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Chemistry of Rainwater in The Massif Central (France) : A Strontium Isotope and Major Element Study
Chemistry of Rainwater in The Massif Central (France) : A Strontium Isotope and Major Element Study
941±952, 1998
# 1998 Elsevier Science Ltd
All rights reserved. Printed in Great Britain
PII: S0883-2927(98)00029-8 0883-2927/98 $ - see front matter
Philippe NeÂgrel*
BRGM Service GeÂologique National, Avenue C. Guillemin, BP 6009, 45060 OrleÂans Cedex 2, France
and
SteÂphane Roy{
Laboratoire de GeÂochimie et Cosmochimie, Institut de Physique du Globe de Paris, U.F.R. des
Sciences de la Terre, Universite de Paris VII. Tour 14±24, 3 eÂt., 4 place Jussieu, 75252 Paris, France
AbstractÐAtmospheric aerosols (sea salt, crustal dust, and biogenic aerosols) are the primary source of
dissolved species in rainwater as well as one of the sources of dissolved species in river water. Chemical
weathering studies require quanti®cation of this atmospheric input. The crustal component of atmos-
pheric input can have various origins, both distant and local. The proportions of the various inputs
(marine, distant or local) are determined in this study.
Strontium isotope ratios and Ca, Na, K, Mg, Al, Cl, SO4, NO3 and Sr concentrations were measured
in rainwater samples collected in the Massif Central (France) over a period of one year. Each sample,
collected automatically, represents a monthly series of rain events. Chemical composition of the rain-
water samples varied considerably and the 87Sr/86Sr ratios ranged between 0.709198 and 0.713143.
Using Na as an indicator of marine origin, and Al for the crustal input in rain samples, the pro-
portion of marine and crustal elements was estimated from elemental ratios. A marine origin of 4 to
100% of Cl, of 0.6 to 20% of the SO4, of <1 to 10% of Ca, <1 to 40% of K, 4 to 100% of Mg and
1 to 44% of Sr was determined.
Strontium isotopes were used to characterize the crustal sources. The 87Sr/86Sr ratios of the crustal
sources varied considerably from 0.7092 to 0.71625 and indicate the occurrence of multiple sources for
the crustal component in the analysed rainwaters. # 1998 Elsevier Science Ltd. All rights reserved
Strontium isotope ratios in precipitation have below the funnel inside the box. From the base of the fun-
been reported by several authors. Graustein and nel, water ¯ows through a 165 mm nylon mesh ®lter to
prevent fallout of large particulate matter (leaves, insects)
Armstrong (1983) and Gosz and Moore (1989) and contamination of the sample. Samples were normally
reported 87Sr/86Sr values between 0.7088 and 0.7200 removed once a month, and more often during periods of
for rain in New Mexico. Aberg et al. (1989) found heavy rainfall.
large variations in dry plus wet deposition (0.711± The sampling site is in an open area (altitude 340 m),
far from dirt roads or other sources of contamination, in
0.717) in central Sweden. Anderson et al. (1990) the Massif Central (Fig. 1) between the towns Issoire and
reported values ranging between 0.7098 and 0.7194 Clermont-Ferrand, near Sainte Marguerite and was
in snow from central Scandinavia. NeÂgrel (1992) selected to minimise local sources of contamination. There
measured values between 0.70968 and 0.71277 in are no trees or rock outcrops in the vicinity of the collec-
rainwater over the Congo Basin. Dupre et al. tor. Site accessibility was a major consideration for easy
maintenance during the winter months. The
(1994) have shown that in a rain event collected in Mediterranean is 300 km to the S and the Atlantic Ocean
the Congo Basin, the isotope composition of Sr var- is 380 km to the W. The nearest towns, Clermont-Ferrand
ies considerably (0.71035±0.71326). Herut et al. and Issoire, are located 15 km to the NW, and 14 km to
(1993) have reported a small range in Sr isotopes the S, respectively.
(0.70792±0.70923) in rainwater of Israel. Seimbille
et al. (1989) have reported a small range in Sr iso-
topes (0.70829±0.70895) in rainwater of the Parisian Analytical methods
Basin. These variations are explained by mixing
between several sources in the atmosphere and by Conductivity, temperature and pH were determined on
site on a 50 ml aliquot of monthly collections. Electrical
atmospheric circulations. conductivity and water temperature were determined with
Data are for major (Cl, SO4, NO3, Al, Ca, Na, a microprocessor conductivity meter WTW LF96 standar-
Mg and K) and trace (Sr) element concentrations dized to 208C for the measurement of electrical conduc-
and 87Sr/86Sr ratios in rainwaters (hereafter refered tivity. pH was measured with an Ingold electrode and an
Orion 250 pH-meter calibrated with standard buers (pH
to PSM which stands for the name of the sampling
4.01 and 6.87).
site Sainte Marguerite) collected in the Massif All samples were ®ltered through a pre-washed 0.2 mm
Central (France). The aim of this study was to use Millipore PVDF ®lter with a pre-cleaned Nalgene holder
Sr isotope ratios correlatively with major and trace before analysis. One 250 ml aliquot of the ®ltered rain
elements in order to determine the dierent sources sample was placed in a Nalgene polypropylene bottle.
