Applied Geochemistry 41 (2014) 34–48

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Applied Geochemistry
journal homepage: www.elsevier.com/locate/apgeochem

Deciphering the impact of land-uses on terrestrial organic matter

and mercury inputs to large boreal lakes of central Québec using lignin
biomarkers
Matthieu Moingt ⇑, Marc Lucotte, Serge Paquet, Bassam Ghaleb
GEOTOP, Institut des Sciences de l’Environnement, Université du Québec à Montréal, C.P.8888, suc. Centre-Ville, Montréal, Québec H3C 3P8, Canada

a r t i c l e i n f o a b s t r a c t

Article history: To evaluate watershed impacts of anthropogenic activities on terrestrial organic matter (TOM) and total
Received 17 June 2013 mercury (THg) dynamics in large boreal lake ecosystems, we studied sediment cores retrieved in eight
Accepted 17 November 2013 large lakes of Québec (Canada). Two lakes with pristine watersheds were considered as reference lakes
Available online 1 December 2013
and six lakes with watersheds affected by different types of anthropogenic activities (e.g. logging and/
Editorial handling by JoAnn M. Holloway
or mining activities) were used to illustrate the influence of land-use on TOM and Hg cycling in lakes.
A Geographical Information System (GIS) approach was used to correlate the evolution of anthropogenic
land-uses from 1979 to 2010 (e.g. logging and mining activities) to TOM and THg contents measured in
sediment cores. In each core, THg concentrations gradually increased over the recent years. Using lignin
biomarkers, we noticed that the presence of both intense logging and mining activities in the watershed
does not necessarily correspond to noticeable changes in the relative amount of terrestrial organic matter
(TOM) exported from the watershed to the sediments and by extension to the level of THg measured in
sediments. Apparently large-scale watersheds show some ‘‘buffering’’ capacity to land-use disturbance.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction It is recognized that terrestrial organic matter (TOM) plays a

Mercury (Hg) dynamics in lakes in central Québec are of special
concern as local populations frequently consume wild fish and are
thus chronically exposed to the contaminant. For over a century,
the release of Hg to the atmosphere associated with anthropogenic
activities resulted in an increase in the heavy metal deposition in
boreal lakes ecosystems (Pacyna et al., 2006). Dry and wet Hg
deposition from anthropogenic sources can reach areas very
distant from their point source emission (Fitzgerald et al., 1998;
Pacyna et al., 2006), thus remote areas such as central Québec
can then be impacted. Hg is then transferred to the lake and
accumulated in sediments where increases in total mercury
(THg) contents have been reported (Lucotte et al., 1995; Rognerud
and Fjeld, 2001). In parallel, central Quebec watersheds are
frequently perturbed by multiple anthropogenic activities such as
logging, mining, road construction and urbanization. Those pertur-
bations modify the natural Hg fluxes from the watersheds to the
aquatic systems and could be responsible for supplementary
amounts of Hg reaching the lakes, which have the potential to be
incorporated into the food web (Ikingura and Akagi, 1996; Lavoie
et al., 2010; Soto et al., 2011; Watras et al., 1998).
⇑ Corresponding author. Tel.: +1 514 987 3000x3523; fax: +1 514 987 3635.
E-mail address: matthieumoingt@yahoo.fr (M. Moingt).
major role in the transport of contaminants from the watershed
to the lake (Coquery and Welbourn, 1995; Moingt et al., 2010;
Ouellet et al., 2009; Teisserenc et al., 2010). Lake sediments repre-
sent a powerful tool to reconstruct both Hg and TOM transfers
from the watersheds to the aquatic systems. Lignin biomarkers
have been used to evaluate both TOM fluxes and quality reaching
sediments (Dittmar and Lara, 2001; Hedges et al., 1997; Hu et al.,
1999; Ouellet et al., 2009) and lignin degradation biomarkers have
been widely exploited for the study of TOM dynamics in soils,
water column, and sediments (Chabbi and Rumpel, 2004; Houel
et al., 2006; Ouellet et al., 2009). In comparison with bulk carbon
analysis, lignin biomarkers in sediment cores bring new informa-
tion on the nature of TOM fluxes from watersheds to lakes and help
to reconstruct historical watershed modifications. Moreover,
because Hg is known to have affinity for TOM (Kainz et al., 2003;
Kolka et al., 1999; Yang et al., 2007), lignin biomarkers could yield
new information on Hg dynamics in boreal lakes. Lignin alkaline
oxidation by copper oxide (CuO) produces short-chain phenols
comprising ketone, aldehyde and/or carboxylic acid functionalities
present in the parent lignin macropolymer. These major oxidation
products are grouped into four major monomer families: vanillyl
(V), syringyl (S), cinnamyl (C) and p-hydroxyphenols (P) (Goñi
and Hedges, 1992; Goñi et al., 1993; Hedges and Ertel, 1982).
The relative proportions of these monomeric subunits allow dis-
crimination between different types of vascular plant tissues, and

