampled from a wall mortar. As mortars are
typically made from a mixture of sand, a binder (mud or clay, in this case) and water, the results
of the 14C dating will be biased by the age of its original components and the mortar manu-
facturing procedure. Moreover, the post-construction physico-chemical environment is differ-
ent from that of soils. Neither SOMEX nor SOMRES could provide a reliable date for the
construction of the wall; rather they would represent either the age of the organic material used
for the mortar (Sanjurjo-Sánchez 2016).

Agricultural Setting
The other samples of Group B correspond to agricultural contexts. Their lithology is also
alkaline, although not ultramafic as Punta dos Prados: the samples from Cidade de Cultura
(Santiago) and Santa Lucía (Eixo, Santiago) originate from soils developed on amphibolite and
those from Coto do Castrelo (Lalín) from a soil formed on schists with amphibolite inclusions.
Their AGEEX varies in a narrow range between 730 and 1330 cal BP, which corresponds to the
Medieval Period, and is consistent with knowledge on terraces construction in Galicia, which
became widespread during the Germanic Period (Ballesteros Arias 2010; Ballesteros Arias and

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 Effect of Age on Soil Organic Matter Composition 19

Blanco Rotea 2009; Ballesteros Arias et al. 2006; Ferro-Vázquez et al. 2014; Ferro-Vázquez
et al. 2015). On the contrary, dating of the SOMRES fractions gives AGERES >1800 cal BP
(Table 2), which are considered too early and not consistent with other information on the sites.
PySOM is abundant in these samples, especially in the residues, whereas microbial SOM
dominates the extracts. These residues therefore probably contain pyrogenic old C from fire
derived OM, the signal of which, again, would have been amplified by microbial degradation,
which is in turn catalysed by a lithology that favours a fast SOM turnover and therefore a large
DISCREP.

The sample from A Pousada (Bornais, Santiago) corresponds to a pavement clay mortar
(Blanco-Rotea et al. 2010). It is also a typical Group B sample with low C content, high
DISCREP and large proportion of microbial SOM in the extract. However, its age is con-
siderably older (AGEEX 2620 cal BP, AGERES 5810 cal BP) than the other samples from
agricultural settings and, as in the case of the Montealegre mortar, it is probably not repre-
sentative of the age of the construction of the pavement but of original constituents of the fabric
used for manufacturing (Sanjurjo-Sánchez 2016).

The other two samples from agricultural settings correspond to Group A. They are from terrace
soils in Montenegro (Morrazo) that developed on granite. These samples returned similar
results for 14C dating (AGEEX of 1240 cal BP and AGERES of 1330 cal BP, both of which are
consistent with the archaeological evidence for this site, Gianotti García and Cancela Cereijo
2005) and hence DISCREP is low. Also consistent with the rest of the samples from Group A,
they have relatively high C content and C/N ratio. The good SOM preservation appears to have
mitigated the influence of old inherited SOM in the SOMRES fraction.

It follows from these results that DISCREP is not affected by differences in archaeological
setting, because Iron Age hillforts and medieval agricultural terraces have both Group A (low
DISCREP) as well as Group B (high DISCREP) samples. Still, some differences between
archaeological settings can be found. The C/N ratio is, on average, lower (11 ± 1) for agri-
cultural sites than for hillforts (16 ± 6) (p < 0.05), whereas N-compounds (both Py-GC-MS and
THM-GC-MS) are more abundant in the in the SOMEX of agricultural than of hillfort sites,
which probably reflects a general difference in use and perhaps fertilization practices and a
faster turnover in agricultural contexts. Moreover: (1) the SOMRES fractions of the agricultural
terraces have higher PySOM content than the hillforts (p < 0.05 for pyrolysis products naph-
thalene, biphenyl and sum of PAHs), which may be related to slash-and-burn agriculture
(or slash-and-char), and (2) SOMEX in terraces is enriched in microbial THM products, and
also some products of oxidized lignin (P6, G6). To the contrary, the SOMEX from hillforts is
enriched in relatively oxidized PySOM and root derivatives.