Polypropylene storage bottles were cleaned with pH 2
(sea salt and crustal sources) of chemical elements ultra-pure water (Milli-Q water system plus redistilled con-
in rainwaters.
METHODOLOGY
centrated HNO3) and conditioned with ultra-pure water average in some places. Most of the rain fell in 3 to
for several weeks. Samples were acidi®ed to pH 2 with
5 days. In July and August, rainfall was below aver-
redistilled concentrated HNO3 and analysed for 87Sr/86Sr,
and for major and trace elements. A 100 ml aliquot of age despite several storms. In September, rainfall
each ®ltered rain sample was placed in polyethylene bot- was 2 to 3 times higher than average. In October,
tles for anion and HCO3 determinations. rainfall was above average, especially during the
Major element concentrations were measured in the lab-
last 10 days. In November, 60 to 80% of the aver-
oratory using atomic absorption spectrometry (Ca, Na,
K), ion chromatography (Cl, SO4), and ICP-MS (Al, Mg, age monthly rainfall fell during the ®rst 10 days,
Sr). Accuracy was better than 210% (Ca, Na, K, Cl, SO4) and rainfall during the rest of the month was below
and 5% (Al, Mg, Sr). Bicarbonate was analysed by HCl ti- average. In December, the rainfall was far below
tration and Gran's method. Low values close to 0 were
average. In January and February 1995, rainfall
obtained as observed earlier by Wedraogo-Dumazet (1983)
on rain collected in southeastern France. was 1.2 to 2 times greater than the monthly aver-
Chemical separation and mass spectrometry procedures age. The highest total monthly rainfall was
for Sr followed the standard method used at BRGM. measured in February. In March, rainfall was
Strontium was separated by using a cation exchange col-
below average (by a factor of 1.1 to 1.5).
umn (DOWEX AG50X8) with 2N HCl as eluant. Total
blanks for Sr are less than 0.5 ng and were negligible with Average air mass trajectories in Corsica (Loye-
regard to the total Sr analysed in rain waters. After chemi- Pilot and Morelli, 1988; Losno et al., 1991), in
cal separation, 1/5 of each sample was placed on a single Paris (Jarezo, 1987) and in the Vosges mountains
W ®lament and analysed using a Finnigan MAT 262 mul-
(Colin, 1988), and weather patterns (MeÂteÂorologie
tiple collector mass spectrometer. The 87Sr/86Sr ratios were
normalized to 86Sr/88Sr = 0.1194. An average internal pre- Nationale, Centre DeÂpartemental du Puy de DoÃme)
cision of 210 10ÿ6 (2s) was obtained during this study. enabled sectorizing air mass origins. Four sectors
The reproducibility of the 87Sr/86Sr ratios measurement can be identi®ed as shown in Fig. 1. The ®rst is
was tested through duplicate analyses of the NBS 987
westerly and mainly of marine origin (Atlantic
standard and the mean value appears to be close to
0.710228220 10ÿ6 (2s; n = 110). Ocean) but the air mass passes over the Aquitanian
Basin with sedimentary deposits and the western
part of the Massif Central. The second is NE±NW
RESULTS and is of both marine (North Atlantic and North
Sea) and continental (Great Britain) origin and
Meteorological data passes over a more or less industrialized area. The
third is easterly and completely continental, passing
Meteorological data were obtained from the local over polluted areas (Germany and eastern Europe).
oce of the National Meteorological Service The fourth is SE±SW and is of marine origin, poss-
located 4 km from the collector for the period from ibly carrying natural aerosols from Africa and pol-
April 1994 to March 1995. In April 1994, total rain- lution from Spain. Jarezo (1987) and Colin (1988),
fall was 1.5 to 3 times higher than the average studied rain events and weather patterns over
monthly value for April. There were 23 rainy days. France and showed that the W sector is predomi-
In May, precipitation was above average in most of nant (52% of rain events) and the E sector never
the area, although in some places it was below aver- exceeds 5%. The NE±NW and SE±SW sectors rep-
age. The irregularity of the rainfall is due to the resented 16 and 27% of the rain events, respect-
stormy nature of the period. In June, rainfall was ively. It is assumed that there was similar
for the most part normal, with values slightly below sectorisation during the sampling period, but due to
Table 1. Field data of rainwater samples collected during the one year survey in the Massif Central. Q represents the
amount of collected water expressed in liters. RFA represents the rainfall amount in mm for each collection period.