0883-2927/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.apgeochem.2013.11.008
 M. Moingt et al. / Applied Geochemistry 41 (2014) 34–48
have been used to decipher sources and relative degradation state
of organic matter in several natural ecosystems (Dittmar and Lara,
2001; Hedges and Mann, 1979; Hernes and Benner, 2003). More-
over, several studies have shown that lignin quality is influenced
by hydrologic and soil processes in watersheds (Dalzell et al.,
2007; Hernes et al., 2007).
In this paper, we combined the geochemical study of sediment
data (210Pb dating, THg concentrations, lignin biomarkers) with
watershed characteristics identified through GIS (land-use and
vegetation cover) to evaluate the impact over three decades of
anthropogenic watershed perturbations relative to the increase in
Hg transfers from watersheds to sediments in large lakes ecosys-
tems. We sampled sediment cores in eight large boreal lakes with
surface areas ranging from 15 to 210 km2, six of them presenting
specific disturbances in their watershed such as intensive logging
or mining, and two unperturbed lakes chosen as reference lakes.
Several studies point to anthropogenic perturbations occurring in
the watershed (e.g. logging and mining activities) as a contributor
to the increasing amount of THg reaching lakes sediments. How-
ever, these studies have focused solely on small lakes ecosystems
with surface areas ranging from 0.4 to 1.3 km2 (Garcia and Cari-
gnan, 2000, 2005; Porvari and Verta, 2003; Porvari et al., 2003).
Large lake ecosystems have been ignored despite the fact that they
represent a better picture of socio-economic-environmental land-
uses of the boreal forest region (fishery, mining and logging activ-
ities). Moreover, small lakes only allow the study of one process
one at a time whereas large lake ecosystems integrate a sum of
various processes and include the inertia of the system. Such ap-
proaches will help to gain a more holistic understanding of the cy-
cling of Hg between terrestrial and aquatic systems and the
influence of anthropogenic effects and environmental changes in
the transport of Hg into aquatic ecosystems.
2. Material and methods
2.1. Study sites
Matagami, Ouescapis, Rodayer, Waswanipi, Dickson and
Chibougamau lakes are located in the administrative region of
Northern Quebec (Fig. 1). Lakes characteristics (location, altitude,
lake area, drainage area, ratio of drainage area to lake area (DA/
LA)) are specified in Moingt et al. (2013). Matagami Lake is a
43 km long and 14 km wide lake in a swampy region of Northern
Quebec and represents the confluence point of Allard, Bell, Goua-
ult and Waswanipi rivers. Perturbations in the watershed include
road construction, logging, mining and golf activities. Ouescapis
and Rodayer lakes are located approximately 70 and 120 km
north of Matagami Lake, respectively. None of these lakes show
any substantial perturbations in their watershed. Waswanipi Lake
is situated about 100 km south-east from Matagami Lake to
which it is linked upstream by the Waswanipi River. Waswanipi
Lake presents a watershed perturbed with logging and mining
activities and several gravel roads. Dickson Lake is located about
180 km south-east from Matagami Lake. This lake has a history of
intense logging activity in its watershed. Chibougamau Lake is lo-
cated approximately 10 km south of the town of the same name.
This lake is the source of the Chibougamau River and is inter-
spersed with several islands, deep and large bays. The watershed
of Chibougamau Lake has been intensely used for mining activi-
ties (Petit et al., 2011). Des Jardins East and West lakes (total area
of 15.02 km2) are located in the Témiscamingue region further
south (Fig. 1). Des Jardins East Lake flows into Des Jardins West
Lake and their watersheds are covered by mature mixed wood
forests. Perturbations in the watershed include gravel roads and
logging activities.
35
2.2. Landscape and historical analysis
Landscape analyses were performed following the method de-
scribed in details by Moingt et al. (2013). Briefly, landscape charac-
terization was performed with raster satellite images from Landsat
7 satellite imagery with image processing using GIS Geographic
Resources Analysis Support System (GRASS 6.4; http://grass.-
fbk.eu/) software in order to decipher the morphology and the land
cover of watersheds. The Canadian digital elevation data (scale: 1/
50,000), extracted from the hypsographic and hydrographic ele-
ments of the National Topographic Data Base (Tahvanainen and
Haraguchi, 2013) were also used. For the purposes of our study,
the watershed is defined as the land area draining either directly
into a lake or into the first lake upstream corresponding to an order
3 watershed level which has been described as the level influenc-
ing the most the associated aquatic ecosystem (Beaulne et al.,
2012; Slauenwhite and Wangersky, 1996). In order to determine
the mean watershed slope and to identify different slope classes
(intervals of 2% from 0% to 20%, e.g. 0–2%) within each watershed,
the slope of each pixel was calculated. Land cover was estimated
by applying the Maximum Likelihood Classification (MLC) algo-
rithm modified by Neteler and Mitasova (2008) to the entire set
of visible spectral bands. Historical reconstructions were based
on observations coming from satellite images over a 30 year period
(1979–2011).
2.3. Sediment sampling
We used a pneumatic Mackereth corer to sample lake sedi-
ments during sample missions in 2009 and 2010. This type of corer
presents the advantage of reducing both perturbations at the
water–sediment interface and sediment compaction. During the
sampling, a 1.5-m long Plexiglas tube (diameter 10 cm) is slowly
pushed into the sediment using compressed air. Then, sediment
cores were sub-sampled in 20 mL glass vials (pre-combusted at
500 °C for 3 h to avoid carbon contamination of the vessels and
capped with TeflonÒ liners) every centimeter using a TeflonÒ spat-
ula. For each slice we only conserved the center of the core to avoid
cross-contamination between samples. Finally, samples were
freeze-dried prior to analysis. In order to integrate spatial varia-
tions in watershed to lake TOM and Hg transfers, coring was per-
formed at the focal point of the lake (Hakanson and Jansson,
1983; Teisserenc et al., 2010).
2.4. Chemical analyses
2.4.1. 210Pb radiometric measurements
Sedimentation rates were determined by radiometric measure-
ment of 210Pb activity using alpha spectrometric measurement of
the activity of the daughter product 210Po (Flynn, 1968) and
assuming secular radioactive equilibrium between the two iso-
topes. Aliquots between 0.2 and 0.4 g of sediments were spiked
with 209Po yield tracer and digested in Teflon vials using a concen-
trated 5:4:1 mixture of HNO3:HCl:HF. Addition of H2O2 was per-
formed to eliminate organic carbon (OC) in the sample. The
residue was then converted to a chloride salt by repeated evapora-
tion with 6 M HCl. Before the last evaporation was complete, the
remaining solution was centrifuged and the supernatant was
collected in order to get rid of black carbon. Then, approximately
100 mL of 0.5 M HCl was added to the collected supernatant to de-
crease the concentration of the solution. Then 1.5 mL of 1 M ascor-
bic acid was added to reduce Fe3+ into Fe2+. Po isotopes where
deposited on a spinning Ag disk (Hamilton and Smith, 1986) and
the activity measured by a-spectrometry using ORTEC silicon
surface barrier detectors coupled with a PC running under Maestro
data acquisition software. Blanks were run through the same
36 M. Moingt et al. / Applied Geochemistry 41 (2014) 34–48
Fig. 1. Location of studied lakes on a Quebec map.
procedure. Chronology was established using downcore unsup-
ported 210Pb, a constant initial concentration model (CIC), and
dividing nonlinear profiles into linear segments assuming constant
sedimentation for each of these segments (Appleby and Oldfield,
1992). 210Pbex corresponds to the excess of 210Pb in sediments
(i.e. the difference between the total 210Pb activity at depth (i)
minus the value of 210Pb supported activity). 210Pb supported activ-
ity corresponds to the average of measured values at the bottom of
the core when 210Pb activity does not vary anymore.
2.4.2. Total mercury analyses
Replicate THg analyses were performed by cold vapor atomic
fluorescence spectrometry (CV-AFS) following the protocol devel-
oped by Bloom and Fitzgerald (1988) and adapted by Pichet et al.
(1999). Briefly, a combination of 16 M HNO3:6 M HCl (10 mL:1 mL)
is added to approximately 250 mg of ground, freeze-dried sedi-
ment and then heated to 120 °C for 6 h. The remaining solution
is brought back to a volume of 30 mL with NANOpureÒ water
and analyzed by atomic fluorescence. Hg calibration was done by
injecting known quantities of Hg (II) (400–1000 pg of Hg). The
detection limit for a 250 mg sample was 0.1 ng/g. The accuracy
of the method was verified using the Mess-3 certified standard
(NRC Canada). With an average value of 87 ± 3 ng/g for seven ali-
quots, our results fell within the certified value (92 ± 9 ng/g).
2.4.3. Lignin biomarkers analyses
In order to conduct lignin biomarkers analyses, percentage of
OC for each sample was measured performing total carbon and
nitrogen analyses using a CE-Instruments model NC2500™ ele-
mental analyzer with a relative precision of ±5% (1r). Replicate
measurements on samples, treated and untreated by vapor acidifi-
cation, were performed to verify that the inorganic carbon fraction
was negligible. Acidified sample measurements systematically fell
within the range of the non-acidified sample, thus demonstrating
that total carbon content can be considered as OC content.
Sediment samples were subjected to alkaline cupric oxide (CuO)
oxidation according to a modified protocol from the initial method
described by Goñi and Montgomery (2000). For each sample,
3.0 ± 0.1 mg of OC and CuO (330 ± 4 mg) were mixed in about
3.2 mL of 2 N NaOH in a reaction bomb purged with N2. Oxidations
were conducted with a Hewlett Packard 5890A™ gas chromato-
graph oven modified by PRIME FOCUS Inc. (Seattle, WA) and fitted
with 12 Monel-400 alloy (Ni:Cu:Fe 65:32:3 wt%) reaction vessels.
Reaction bombs were heated to 150 °C for 150 min with an initial
temperature gradient of 4.2 °C/min for 30 min. After oxidation,
50 lL of the internal standard cinnamic acid and ethyl-vanillin
was added to the bomb and the supernatant was decanted and
acidified to pH 1 with HCl (2 N). The organic phase was then li-
quid–liquid extracted using ethyl acetate and dried by rotary evap-
oration. Finally, the extract was dissolved another time in pyridine
and derivatized with N,O-bis(trimethylsilyl)trifluoroacetamide
(BSTFA) and trimethylchlorosilane (TCMS; 99:1). A 2-lL extraction
fraction was analyzed by GC/MS (Varian 3800/Saturn 2000™)
fitted with a fused capillary column (DB-1 from J&W, 60 m,
320 lm). The injector and the detector were held at 300 °C and
He was used as carrier gas in splitless mode. The initial column
 M. Moingt et al. / Applied Geochemistry 41 (2014) 34–48 37

Table 1
Comparison and variability of lignin CuO oxidation parameters measured from a reference sediment: SAG 05 (estuarine sediment). Values from Louchouarn et al. (2000) and
Houel et al. (2006) were generated using conventional oven and microwave oven respectively.