Burial Mounds
The AGERES values of the samples from megalithic tombs (i.e. four samples from Ortigueira
and one sample from Toques, all of them corresponding to Group C), clearly exceed the
expected ages for megalithic contexts in Galicia. This is particularly the case for the SOMRES
fractions from Forno dos Mouros from Ortigueira, which were dated 9100–13000 yr cal BP
(Table 2). This range is much older than the age representative of different phases of mound
formation and use: it is 2000–6000 yr prior to earliest megalith architecture in NW Spain (Prieto
Martínez et al. 2012). Their SOMRES has large proportions of PySOM and C16 and C18 fatty
acids. Although fires or hearths beneath tumuli have been documented in other megalithic sites
of NW Spain (Fábregas Valcarce 1988; Criado Boado and Fábregas Valcarce 1989), this is not

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CC 42 3 :586 84 6 C6 CC 5 : 8 / ,
 20 C Ferro-Vázquez et al.

the case for the Forno dos Mouros burial mounds (Mañana-Borrazás 2005). The abundance of
PySOM in these samples is, therefore, probably due to wildfires, which have been demonstrated
to be frequent in this period (Kaal et al. 2008b). Their AGEEX is between 4600 and 6400 cal BP,
which is more consistent with the chronology of the cultural period (Neolithic) and is
in agreement with other dates measured in the same site and similar stratigraphic context
(Mañana-Borrazás 2005; Mañana-Borrazás et al. 2014). As a result, the DISCREP for these
samples is high.

In contrast, the sample from Forno dos Mouros from Toques has a more similar AGERES
(6470 cal BP) and AGEEX (6100 cal BP). Both dates are acceptably within the time frame of the
megalithic period in NW Spain (Prieto Martínez et al. 2012), although AGERES is considered too
old when compared with previous research on this site (Criado Boado et al. 1991; Steelman et al.
2005). The sample comes from the infilling of a structure made after the megalith was abandoned,
during the Bell Beaker period (Martínez Prieto et al. 2008). However, this infilling consists of
material from the mound itself, which explains the consistency of the dates with the Megalithic
period. This sample has a much higher C content (7.6%) than the samples from Ortigueira (1.7–
3.6%) and higher C/N ratio (17 vs. 12–14) (Table 2). The SOMRES has relatively high proportions
of phenols and carbohydrates products (revealed by Py-GC-MS) whereas the SOMEX fraction is
enriched in pyrolysates from root detritus, as shown by THM-GC-MS results. It therefore shares
several compositional similarities with the samples from Group A (Figure 3b), consistent with a
better preservation state, especially in the SOMRES. This seems to have resulted in a much lower
DISCREP than the other samples from the megaliths setting, where degradation would have
caused more pronounced relative accumulation of inherited PySOM and degraded lipids in
SOMRES, leading to age overestimations in the NaOH-insoluble fraction. This difference coincides
again with a more acidic lithological setting for Toques (ortogneis) compared to Ortigueira (schists
and slate parent materials, mineralogically more alkaline).

Finally, the sample 1614 is, in contrast to the rest of the megalithic samples, not from a burial
mound itself, but from a small trench in a presumably megalithic site in Monte Lobeira
(Vilanova de Arousa). This Group A sample has high C content (12.7%), C/N (22.2) and gave
near identical ages for AGEEX and AGERES (2800 cal BP). This age is younger than expected
for a megalithic setting. However, due to the fact that the sample analyzed is from a trench fill
and not from a burial mound, and also because the site is known to have been used after the
megalithic era (López-Romero and Mañana Borrazás 2013), this date was considered accep-
table from an archaeological perspective. PySOM is abundant in the residue, which is in
agreement with field observations (abundant charcoal; López-Romero and Mañana Borrazás
2013). However, owing to either the relatively good preservation of non-pyrogenic SOM or
because fire occurred simultaneously with deposition, presence of PySOM did not boost
DISCREP. Microbial SOM is scarce in both fractions, confirming a good preservation state of
the SOM. Accordingly, and consistently with the rest of the samples from Group A, this sample
comes from a soil developed in granodiorite, which is an acidic lithological material.