SAG 05
This study (n = 9) Louchouarn et al. (2000) (n = 11) Houel et al. (2006) (n = 6)
Average SD Average SD Average SD
Lambda 3.50 0.23 3.53 0.17 2.81 0.31
Sigma 8 7.41 0.48 ND ND ND ND
S 0.70 0.20 0.56 0.05 0.44 0.03
V 2.57 0.29 2.73 0.11 2.11 0.29
C 0.23 0.04 0.23 0.04 0.26 0.04
P 0.30 0.03 0.54 0.10 0.34 0.04
S/V 0.28 0.11 0.21 0.02 0.21 0.03
C/V 0.09 0.02 0.08 0.01 0.13 0.02
P/(V + S) 0.09 0.01 ND ND 0.14 0.02
3,5-Bd/V 0.10 0.02 0.08 0.02 0.11 0.01
(Ac/Ad)S 0.20 0.07 0.38 0.05 0.47 0.13
(Ac/Ad)V 0.37 0.03 0.38 0.05 0.48 0.09

oven temperature was set at 100 °C with a temperature gradient of
4 °C/min to 320 °C followed by a holding time of 10 min.
Replicate analyses of the SAG 05 ‘‘standard’’ sediment sample
(n = 9) showed that the analytical variability of the alkaline CuO
oxidation products and major indicators range from 6% to 38% (Ta-
ble 1). The intercomparison of this standard sediment analyses
shows that the composition parameters and the yields of the pres-
ent study are comparable to those obtained by both microwave
digestion and traditional oven method (Table 1).
2.4.4. Statistical analyses
Statistical tests were applied to the regression observed
between the enrichment in THg from the deeper sections of the
cores to the surface ones. Such tests were also applied to the mor-
phological characteristics of the watersheds. In all cases, normal
distribution of residuals was tested by performing a Shapiro–Wilk
goodness of fit test, using a statistical analysis program (JMP 7) and
accepted W values >0.05. The F-ratio was then computed in order
to evaluate the effectiveness of the model and the student para-
metric test (t-test) was processed to evaluate the pertinence of
regression parameters (p < 0.05).
3. Results
3.1. 210
Pb dating
Figs. 2–4 present the results for radiometric measurements
realized on lake sediment cores. In surface sediments, 210Pb
activities are 32, 42, 18, 37, 14 and 15 dpm/g for Ouescapis, Roda-
yer, Waswanipi, Chibougamau, Dickson and Matagami lakes
respectively.
Water content of each sample was determined by weighing
sediment before and after freeze-drying in order to correct the sed-
iment accumulation rate because of possible compaction of the
core during sampling. After calculation, sedimentation rates ob-
tained taking or not into account dry bulk density of each sediment
layer were not different suggesting a minor impact of compaction
in our case. Thus, sedimentation rates were directly estimated
using the slope of the relationship between depth (cm), the natural
logarithm of 210Pbex and the 210Pb decay constant.
Desjardins Lake has an estimated sedimentation rate of
0.22 ± 00.6 (Lucotte et al., 1995; Teisserenc et al., 2010). Estimated
sedimentation rates are 0.11, 0.05, 0.05, 0.03, 0.05 and 0.31 cm/
year for Ouescapis, Rodayer, Waswanipi, Chibougamau, Dickson
and Matagami lakes respectively. Only Matagami Lake seems to
present a modification of its sedimentation rate through time
(Fig. 4). Indeed, we can observe an inflexion point around 6 cm
depth where the sedimentation rate rapidly shifts from 0.11 to
0.31 cm/year. Due to the unusual 210Pb profile in Matagami Lake’s
sediment core, 137Cs measurements have been performed in order
to verify the estimated sedimentation rates in this lake. Fig. 4 pre-
sents 137Cs activity and 210Pb age previously estimated vs. depth in
the sediment core. 137Cs is an anthropogenic radionuclide which
has been released in important amounts because of nuclear tests.
137
Cs started to fallout on land surfaces circa 1952 (Davis et al.,
1984) and peaks of 137Cs are generally observed circa 1963 in sed-
iments cores (Ali et al., 2008). In Fig. 4, we notice that the peak of
137
Cs corresponds to a 210Pb age of approximately 45 years which
is in agreement with the date of 1963. Thus, 137Cs confirms the
ages previously estimated by 210Pb dating.
Based on sedimentation rates estimated by 210Pb dating, a
straight horizontal line symbolizes an age of 100 years in each sed-
iment core in Figs. 5, 6, 10 and A1 and A2 from the Appendix A.
3.2. Spatial, historical analysis of lakes and drainage areas and THg
contents in lakes sediment cores
Spatial and historical analysis of lakes, drainage areas and THg
contents in lakes sediment cores of the present study have been pre-
viously performed, measured and described by Moingt et al. (2013).
Data from Moingt et al. (2013) summarized the principal bio-mor-
phological parameters and THg results of the studied lakes are pre-
sented respectively in Tables A1 and A2 from the Appendix A.
Based on 210Pb dating, the increases in THg in reference lakes
correspond to about the start of the industrial era (Appendix A,
Fig. A1). The Hg anthropogenic sedimentary enrichment factor
(ASEF) values come to 2.7 and 2.8 for Ouescapis and Rodayer lakes
respectively. These ASEF values are similar to those frequently re-
ported in the literature for pristine North American lakes of the
boreal domain (Lindberg et al., 2007; Lucotte et al., 1995).
Three out of six lakes (Des Jardins East, Des Jardins West and
Waswanipi) with perturbed watersheds are characterized by Hg
ASEF values inferior to 3 since the beginning of the industrial era.
i.e. similar to those of the two pristine lakes (Appendix A,
Fig. A2). The three remaining lakes (Chibougamau, Matagami and
Dickson) present much higher Hg ASEF values (3.8, 5.4 and 15
respectively; Appendix A, Table A2).
3.3. Lignin biomarkers measurements
Lambda and Sigma 8 indicators are commonly used to estimate
the relative amount of TOM in sediments (Houel et al., 2006;
38 M. Moingt et al. / Applied Geochemistry 41 (2014) 34–48
Fig. 2. Total 210Pb activity (full black rhombs) and natural logarithm of unsupported 210Pb activity (white rhombs) vs. depth in reference lakes sediment cores (i.e. Ouescapis
and Rodayer lakes).
Teisserenc et al., 2011). Lambda corresponds to the sum of vanillyl,
syringyl and cinnamyl phenols per 100 mg of OC whereas Sigma 8
represents the same sum of compounds but normalized for 10 g of
sample. Thus, Lambda corresponds to the relative amount of terrig-
enous OM with respect to the total OC content of a sediment sam-
ple and Sigma 8 corresponds to the relative amount of terrigenous
OM to a sediment sample. Fig. 5 presents Lambda and Sigma 8
indicators profiles for reference lakes (i.e. Ouescapis and Rodayer
lakes) in the first 40 cm of the sediment cores. Lambda profiles
are similar for Ouescapis and Rodayer lakes with values ranging
from 0.71 to 1.51 mg/100 mg of OC and from 0.68 to 1.76 mg/
100 mg of OC respectively. Sigma 8 ranges from 1.71 to 3.76 mg/
10 g of sample and from 1.17 to 4.08 mg/10 g of sample for Oues-
capis and Rodayer lakes respectively.
Fig. 6 presents Lambda and Sigma 8 indicators profiles in lakes
presenting various types of perturbations in their watersheds. Con-
sidering Lambda values, only Matagami Lake shows major devia-
tion from the 0.5 to 2.0 mg/100 mg of OC range observed in the
two reference lakes with values as high as 7.94 mg/100 mg of OC.
On the other hand, Sigma 8 values present a wide range of values
comprised between 0.02 and 48.14 mg/10 g of sample (Fig. 6).
In Figs. 7–9, we present the mean values of lignin biomarkers
and the corresponding standard deviation for the last 100 year per-
iod, estimated using 210Pb dating, of each sediment core. Mean
Lambda values are comprised between 0.77 ± 0.07 and
3.59 ± 2.10 mg/100 mg of OC (Fig. 7) which is in agreement with
values reported for large lake sediments in the literature (Hyodo
et al., 2008; Orem et al., 1997; Petit et al., 2011; Tareq et al.,
2011). Reference lakes present the lowest Lambda values. With
the exception of Matagami Lake, which present important Lambda
variations through time, all the lakes have Lambda values that are
relatively stable during the last 100 year period (Fig. 7).
S/V ratios are generally used to estimate the contribution of
angiosperm species to TOM contents in lake sediments (Hedges
and Mann, 1979; Tesi et al., 2008). Mean S/V ratio values vary from
0.22 ± 0.07 to 0.39 ± 0.02 (Fig. 8). P/(V + S) ratio is used as indicator
of the degradation state of TOM (Dittmar and Lara, 2001; Opsahl
and Benner, 1995) since demethoxylation leads to the selective
loss of OCH3 group in S and V families whereas p-hydroxyphenols
are not affected (Hedges and Ertel, 1982). 3,5-Bd/V is an indicator
of OM maturation in soils (Houel et al., 2006; Prahl et al., 1994).
Mean P/(V + S) values range from 0.16 ± 0.05 to 1.07 ± 0.08
whereas mean 3,5-Bd/V values are comprised between
0.14 ± 0.06 and 0.70 ± 0.15. Fig. 9 shows that when all lakes are
considered together, P/(V + S) and 3,5-Bd/V ratios are not corre-
lated (r = 0.53; p = 0.2825). If Chibougamau Lake is excluded, we
then find a strong correlation between those two ratios (r = 0.95;
p = 0.0150).
Lignin phenol results are summarized in Table A3 in the Appen-
dix A.
4. Discussion
Although sampling one core per site at the focal point of a given
large lake does not allow observing site-specific inhomogeneities,
it remains an efficient way to obtain a global signal integrating
both TOM and Hg dynamics at the watershed scale (Hakanson
and Jansson, 1983; Moingt et al., 2013; Teisserenc et al., 2010).
 M. Moingt et al. / Applied Geochemistry 41 (2014) 34–48
Fig. 3. Total 210Pb activity (full black rhombs) and natural logarithm of unsupported 210Pb activity (white rhombs) vs. depth in Dickson, Chibougamau and Waswanipi lakes
sediment cores.
4.1. Lambda and Sigma 8 indicators
In reference lakes, the relative stability of Lambda along the
sediment cores (Fig. 5) indicates that little changes occurred in
the ratio of allochthonous vs. autochthonous organic matter over
time. The magnitude of variation in Sigma 8 along the core profiles
is higher than that of Lambda (Fig. 5). Given that these two indica-
tors have the same trends along the profiles, their variations are
unlikely due to variations in the amount of inorganic matter com-
ing from the watershed but rather due to changes in TOM fluxes.
Contrary to sediment cores of reference lakes, Lambda profiles
in sediment cores of Matagami and Dickson lakes present marked
variations (Fig. 6) suggesting shifts in the ratio of allochthonous vs.
autochthonous sedimentary organic matter. Matagami Lake’s sed-
iment core presents sporadic and important variations of the
Lambda indicator suggesting that specific events induced tempo-
rary variations in sedimentary OM fluxes trough the time. Because
those changes are observed before and after the onset of the indus-
trial era, we cannot attribute those modifications to either natural
events or anthropogenic activities over the last 100 years. The
Lambda profile of Dickson Lake shows a modification of the indica-
tor occurring at 20 cm depth (Fig. 6) which, by extrapolation of the
sedimentation rate, would correspond to the year 1600. This mod-
ification is sudden and permanent suggesting an important salient
event, which modified the sedimentary regime of OM in the lake.
Similar observations have been reported in other lakes (Hyodo
et al., 2008; Louchouarn et al., 1993; Teisserenc et al., 2013). More-
over, because this event happened before the European settlement
of this region, we can assume that it corresponds to a major natural
39
event. In each perturbed lake, Lambda and Sigma 8 core profiles are
similar suggesting that the variations observed for the Lambda
indicator are due to variations in TOM fluxes coming from the wa-
tershed and not to fluctuations of the primary production into the
water column of the lake (Houel et al., 2006; Rezende et al., 2010).
4.2. Impact of mining and logging activities on TOM fluxes: coupling
lignin biomarkers and a GIS approach
Using a GIS approach allowed us to confirm that the two refer-
ences lakes have not been intensely exposed to logging and/or
mining activities since 1979 whereas Waswanipi, Chibougamau,
Matagami, Dickson and Des Jardins lakes watersheds have been
widely logged and/or used by mining industries over the same per-
iod of time (Moingt et al., 2013).
4.2.1. Impact of logging activities
Lignin biomarkers in lake sediments reflect the nature of vege-
tation cover and soil types in the lake watershed and thus can be
used to identify the impact of logging activities on TOM fluxes
reaching the lakes (Brandenberger et al., 2011; Gordon and Goñi,
2003; Hedges and Mann, 1979; Louchouarn et al., 1999). Sedi-
ments impacted by logging activities are characterized by higher
Lambda values than those of pristine lakes because of increased
transfers of TOM from watersheds to aquatic systems in deforested
areas (Brandenberger et al., 2011; Loh et al., 2012). Fig. 7 presents
the mean Lambda values measured in sediments covering the last
100 year period for the studied lakes. Des Jardins E. and W. lakes
are not considered because the difference in latitude between
40 M. Moingt et al. / Applied Geochemistry 41 (2014) 34–48

Fig. 4. Total 210Pb activity vs. depth (A) and natural logarithm of unsupported 210Pb activity vs. depth (B) in Matagami Lake. 137Cs activity vs. depth (C) and 137Cs activity and
210
Pb age vs. depth (D) in the sediment core of Matagami Lake.

Fig. 5. Lambda (full black rhombs) and Sigma 8 (white diamonds) indicators vs. depth in reference lakes. Error bars are not visible at this scale. The straight black lines
represent an age of 100 years for each core based on 210Pb dating.

those lakes and reference lakes could explain a difference in the re-
gime of the lakes as suggested by the high Sigma 8 values encoun-
tered for Desjardins Lakes (Fig. 6). Sediments of Waswanipi and
Chibougamau lakes present mean Lambda values over the last
100 year period similar to those measured in reference lakes
(Fig. 7) and not different from the Lambda values measured in
the part of the core older than 100 years (Fig 6). Those observations
suggest minor impact of logging activities on TOM fluxes at the
watershed scale despite the fact they have been intensely impacted
by logging activities since 1979 (Moingt et al., 2013). In contrast,
sediments of Dickson and Matagami lakes display mean Lambda
values over the last 100 years significantly higher than those of
 M. Moingt et al. / Applied Geochemistry 41 (2014) 34–48 41

Fig. 6. Lambda (full black rhombs) and Sigma 8 (white diamonds) indicators vs. depth in lakes presenting various types of anthropogenic perturbations occurring in their
watersheds. Error bars are not visible at this scale. The straight black lines represent an age of 100 years for each core based on 210Pb dating.