Implications for Dating of SOM in Archaeological Contexts

According to (Kristiansen et al. 2003), a low discrepancy between fractions signifies that the
SOM was probably derived from an ecosystem where SOM was rapidly rejuvenated, whereas
discrepancies larger than for instance a few decades between the NaOH-soluble and -insoluble
fractions would indicate that the SOM originally was not a homogenous pool, more specifically
that it was influenced by incorporation of younger SOM. However, this interpretation stems
from the aim of dating the soil, rather than obtaining the archaeological age.

2565 7 CC 42 3 :586 8 4 6 0 : 6 :C 7 1: : 68 .D 2C D3 64C C C 6 ,2 3 :586 , 6 C6 7 D 6 2 2: 23 6 2C

CC 42 3 :586 84 6 C6 CC 5 : 8 / ,
 Effect of Age on Soil Organic Matter Composition 21

Our results show that dating the NaOH-insoluble SOM generally produces overestimations of
the archaeological age. Intense microbial degradation would have resulted in microbial SOM in
the extracts and exacerbated inheritance effects of the more recalcitrant PySOM and aliphatic
biopolymers, as degradation eliminated relatively palatable coetaneous organic matter such as
lignin and plant-derived polysaccharides. The degree to which SOM has been affected by
degradation results from the combined effect of its original intrinsic recalcitrance (SOM
inherited from earlier burning events is more resistant to degradation than e.g. fresh poly-
saccharides) and the edaphic chemical and mineralogical environment.

Considering the evidence of root-derived SOM from THM-GC-MS, especially in the samples
from Group A, which have high SOM content and low DISCREP, it would be tempting to
conclude that the 14C ages of NaOH-insoluble SOM are to some extent affected not only by
inheritance of older SOM (mainly PySOM), but also by rejuvenation through later root input,
which could actually have partially counterbalanced the inheritance effect. Nevertheless, we
believe the presence of root-detritus should not be interpreted in terms of rejuvenation, but in
terms of SOM preservation: their markers, and those of intact lignin, can only be detected if the
intensity of degradation was low.

Our results therefore support previous research that proposed to use 14C ages of NaOH-soluble
SOM (AGEEX) for 14C dating of archaeological events(Kaal et al. 2008b; Albrecht and Kühn
2011; Pietsch and Kühn 2014). At the same time, given the effect of the physico-chemical
environment on DISCREP, its characterization may also, when combined with the study of
molecular composition, give insights on stabilization and turnover of different SOM
constituents.

CONCLUSIONS
The analysis of archaeological samples from NW Spain by pyrolysis-GC-MS and THM-GC-
MS provided insights into the molecular composition of the different fractions isolated from
SOM using an acid-alkali-acid treatment. The SOM is largely composed of a mixture of
microbial SOM, pyrogenic organic matter and aliphatic recalcitrant molecules, at least in part
from roots. Alkali-extractable SOM, which accounts for roughly two-thirds of total SOM, has a
larger proportion of microbial detritus than the residual SOM. This would traditionally be
attributed to rejuvenation in the extractable fraction. However, since archaeological evidence
unambiguously shows that the 14C age of the insoluble fraction is far older than would
be expected from associated cultural material, it is concluded that microbial SOM is not a
source of age bias. It is, however, relevant as it is evidence of the degradation of SOM (including
elimination of the palatable lignin and polysaccharide contents of plant debris). The statistical
analysis of the results by partial least squares regression suggested that the insoluble fraction
contains inherited fire-derived SOM and aliphatic biopolymers that are the source of the age
overestimations in the residual fraction. The extent of the discrepancies between the NaOH-
soluble and -insoluble fractions appears to be related with the intensity of mineralization,
because a larger degradation degree exacerbates the inheritance effect. In the studied samples,
the intensity of degradation is controlled by (1) molecular recalcitrance of in particular pyro-
genic matter and (2) the geochemical environment of the sample matrix which determines the
degree of SOM protection through the availability of free or poorly-crystalline Al for organo-
mineral complexation reactions. The relative importance of these two SOM preservation
mechanisms could not be established.