reference lakes suggesting at first that logging activities in these
lakes may have increased TOM fluxes reaching the lake. However,
in Dickson Lake, there is no difference between measured Lambda
values in recent sediments and in sediments older than 100 years
once again suggesting a minor impact, at the watershed scale, of
logging activities on the amount of TOM reaching lake sediments.
In Matagami Lake we can observe strong variations in the
Lambda values both in recent sediments and in sediments older
than 100 years. In the last 100 years, we can observe two major
peaks of Lambda at ten and three centimeters. The beginning of
the deeper peak corresponds to an event older than 100 years
and then could not be related to logging activities which start in
42 M. Moingt et al. / Applied Geochemistry 41 (2014) 34–48
Fig. 7. Mean Lambda values and associated standard deviation measured in
sediments covering the last 100 year period for the lakes of the study based on 210Pb
dating. Gray area distinguishes reference lakes from the others lakes of the study.
Fig. 8. Mean S/V ratio values and associated standard deviation measured in
sediments covering the last 100 year period for the lakes of the study based on 210Pb
dating. Gray area distinguishes reference lakes from the others lakes of the study.
the middle of the 1960s in the Matagami region. The beginning of
the second peak corresponds to the nineties which can be
associated with the most intense period of forest cutting in the
Matagami Lake watershed based on GIS results (Moingt et al.,
2013). Then, due to the high natural variability of the Lambda val-
ues, it is not possible to definitively relate any peak to anthropo-
genic activities.
Logging activities are known to trigger the lixiviation of TOM
normally found in soils (Farella et al., 2001). Transfers of TOM from
logged watersheds to aquatic systems are then characterized by
lower S/V signatures, characteristic of humified TOM after pedo-
genesis (Teisserenc, 2009). Sediments in lakes impacted by logging
activities in their watersheds should then also record lower S/V ra-
tios than those of pristine lakes. Fig. 8 presents the mean S/V ratio
values measured in sediments covering the last 100 year period for
the lakes of the study. Those values are low when compared to S/V
Fig. 9. Mean P/(V + S) ratio vs. mean 3,5-Bd/V ratio values and associated standard
deviation measured in sediments covering the last 100 year period (full black
rhombs) and the period before the industrial era (white squares) for the lakes of the
study based on 210Pb dating.
ratios of pure angiosperm sources (Goñi and Hedges, 1992; Hedges
and Ertel, 1982; Hedges and Mann, 1979), suggesting a significant
contribution of gymnosperm species. However, Teisserenc (2009)
showed that a comparison of S/V ratio in sediments to S/V ratio
in soils would be a better tool for historical reconstruction of ter-
restrial inputs to aquatic systems since soils are a better integrator
of vegetation cover diversity, degradation and adsorption pro-
cesses affecting TOM composition (Hernes et al., 2007; Louchouarn
et al., 1999; Prahl et al., 1994; Sánchez-García et al., 2009). Our
mean S/V ratio values for the last 100 year period are in agreement
with the values reported by Teisserenc (2009) in boreal upper soils
suggesting then that the organic horizon of soils is the major con-
tributor of sedimentary TOM. It is also suggesting that in boreal
ecosystems, although the landscape is dominated by gymno-
sperms, angiosperms are important contributors to sedimentary
TOM since gymnosperms do not produce syringyls (Hedges and
Mann, 1979; Hedges and Parker, 1976). Unfortunately, because of
the strong variability of S/V values in the sediment core, this lignin
indicator cannot be used to confirm that Matagami Lake sediments
are actually significantly impacted by logging activities occurring
in their watershed.
P/(V + S) and 3,5-Bd/V ratios are used to estimate the level of
degradation and the degree of maturation of TOM respectively
(Dittmar and Lara, 2001; Houel et al., 2006). Moreover, 3,5-Bd/V ra-
tios could be used to distinguish TOM from organic and inorganic
soil horizons (Houel et al., 2006). Fig. 9 presents mean P/(V + S)
and 3,5-Bd/V ratios measured in sediments over the last 100 year
period for the lakes of the study. Chibougamau Lake probably does
not fit into the regression observed in Fig. 9 for two reasons: (i)
p-hydroxyphenols amount measured in sediments over the last
100 years is similar to the one measured in the other sediment
cores, and (ii) both syringyl and vanillyl contents are the lowest
compared to the other lakes cores examined in this study
(0.06 ± 0.04 and 0.24 ± 0.04 mg/100 mg of OC respectively). Chibo-
ugamau Lake has the lowest sedimentation rate of all the lakes of
this study which could explain really low levels of syringyl phenols
since they are more sensitive to degradation processes than the
others phenol families (Houel et al., 2006; Opsahl and Benner,
1995). Both Matagami and Dickson lakes present significantly low-
er P/(V + S) and 3,5-Bd/V ratios suggesting that sedimentary TOM
in those lakes comes from the upper soil organic horizon (Houel
et al., 2006; Teisserenc, 2009), which is in agreement with the fact
 M. Moingt et al. / Applied Geochemistry 41 (2014) 34–48
that draining processes are more superficial in clear-cut land in
comparison to natural forest cover (Farella et al., 2001). However,
despite this observation, in the case of large lakes boreal ecosys-
tems, at a watershed scale our data suggest that logging activities
globally does not seem to have a noticeable impact on sedimentary
TOM signatures and fluxes. Then large-scale watersheds show
some ‘‘buffering’’ capacity to logging disturbances since about
30% of cut in a watershed is needed to start showing an impact
on sedimentary TOM (Moingt et al., 2013). Our study is based on
large lakes with large watersheds (watershed areas comprised be-
tween 58 and 1084 km2), then the system’s inertia is most likely
responsible for this ‘‘buffering’’ capacity since it increases the
amount of time needed for the perturbation to reach the system.
Indeed, during the transfer of organic matter from the terrestrial
system to the aquatic system, several processes could contribute
to mask and/or dilute the signal of the perturbation (e.g. OM deg-
radation, OM incorporation into soils, fractionation of the TOM
pool).
4.2.2. Impact of mining activities
The presence of mine tailing in the watershed normally in-
creases the amount of inorganic component of sediment reaching
the lake (Petit et al., 2011). This increase should then induce a de-
crease in the Sigma 8 in lake sediments by diluting the TOM signal
in the sediment sample. However, Fig. 6 shows that for the four
lakes presenting mining activities in their watersheds, Sigma 8 is
stable or slightly increases. Moreover, soil erosion normally trig-
gers higher rates of transfer of dissolved and particulate nutrients
Fig. 10. THg (ng/g) and Sigma 8 (mg/10 g of sample) vs. depth in Matagami and Dickson lakes sediment cores. The straight black line represents an age of 100 years based on
210
Pb dating.
Fig. A1. Total mercury contents vs. depth in reference lakes (i.e. Ouescapis and Rodayer lakes). The straight black lines represent an age of 100 years for each core based on
210
Pb dating. Figure modified from Moingt et al. (2013).
43
from the watershed to the water column (Fraser et al., 1999; Klee-
berg et al., 2008; Sharpley et al., 2001). These additional nutrient
loads then enhance the production of aquatic biota. A change in
the primary production of the lake can be detected by the study
of the Lambda indicator since it is proportional to the allochtho-
nous/autochthonous ratio of OM in a sediment sample. Over the
last 100 year period, only Matagami Lake presents variations in
the Lambda indicator (Fig. 6). In this case, Lambda variations along
the core cannot be associated with changes in primary production
as explained previously in Section 4.1. The onset of mining activi-
ties in the watershed could also induce a change in TOM sources.
First, excavation processes bring to the surface important amounts
of TOM from deeper soil horizon with lignin signatures impacted
by pedogenesis (i.e. high P/(V + S) and 3,5-Bd/V ratios). Second,
mining activities enhance drainage and erosion rates of surface soil
horizons (Mäkinen et al., 2010) characterized by less degraded
TOM (i.e. low P/(V + S) and 3,5-Bd/V ratios). However, studied lakes
with mining activities in their watersheds do not present any
change of the P/(V + S) vs. 3,5-Bd/V signatures from the pre-indus-
trial period to present (Fig. 9). Biomarkers data then suggest that in
large lakes with large watersheds, the impact of mining activities
on TOM fluxes is negligible when considering sediment cores inte-
grating the whole watershed.
4.3. Combined transfers of TOM and Hg from watersheds to lakes
210
Pb dating allows us to confirm that for all the lakes of the
present study the significant increase in THg contents in sediment
44 M. Moingt et al. / Applied Geochemistry 41 (2014) 34–48
Fig. A2. Total mercury contents vs. depth in lakes presenting various type of anthropogenic perturbations in their watershed. The straight black lines represent an age of
100 years for each core based on 210Pb dating. Figure modified from Moingt et al. (2013).
coincide with the beginning of the industrial era (Appendix A,
Figs. A1 and A2).
THg contents increase in the last 100 years is not necessarily
associated with an increase in the Lambda and Sigma 8 indicators
(Figs. 5 and 6), which would indicate an increase in TOM inputs
reaching lake sediments. Then, the results of the present study
show that in large boreal lake ecosystems there is no clear evi-
dence of an impact of land-uses occurring in the watershed on both
sedimentary TOM and THg contents. This lack of correlation be-
tween the evolution of Lambda and Sigma 8 indicators and THg
contents along a sediment core could be due to the fact that the
amount of TOM naturally transferred to the lake is widely suffi-
cient to scavenge and bind the amount of Hg being deposited from
the atmosphere even with this amount increasing over the last
150 years due to the industrial era while TOM fluxes remain rela-
tively constant. However, this observation is not valid for Mata-
gami and Dickson lakes (Fig. 10).
Considering Matagami Lake, sporadic variations in the Sigma 8
indicator are observed before and after the onset of the industrial
era. Before that era, Sigma 8 variations are not correlated to THg
fluctuations whereas over the last century, trends in Sigma 8 and
THg contents do correlate (r = 0.93, p = 0.0187). This pattern sug-
gests that THg peaks measured in sediments over the last 100 year
period are due to transfers of recently deposited atmospheric Hg
from the watersheds to the lakes. Moreover, because an increase
in TOM fluxes induces an increase in THg contents in sediments,
any contemporary watershed perturbation (natural and/or anthro-
pogenic) influencing TOM fluxes will affect sediment THg levels.
In Dickson Lake, an important increase in the Sigma 8 indicator
at 20 cm depth is observed and corresponds to a sharp increase in
THg in sediments (r = 0.87, p < 0.0001). An extrapolation of 210Pb
dating results allows us to situate this event 400 years ago and
thus conclude that this anomaly corresponds to a natural event.
Moreover, after this event, both Sigma 8 and THg did not come
back to their initial levels suggesting a drastic change in the wa-
tershed lake regime after natural flooding or landslide for example.
Teisserenc et al. (2013) observed the same pattern in flooded lakes
for both Lambda and THg in sediment cores and concluded that
this pattern was also evidence of a close association between
TOM and THg loading. Dickson Lake is also a good example show-
ing the importance of sedimentation rates to better understand the
Hg cycle in boreal lakes ecosystems. In this lake, the ratio between
THg baseline concentration and THg peak at the surface is 15 (i.e.
ASEF = 15). However, knowing that most of the THg increase ob-
served in the sediment core is pre-industrial era, probably due to
a natural change of the regime of the lake, for a representative ASEF
we have to change the THg baseline content previously considered.
The new ASEF becomes 3.2, which is more typical of other North
American lakes reported in the literature (Kamman and Engstrom,
2002; Lucotte et al., 1995; Swain et al., 1992).
5. Conclusion
Over the last decade, several publications based on the study of
small lakes point to anthropogenic perturbations occurring in the
 M. Moingt et al. / Applied Geochemistry 41 (2014) 34–48 45

Table A1
Biogeomorphological characteristics of the lakes of the present study as presented in Moingt et al. (2013). %TWA = percentage of the total watershed area, Gr = gravel roads,
L = logging activities, U = urbanization, G = golf.

Lake Localization Altitude Lake area Drainage DA/LA Mean Year Water Coniferous Mixed forest, Unforested Number of Major
lat./long. (m) (km2) area (km2) slope (%) (%TWA) (%TWA) deciduous >50% (%TWA) mines in the disturbances
(TWA%) watershed
Des Jardins 46°390 N 320 15.02 207.39 13.81 5.85 2001 9.62 0.00 33.66 3.57 x Gr, L
78°150 W 2004 10.04 0.00 18.46 0.37
2010 9.56 0.00 43.36 2.27
Ouescapis 50°150 N 278 36.41 107.94 2.96 4.84 1979 0.00 0.00 7.01 2.35 x Gr
76°600 W 1990 0.00 0.00 1.80 1.80
2010 0.02 0.00 5.12 13.98
Rodayer 50°510 N 249 22.31 57.7 2.59 1.34 1979 1.93 0.00 13.94 3.65 x Gr
77°410 W 1990 2.12 0.00 5.33 0.95
2010 2.43 0.00 3.27 2.44
Waswanipi 49°330 N 267 200.69 1483.66 7.39 2.02 1979 1.41 0.00 12.05 7.35 3 Gr, L
76°270 W 1990 0.65 0.00 5.47 20.38
2010 1.36 0.00 7.16 15.61
Chibougamau 49°500 N 378 201.06 769.87 3.83 4.45 1999 8.68 0.00 18.66 16.31 14 Gr, L, U
74°130 W 2002 8.76 0.00 21.13 5.82
2009 8.61 0.00 19.17 10.18
Dickson 49°380 N 342 10.00 227.59 22.76 3.23 1979 0.85 0.00 11.63 5.65 1 Gr, L
75°110 W 1990 1.58 0.00 2.63 12.65
2010 1.30 0.00 10.37 7.78
Matagami 49°500 N 248 209.86 951.36 4.53 2.84 1979 2.15 0.00 12.94 8.72 7 Gr, L, U, Go
77°370 W 1990 0.24 0.00 8.46 27.27
2010 1.14 0.00 12.15 8.28

Table A2 of the TOM pool, incorporation of Hg into wetlands, Hg adsorption

Mercury characteristics in lake sediment cores. Data are from Moingt et al. (2013). on the soil mineral phase, which could contribute to mask and/or
Lake THg baseline in THg peak in ASEF EHg dilute the signal of the perturbation.
sediment (ng/g) sediment (ng/g) Irrespective of the presence or absence of an impact from land-
(ng/g) use, this study underlines the importance of TOM, based on lignin
Des Jardins 169 364 2.2 196 biomarkers results, as a vector of Hg transfer from the watershed
Ouescapis 33 89 2.7 56 to the receiving lakes since sedimentary Hg enrichment seems to
Rodayer 24 67 2.8 43
be directly proportional to the amount of TOM coming from the
Waswanipi 40 98 2.5 58
Chibougamau 40 150 3.8 110 watershed (Sigma 8 indicator). This is critical since TOM flows nat-
Dickson 6 90 15 84 urally from watershed soils and has thus contributed to a marked
Matagami 16 87 5.4 (surface) 71 increased accumulation of atmospheric Hg in lake sediments. Then,
15.0 (peak)
any natural and/or anthropogenic modification increasing TOM
fluxes from the watershed to the lake can increase the amount of
Hg reaching the lake, this supplementary Hg having the potential
watershed (e.g. logging and mining activities) as a contributor to
to be methylated and then incorporated into the aquatic food
the increasing amount of THg reaching lakes sediments (Garcia
chain. Because most of the atmospheric/deposited Hg is associated
and Carignan, 2000, 2005; Porvari and Verta, 2003; Porvari et al.,
with ground vegetation and with soils (Hintelmann et al., 2002;
2003). In contrast to these findings on watersheds for small lakes,
Ouellet et al., 2009) a decrease in Hg emissions should ultimately
the present study demonstrates that the impact of major anthropo-
lead to a decrease in the amount of Hg transferred from the wa-
genic activities (e.g. extensive logging, mining) occurring in the
tershed to the lake. A solid knowledge of both bio-morphological
watershed of large boreal lakes is not necessarily discernible in
parameters (e.g. mean slope, vegetation cover; Moingt et al.,
Hg and TOM concentrations in sediment cores integrating the
2013) and TOM inputs to the lake could help to identify water-
whole watershed. Indeed, in most of the lakes with anthropogenic
sheds at higher risk of exporting Hg to the lake in order to limit
perturbations in their watersheds, THg profiles are typical of atmo-
the human health risk by fish consumption.
spheric/deposition impacted sediments (i.e. ASEF around 3)
whereas the sedimentary lignin signature does not change after
the beginning of those activities in the watershed. However, in Acknowledgments
highly impacted watersheds (e.g. forest clearing in the order of
30% the watershed surface over 10 years) both Hg and organic mat- This project was financed through the CARA (Clean Air Regula-
ter contents can be influenced. This study indicates that large-scale tory Agenda) program of Environment Canada. We would like to
watersheds are characterized by some ‘‘buffering’’ capacity to land- thank Sophie Chen for her assistance in the laboratory and Jean-
use disturbance, which would be more likely due to the system’s Sébastien Beaulne for his help during the sampling work.
inertia since it increases the amount of time needed for a perturba-
tion to reach the system. Indeed in large watershed boreal ecosys- Appendix A. Appendix
tems, THg and TOM are more likely to be impacted by processes,
such as OM degradation, OM incorporation into soils, fractionation See Figs. A1 and A2 and Tables A1–A3.
Table A3

46
Primary lignin–phenol results. In each core, the gray area corresponds to the portion of the core younger than 100 years. allo = allochthonous, auto = autochthonous.