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CC 42 3 :586 84 6 C6 CC 5 : 8 / ,
 22 C Ferro-Vázquez et al.

ACKNOWLEDGMENTS
Cruz Ferro-Vázquez has been funded by the People Programme (Marie Curie Actions) of the
European Union’s Horizon 2020 Programme (tRRACES-H2020-MSCA-IF-2014-657355).
Radiocarbon analyses have been funded by the Institute of Heritage Sciences from the Spanish
National Research Council (Incipit-CSIC) and the Consolider Programme CSD2007-0058
(MINECO, Spain). We are grateful to the anonymous reviewers and associate editor for their
valuable suggestions.

SUPPLEMENTARY MATERIAL
To view supplementary material for this article, please visit https://doi.org/10.1017/RDC.2018.62

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CC
2565 7
42 3 :586

APPENDIX
Conventional 14C ages (and error), F14C values (and error), calibration probability ranges, relative area for each interval, and median of the
CC

probability distribution for A) SOMBULK, B) SOMRES, and C) SOMEX.

84

Table A1 ■
42 3 :586 8 4 6 0 : 6 :C
6 C6

14
A) Lab code Sample code C ± F14C ± Calibration ranges (2σ) Relative area AGEBULK
CC

CNA1575.3.2 CC1-4 1040 30 0.8785 0.003 cal BP 918: cal BP 990 0.94 950
5 : 8

cal BP 991: cal BP 997 0.01

cal BP 1029: cal BP 1049 0.05
CNA1577.3.1 MU010626U03 2690 35 0.7156 0.003 cal BP 2751: cal BP 2853 1.00 2790
CNA1579.3.1 MU020201B01 M-9 1200 35 0.8614 0.004 cal BP 1006: cal BP 1025 0.03 1130
7 1: : 68
/ ,

cal BP 1053: cal BP 1187 0.87

cal BP 1204: cal BP 1256 0.10

Effect of Age on Soil Organic Matter Composition 27

CNA1582.3.1 MU020829A01-10 6660 40 0.4367 0.002 cal BP 7460: cal BP 7590 1.00 7530
CNA1583.3.1 MU020906A01-2 3950 35 0.6117 0.003 cal BP 4259: cal BP 4263 0.00 4410
cal BP 4288: cal BP 4451 0.78
.D

cal BP 4463: cal BP 4519 0.22

CNA1584.3.1 MU020906A01-4 5060 35 0.5330 0.002 cal BP 5722: cal BP 5906 1.00 5820
2C

CNA1585.3.1 MU020906A01-6 6180 40 0.4035 0.002 cal BP 6952: cal BP 7176 0.99 7080
cal BP 7222: cal BP 7233 0.01
CNA1590.3.1 MU030924Z08 2350 40 0.7467 0.004 cal BP 2208: cal BP 2224 0.01 2360
D3 64C C C 6 ,2 3 :586 ,

cal BP 2307: cal BP 2491 0.97

cal BP 2605: cal BP 2605 0.00
cal BP 2643: cal BP 2656 0.01
cal BP 2665: cal BP 2676 0.01
CNA1592.3.1 MU040301H01 (4) 1230 35 0.8581 0.004 cal BP 1067: cal BP 1194 0.66 1160
cal BP 1196: cal BP 1262 0.34
CNA1593.3.1 MU040301H01 (9) 1310 35 0.8499 0.004 cal BP 1181: cal BP 1215 0.30 1250
6 C6

cal BP 1219: cal BP 1294 0.70

CNA1594.3.1 MU040809I02 1610 35 0.8184 0.004 cal BP 1407: cal BP 1567 1.00 1490
7 D 6 2 2: 23 6 2C

CNA1603.3.1 MU070129H01 M-13 1320 35 0.8487 0.004 cal BP 1182: cal BP 1212 0.25 1260
cal BP 1224: cal BP 1298 0.75
CC
2565 7
42 3 :586