M. Moingt et al. / Applied Geochemistry 41 (2014) 34–48

 M. Moingt et al. / Applied Geochemistry 41 (2014) 34–48 47

References Houel, S., Louchouarn, P., Lucotte, M., Canuel, R., Ghaleb, B., 2006. Translocation of
soil organic matter following reservoir impoundment in boreal systems:
implications for in situ productivity. Limnol. Oceanogr. 51, 1497–1513.
Ali, A.A., Ghaleb, B., Garneau, M., Asnong, H., Loisel, J., 2008. Recent peat
Hu, F.S., Hedges, J.I., Gordon, E.S., Brubaker, L.B., 1999. Lignin biomarkers and pollen
accumulation rates in minerotrophic peatlands of the Bay James region,
in postglacial sediments of an Alaskan lake. Geochim. Cosmochim. Acta 63,
Eastern Canada, inferred by 210Pb and 137Cs radiometric techniques. Appl.
1421–1430.
Radiat. Isot. 66, 1350–1358.
Hyodo, F., Tsugeki, N., Azuma, J.-I., Urabe, J., Nakanishi, M., Wada, E., 2008. Changes
Appleby, P.G., Oldfield, F., 1992. Application of 210Pb to sedimentation studies. In:
in stable isotopes, lignin-derived phenols, and fossil pigments in sediments of
Uranium Series Disequilibrium. Application to Earth, Marine and
Lake Biwa, Japan: implications for anthropogenic effects over the last 100 years.
Environmental Sciences. Oxford University Press, pp. 731–778.
Sci. Total Environ. 403, 139–147.
Beaulne, J.-S., Lucotte, M., Paquet, S., Canuel, R., 2012. Modeling mercury
Ikingura, J.R., Akagi, H., 1996. Monitoring of fish and human exposure to mercury
concentrations in northern pikes and walleyes from frequently fished lakes of
due to gold mining in the Lake Victoria goldfields, Tanzania. Sci. Total Environ.
Abitibi-Témiscamingue (Québec, Canada): a GIS approach. Boreal Environ. Res.
191, 59–68.
17, 277–290.
Kainz, M., Lucotte, M., Parrish, C.C., 2003. Relationships between organic matter
Bloom, N.S., Fitzgerald, W.F., 1988. Determination of volatile mercury species at the
composition and methyl mercury content of offshore and carbon-rich littoral
picogram level by low temperature gas chromatography with cold-vapor
sediments in an oligotrophic lake. Can. J. Fish. Aquat. Sci. 60, 888–896.
atomic fluorescence detection. Anal. Chim. Acta 208, 151–161.
Kamman, N.C., Engstrom, D.R., 2002. Historical and present fluxes of mercury to
Brandenberger, J., Louchouarn, P., Crecelius, E., 2011. Natural and post-urbanization
Vermont and New Hampshire lakes inferred from 210Pb dated sediment cores.
signatures of hypoxia in two basins of Puget sound: historical reconstruction of
Atmos. Environ. 36, 1599–1609.
redox sensitive metals and organic matter inputs. Aquat. Geochem. 17, 645–670.
Kleeberg, A., Schapp, A., Biemelt, D., 2008. Phosphorus and iron erosion from non-
Chabbi, A., Rumpel, C., 2004. Decomposition of plant tissue submerged in an
vegetated sites in a post-mining landscape, Lusatia, Germany: impact on
extremely acidic mining lake sediment: phenolic CuO-oxidation products and
aborning mining lakes. CATENA 72, 315–324.
solid-state 13C NMR spectroscopy. Soil Biol. Biochem. 36, 1161–1169.
Kolka, R.K., Grigal, D.F., Verry, E.S., Nater, E.A., 1999. Mercury and organic carbon
Coquery, M., Welbourn, P.M., 1995. The relationship between metal concentration
relationships in streams draining forested upland/peatland watersheds. J.
and organic matter in sediments and metal concentration in the aquatic
Environ. Qual. 28, 766–775.
macrophyte Eriocaulon septangulare. Water Res. 29, 2094–2102.
Lavoie, R.A., Hebert, C.E., Rail, J.-F., Braune, B.M., Yumvihoze, E., Hill, L.G., Lean,
Dalzell, B.J., Filley, T.R., Harbor, J.M., 2007. The role of hydrology in annual organic
D.R.S., 2010. Trophic structure and mercury distribution in a Gulf of St.
carbon loads and terrestrial organic matter export from a midwestern
Lawrence (Canada) food web using stable isotope analysis. Sci. Total Environ.
agricultural watershed. Geochim. Cosmochim. Acta 71, 1448–1462.
408, 5529–5539.
Davis, R.B., Hess, C.T., Norton, S.A., Hanson, D.W., Hoagland, K.D., Anderson, D.S.,
Lindberg, S., Bullock, R., Ebinghaus, R., Engstrom, D., Feng, X., Fitzgerald, W., Pirrone, N.,
1984. 137Cs and 210Pb dating of sediments from soft-water lakes in New England
Prestbo, E., Seigneur, C., 2007. A synthesis of progress and uncertainties in attributing
(U.S.A.) and Scandinavia, a failure of 137Cs dating. Chem. Geol. 44, 151–185.
the sources of mercury in deposition. AMBIO: A J. Hum. Environ. 36, 19–33.
Dittmar, T., Lara, R.J., 2001. Molecular evidence for lignin degradation in sulfate-
Loh, P.S., Chen, C.-T.A., Anshari, G.Z., Wang, J.-T., Lou, J.-Y., Wang, S.-L., 2012. A
reducing mangrove sediments (Amazônia, Brazil). Geochim. Cosmochim. Acta
comprehensive survey of lignin geochemistry in the sedimentary organic
65, 1417–1428.
matter along the Kapuas River (West Kalimantan, Indonesia). J. Asian Earth Sci.
Farella, N., Lucotte, M., Louchouarn, P., Roulet, M., 2001. Deforestation modifying
43, 118–129.
terrestrial organic transport in the Rio Tapajós, Brazilian Amazon. Org.
Louchouarn, P., Lucotte, M., Mucci, A., Pichet, P., 1993. Geochemistry of mercury in
Geochem. 32, 1443–1458.
two hydroelectric reservoirs in Quebec, Canada. Can. J. Fish. Aquat. Sci. 50, 269–
Fitzgerald, W.F., Engstrom, D.R., Mason, R.P., Nater, E.A., 1998. The case for
281.
atmospheric mercury contamination in remote areas. Environ. Sci. Technol.
Louchouarn, P., Lucotte, M., Farella, N., 1999. Historical and geographical variations
32, 1–7.
of sources and transport of terrigenous organic matter within a large-scale
Flynn, W.W., 1968. The determination of low levels of polonium-210 in
coastal environment. Org. Geochem. 30, 675–699.
environmental materials. Anal. Chim. Acta 43, 221–227.
Lucotte, M., Mucci, A., Hillaire-Marcel, C., Pichet, P., Grondin, A., 1995.
Fraser, A.I., Harrod, T.R., Haygarth, P.M., 1999. The effect of rainfall intensity on soil
Anthropogenic mercury enrichment in remote lakes of northern Québec
erosion and particulate phosphorus transfer from arable soils. Water Sci.
(Canada). Water Air Soil Pollut. 80, 467–476.
Technol. 39, 41–45.
Louchouarn, P., Opsahl, S., Benner, R., 2000. Isolation and Quantification of
Garcia, E., Carignan, R., 2000. Mercury concentrations in northern pike (Esox lucius)
Dissolved Lignin from Natural Waters Using Solid-Phase Extraction and GC/
from boreal lakes with logged, burned, or undisturbed catchments. Can. J. Fish.
MS. Anal. Chem. 72, 2780–2787.
Aquat. Sci. 57, 129–135.
Mäkinen, J., Kauppila, T., Loukola-Ruskeeniemi, K., Mattila, J., Miettinen, J., 2010.
Garcia, E., Carignan, R., 2005. Mercury concentrations in fish from forest harvesting
Impacts of point source and diffuse metal and nutrient loading on three
and fire-impacted Canadian Boreal lakes compared using stable isotopes of
northern boreal lakes. J. Geochem. Explor. 104, 47–60.
nitrogen. Environ. Toxicol. Chem. 24, 685–693.
Moingt, M., Bressac, M., Bélanger, D., Amyot, M., 2010. Role of ultra-violet radiation,
Goñi, M.A., Hedges, J.I., 1992. Lignin dimers: structures, distribution, and potential
mercury and copper on the stability of dissolved glutathione in natural and
geochemical applications. Geochim. Cosmochim. Acta 56, 4025–4043.
artificial freshwater and saltwater. Chemosphere 80, 1314–1320.
Goñi, M.A., Montgomery, S., 2000. Alkaline CuO oxidation with a microwave
Moingt, M., Lucotte, M., Paquet, S., Beaulne, J.-S., 2013. The influence of
digestion system: lignin analyses of geochemical samples. Anal. Chem. 72,
anthropogenic disturbances and watershed morphological characteristics on
3116–3121.
Hg dynamics in Northern Quebec large boreal lakes. Adv. Environ. Res. 2, 81–98.
Goñi, M.A., Nelson, B., Blanchette, R.A., Hedges, J.I., 1993. Fungal degradation of
Neteler, M., Mitasova, H., 2008. Open Source GIS a GRASS GIS Approach. Springer,
wood lignins: geochemical perspectives from CuO-derived phenolic dimers and
New-York, p. 383.
monomers. Geochim. Cosmochim. Acta 57, 3985–4002.
Opsahl, S., Benner, R., 1995. Early diagenesis of vascular plant tissues: lignin and
Gordon, E.S., Goñi, M.A., 2003. Sources and distribution of terrigenous organic
cutin decomposition and biogeochemical implications. Geochim. Cosmochim.
matter delivered by the Atchafalaya River to sediments in the northern Gulf of
Acta 59, 4889–4904.
Mexico. Geochim. Cosmochim. Acta 67, 2359–2375.
Orem, W.H., Colman, S.M., Lerch, H.E., 1997. Lignin phenols in sediments of Lake Baikal,
Hakanson, L., Jansson, M., 1983. Principles of Lake Sedimentology. Springer, New-
Siberia: application to paleoenvironmental studies. Org. Geochem. 27, 153–172.
York.
Ouellet, J.-F., Lucotte, M., Teisserenc, R., Paquet, S., Canuel, R., 2009. Lignin
Hamilton, T.F., Smith, J.D., 1986. Improved alpha energy resolution for the
biomarkers as tracers of mercury sources in lakes water column.
determination of polonium isotopes by alpha-spectrometry. Int. J. Radiat.
Biogeochemistry 94, 123–140.
Appl. Instrum. Part A. Appl. Radiat. Isot. 37, 628–630.
Pacyna, E.G., Pacyna, J.M., Steenhuisen, F., Wilson, S., 2006. Global anthropogenic
Hedges, J.I., Ertel, J.R., 1982. Characterization of lignin by gas capillary
mercury emission inventory for 2000. Atmos. Environ. 40, 4048–4063.
chromatography of cupric oxide oxidation products. Anal. Chem. 54, 174–178.
Petit, S., Lucotte, M., Teisserenc, R., 2011. Mercury sources and bioavailability in
Hedges, J.I., Mann, D.C., 1979. The characterization of plant tissues by their lignin
lakes located in the mining district of Chibougamau, eastern Canada. Appl.
oxidation products. Geochim. Cosmochim. Acta 43, 1803–1807.
Geochem. 26, 230–241.
Hedges, J.I., Parker, P.L., 1976. Land-derived organic matter in surface sediments
Pichet, P., Morrison, K., Rheault, I., Tremblay, A., 1999. Analysis of total mercury and
from the Gulf of Mexico. Geochim. Cosmochim. Acta 40, 1019–1029.
methylmercury in environmental samples. In: Schetagne, R., Lucotte, M.,
Hedges, J.I., Keil, R.G., Benner, R., 1997. What happens to terrestrial organic matter
Thérien, N., Langlois, C., Tremblay, A. (Eds.), Mercury in the Biogeochemical
in the ocean? Org. Geochem. 27, 195–212.
Cycle, Natural Environments and Hydroelectric Reservoirs of Northern Québec.
Hernes, P.J., Benner, R., 2003. Photochemical and microbial degradation of dissolved
Springer, pp. 41–52.
lignin phenols: implications for the fate of terrigenous dissolved organic matter
Porvari, P., Verta, M., 2003. Total and methyl mercury concentrations and fluxes
in marine environments. J. Geophys. Res. 108, 3291.
from small boreal forest catchments in Finland. Environ. Pollut. 123, 181–191.
Hernes, P.J., Robinson, A.C., Aufdenkampe, A.K., 2007. Fractionation of lignin during
Porvari, P., Verta, M., Munthe, J., Haapanen, M., 2003. Forestry practices increase
leaching and sorption and implications for organic matter ‘‘freshness’’. Geophys.
mercury and methyl mercury output from boreal forest catchments. Environ.
Res. Lett. 34, L17401.
Sci. Technol. 37, 2389–2393.
Hintelmann, H., Harris, R., Heyes, A., Hurley, J.P., Kelly, C.A., Krabbenhoft, D.P.,
Prahl, F.G., Ertel, J.R., Goni, M.A., Sparrow, M.A., Eversmeyer, B., 1994. Terrestrial
Lindberg, S., Rudd, J.W.M., Scott, K.J., St.Louis, V.L., 2002. Reactivity and mobility
organic carbon contributions to sediments on the Washington margin.
of new and old mercury deposition in a boreal forest ecosystem during the first
Geochim. Cosmochim. Acta 58, 3035–3048.
year of the METAALICUS study. Environ. Sci. Technol. 36, 5034–5040.
48 M. Moingt et al. / Applied Geochemistry 41 (2014) 34–48
Rezende, C.E., Pfeiffer, W.C., Martinelli, L.A., Tsamakis, E., Hedges, J.I., Keil, R.G., 2010.
Lignin phenols used to infer organic matter sources to Sepetiba Bay – RJ, Brasil.
Estuar. Coast. Shelf Sci. 87, 479–486.
Rognerud, S., Fjeld, E., 2001. Trace element contamination of Norwegian lake
sediments. AMBIO: A J. Hum. Environ. 30, 11–19.
Sánchez-García, L., De Andrés, J.R., Martín-Rubí, J.A., Louchouarn, P., 2009.
Diagenetic state and source characterization of marine sediments from the
inner continental shelf of the Gulf of Cádiz (SW Spain), constrained by
terrigenous biomarkers. Org. Geochem. 40, 184–194.
Sharpley, A.N., Mcdowell, R.W., Kleinmann, P.J.A., 2001. Phosphorus loss from land
to water: integrating agricultural and environmental management. Plant Soil
237, 287–307.
Slauenwhite, D.E., Wangersky, P.J., 1996. Extraction of marine organic matter on
XAD-2: effect of sample acidification and development of an in situ pre-
acidification technique. Mar. Chem. 54, 107–117.
Soto, D.X., Roig, R., Gacia, E., Catalan, J., 2011. Differential accumulation of mercury
and other trace metals in the food web components of a reservoir impacted by a
chlor-alkali plant (Flix, Ebro River, Spain): implications for biomonitoring.
Environ. Pollut. 159, 1481–1489.
Swain, E.B., Engstrom, D.R., Brigham, M.E., Henning, T.E., Brezonik, P.L., 1992.
Increasing rates of atmospheric mercury deposition in midcontinental North
America. Science 257, 784–787.
Tahvanainen, T., Haraguchi, A., 2013. Effect of pH on phenol oxidase activity on
decaying Sphagnum mosses. Eur. J. Soil Biol. 54, 41–47.
Tareq, S.M., Kitagawa, H., Ohta, K., 2011. Lignin biomarker and isotopic records of
paleovegetation and climate changes from Lake Erhai, southwest China, since
18.5 ka BP. Quatern. Int. 229, 47–56.
Teisserenc, R., 2009. Dynamique de la matière organique terrigène et du mercure
dans les lacs et réservoirs boréaux. Institut des Sciences de l’Environnement.
Ph.D. UQAM, Montréal, 2009, p. 182.
Teisserenc, R., Lucotte, M., Houel, S., Carreau, J., 2010. Integrated transfers of
terrigenous organic matter to lakes at their watershed level: a combined
biomarker and GIS analysis. Geochim. Cosmochim. Acta 74, 6375–6386.
Teisserenc, R., Lucotte, M., Houel, S., 2011. Terrestrial organic matter biomarkers as
tracers of Hg sources in lake sediments. Biogeochemistry 103, 235–244.
Teisserenc, R., Lucotte, M., Canuel, R., Moingt, M., Obrist, D., 2013. Combined
dynamics of mercury and terrigenous organic matter following impoundment
of Churchill Falls Hydroelectric Reservoir, Labrador. Biogeochemistry.
Tesi, T., Langone, L., Goñi, M.A., Turchetto, M., Miserocchi, S., Boldrin, A., 2008.
Source and composition of organic matter in the Bari canyon (Italy): dense
water cascading versus particulate export from the upper ocean. Deep Sea Res.
Part I 55, 813–831.
Watras, C.J., Back, R.C., Halvorsen, S., Hudson, R.J.M., Morrison, K.A., Wente, S.P.,
1998. Bioaccumulation of mercury in pelagic freshwater food webs. Sci. Total
Environ. 219, 183–208.
Yang, Y.-K., Zhang, C., Shi, X.-J., Lin, T., Wang, D.-Y., 2007. Effect of organic matter
and pH on mercury release from soils. J. Environ. Sci. 19, 1349–1354.