28 C Ferro-Vázquez et al.
Table A1: (Continued )
CC

14
A) Lab code Sample code C ± F14C ± Calibration ranges (2σ) Relative area AGEBULK
84

CNA1604.3.1 MU070129H01 M-9 1535 35 0.8260 0.004 cal BP 1353: cal BP 1524 1.00 1440
42 3 :586 8 4 6 0 : 6 :C
6 C6

CNA1606.3.1 MU090702B01 5424 35 0.5090 0.002 cal BP 6133: cal BP 6136 0.00 6240
cal BP 6182: cal BP 6296 1.00
CNA1612.3.1 MU100628B01 2120 35 0.7677 0.003 cal BP 1996: cal BP 2158 0.92 2100
CC

cal BP 2259: cal BP 2298 0.08

5 : 8

CNA1614.3.1 MU101105L04 2650 35 0.7187 0.003 cal BP 2741: cal BP 2808 0.90 2770
cal BP 2815: cal BP 2844 0.10
14
B) Lab code Sample code C ± F14C ± Calibration ranges (2σ) Relative area AGERESAGERES
7 1: : 68
/ ,

CNA1575.1.2 CC1-4 1995 25 0.7799 0.002 cal BP 1890: cal BP 1994 1.00 1940
CNA1577.1.2 MU010626U03 5040 30 0.5340 0.002 cal BP 5665: cal BP 5672 0.01 5820
cal BP 5713: cal BP 5900 0.99
CNA1579.1.1 MU020201B01 M-9 2470 25 0.7352 0.002 cal BP 2382: cal BP 2391 0.01 2590
cal BP 2430: cal BP 2716 0.99
.D

CNA1582.1.1 MU020829A01-10 11070 40 0.2521 0.001 cal BP 12808: cal BP 13055 1.00 12940
CNA1583.1.1 MU020906A01-2 8170 40 0.3617 0.002 cal BP 9015: cal BP 9154 0.72 9110
2C

cal BP 9158: cal BP 9255 0.28

CNA1584.1.1 MU020906A01-4 8650 40 0.3406 0.002 cal BP 9538: cal BP 9688 1.00 9600
CNA1585.1.1 MU020906A01-6 8840 35 0.3328 0.002 cal BP 9739: cal BP 9964 0.58 9930
D3 64C C C 6 ,2 3 :586 ,

cal BP 9984: cal BP 10153 0.42

CNA1590.1.1 MU030924Z08 4730 35 0.5555 0.003 cal BP 5325: cal BP 5409 0.38 5470
cal BP 5445: cal BP 5489 0.22
cal BP 5502: cal BP 5583 0.40
CNA1592.1.1 MU040301H01 (4) 1440 25 0.8363 0.002 cal BP 1297: cal BP 1371 1.00 1330
CNA1593.1.1 MU040301H01 (9) 1440 25 0.8362 0.002 cal BP 1297: cal BP 1371 1.00 1330
CNA1594.1.1 MU040809I02 2530 25 0.7303 0.002 cal BP 2495: cal BP 2597 0.50 2620
6 C6

cal BP 2611: cal BP 2638 0.15

cal BP 2684: cal BP 2742 0.35
7 D 6 2 2: 23 6 2C
CC
2565 7
42 3 :586

CNA1603.1.1 MU070129H01 M-13 1850 30 0.7942 0.003 cal BP 1714: cal BP 1866 1.00 1790
CNA1604.1.1 MU070129H01 M-9 2530 30 0.7295 0.003 cal BP 2492: cal BP 2600 0.46 2620
CC

cal BP 2608: cal BP 2640 0.14

cal BP 2679: cal BP 2747 0.40
84

CNA1606.1.1 MU090702B01 5670 35 0.4937 0.002 cal BP 6352: cal BP 6366 0.01 6450
42 3 :586 8 4 6 0 : 6 :C
6 C6

cal BP 6396: cal BP 6542 0.99

CNA1612.1.1 MU100628B01 2370 30 0.7449 0.003 cal BP 2336: cal BP 2485 1.00 2390
CNA1614.1.1 MU101105L04 2700 30 0.7147 0.003 cal BP 2754: cal BP 2854 1.00 2800
CC

CNA1616.1.1 MU110316B01 1310 30 0.8496 0.003 cal BP 1182: cal BP 1213 0.29 1250
5 : 8

cal BP 1223: cal BP 1294 0.71

14
C) Lab code Sample code C ± F14C ± Calibration ranges (2σ) Relative area AGEEX
CNA1575.2.1 CC1-4 820 40 0.9035 0.004 cal BP 673: cal BP 794 1.00 730
7 1: : 68
/ ,

CNA1577.2.1 MU010626U03 2540 40 0.7294 0.004 cal BP 2489: cal BP 2645 0.61 2620
cal BP 2651: cal BP 2671 0.03

Effect of Age on Soil Organic Matter Composition 29

cal BP 2675: cal BP 2750 0.36
CNA1579.2.1 MU020201B01 M-9 1120 40 0.8701 0.005 cal BP 938: cal BP 948 0.02 1030
.D

cal BP 951: cal BP 1094 0.87

cal BP 1105: cal BP 1148 0.07
cal BP 1158: cal BP 1173 0.04
2C

CNA1582.2.1 MU020829A01-10 5710 45 0.4916 0.003 cal BP 6405: cal BP 6573 0.88 6490
cal BP 6579: cal BP 6632 0.12
CNA1583.2.1 MU020906A01-2 4110 45 0.5996 0.003 cal BP 4452: cal BP 4462 0.01 4660
D3 64C C C 6 ,2 3 :586 ,

cal BP 4520: cal BP 4821 0.99

CNA1584.2.1 MU020906A01-4 5060 45 0.5327 0.003 cal BP 5664: cal BP 5674 0.01 5810
cal BP 5682: cal BP 5687 0.01
cal BP 5710: cal BP 5913 0.98
CNA1585.2.1 MU020906A01-6 5490 45 0.5047 0.003 cal BP 6207: cal BP 6355 0.88 6290
cal BP 6362: cal BP 6397 0.12
CNA1590.2.1 MU030924Z08 1910 35 0.7888 0.003 cal BP 1737: cal BP 1765 0.06 1850
6 C6

cal BP 1770: cal BP 1926 0.94

CNA1592.2.1 MU040301H01 (4) 1300 35 0.8507 0.004 cal BP 1180: cal BP 1291 1.00 1242
7 D 6 2 2: 23 6 2C

CNA1593.2.1 MU040301H01 (9) 1340 35 0.8470 0.004 cal BP 1183: cal BP 1211 0.18 1270
cal BP 1227: cal BP 1306 0.82
CC
2565 7
42 3 :586

30 C Ferro-Vázquez et al.
Table A1: (Continued )
CC

14
C) Lab code Sample code C ± F14C ± Calibration ranges (2σ) Relative area AGEEX
84

CNA1594.2.1 MU040809I02 1600 35 0.8201 0.004 cal BP 1406: cal BP 1555 1.00 1480
42 3 :586 8 4 6 0 : 6 :C
6 C6

CNA1603.2.1 MU070129H01 M-13 1210 35 0.8610 0.004 cal BP 1010: cal BP 1022 0.02 1130
cal BP 1055: cal BP 1188 0.85
cal BP 1203: cal BP 1258 0.13
CC

CNA1604.2.1 MU070129H01 M-9 1420 35 0.8385 0.004 cal BP 1286: cal BP 1374 1.00 1320
5 : 8

CNA1606.2.1 MU090702B01 5340 40 0.5146 0.002 cal BP 5995: cal BP 6213 0.95 6110
cal BP 6244: cal BP 6268 0.05
CNA1612.2.1 MU100628B01 2060 35 0.7737 0.003 cal BP 1933: cal BP 2122 1.00 2030
CNA1614.2.1 MU101105L04 2680 35 0.7169 0.003 cal BP 2748: cal BP 2847 1.00 2780
7 1: : 68
/ ,

CNA1616.2.1 MU110316B01 1930 35 0.7866 0.004 cal BP 1813: cal BP 1953 0.97 1880
cal BP 1957: cal BP 1987 0.03
.D
2C
D3 64C C C 6 ,2 3 :586 ,
6 C6
7 D 6 2 2: 23 6 2C