Temperature T (in 8C), pH, electrical conductivity (in mS/cm standardized to 208C) of rainwater samples were measured
in ®eld
Sample
reference PSM Sampling period Q RFA T Cond pH
1 31-3-94/22-4-94 12 120 26 40.9 4.29
2 22-4-94/3-5-94 4 40 14.9 9.26 5.1
3 3-5-94/25-5-94 11 110 12.2 9.15 5.55
4 25-5-94/17-6-94 3.7 37 12.3 14.6 6.2
5 17-6-94/28-7-94 9.5 95 24.3 51.6 6.05
6 28-7-94/18-8-94 11 110 19.6 17.5 4.53
7 19-9-94/5-10-94 12 120 8.6 7.06 6.04
8 5-10-94/27-10-94 11 110 9.7 5.36 4.95
9 27-10-94/17-11-94 11 110 11 4.95 5.22
10 17-11-94/16-12-94 0.5 5 0.8 25.4 4.54
11 16-12-94/17-1-95 2.8 28 5.5 24.6 4.56
12 17-1-95/30-1-95 2 20 16.5 5.05 5.05
13 30-1-95/6-3-95 6.5 65 7.1 7.85 5.76
944 P. Negrel and S. Roy
Table 2. Major (Ca, Na, Mg, K, Al, HCO3, Cl, SO4, NO3) and trace (Sr) concentrations expressed in mmole/l, 87Sr/86Sr
ratios in dissolved load of rainwater samples collected during the one year survey in the Massif Central. d.l refers to the
detection limits and n.d refers to non analysed samples
Sample
reference
87
PSM Sr/86Sr 2s HCO3 Cl SO4 NO3 Ca Na Mg K Al Sr
1 0.710025 1.00E-05 nd 49 51 75.8 12.2 39.1 4.4 4.1 d.l 0.033
2 0.711182 1.10E-05 nd 7.1 23.4 16.9 10.7 6.1 2.1 4.1 d.l 0.030
3 0.709481 1.20E-05 26 7.1 16.1 34.7 8 3.9 1.7 2.6 d.l 0.017
4 0.710418 8.00E-06 24 16.9 19.8 d.l 14.7 9.1 2.1 7.2 d.l 0.034
5 0.70927 1.00E-05 160 31 47.9 41 78.8 20 4.2 23.8 1.56 0.121
6 0.709435 1.70E-05 nd 16.9 33.3 30.6 16 4.8 0.8 3.3 0.19 0.021
7 0.709198 9.00E-06 29 8.5 9.4 12.9 16.7 4.3 1.9 2.3 d.l 0.027
8 0.713143 8.00E-06 nd 10.2 7.3 d.l 2 8.7 1.2 2.6 d.l 0.004
9 0.712257 1.40E-05 nd 13.5 4.2 d.l 1 0.4 1.2 13.6 0.04 0.008
10 0.711326 9.00E-06 nd 13 36.6 54.7 9.5 6.5 6.5 3.8 1.52 0.030
11 0.709513 9.00E-06 nd 44.3 21.6 39.4 12 32.2 8.2 1.8 0.44 0.019
12 0.710773 9.00E-06 nd 14.1 6.1 d.l 3.2 8.7 5.8 3.1 0.04 0.019
13 0.709245 1.10E-05 17 22.6 13.2 19.4 5.7 43.1 4.1 2.3 1.00 0.020
the sampling procedure (sampling periods of up to l. Magnesium content varied 45-fold (0.18 mmole/l
one month), air mass trajectories for individual rain in PSM4 to 8.2 mmole/l in PSM11). No anions were
events are not available. strongly dominant. The mean weighted contents of
Cl (19 mmoles/l), SO4 (23 mmoles/l) and NO3 (26
mmoles/l) were similar. Chloride content varied 6-
Chemical and isotopic data fold (7 mmole/l in PSM2 to 44.3 mmole/l in
PSM11). Nitrate content was below detection limit
Thirteen samples, representing a total of 97 l of in four samples (PSM4, 8, 9 and 12). Sulphate con-
water and 970 mm of rainfall, were collected tent varied 12-fold (4 mmole/l in PSM9 to 51
between March 31, 1994 and March 6, 1995. The mmole/l in PSM1). Strontium ranged between 0.004
®eld data are given in Table 1, and the water chem- mmole/l (PSM8) and 0.034 mmole/l (PSM4).
istry and Sr isotope values are given in Table 2.
The ion imbalance between cations and anions in
During the PSM5 period (17/6/94±28/7/94), con-
rainwaters collected in France is well-documented
ductivity increased to 52 mS/cm, then decreased to 5
mS/cm during the periods PSM8 (5/10/94±27/10/94), (Losno et al., 1991; Galloway et al., 1982;
PSM9 (27/10/94±17/11/94 and PSM12 (17/1/95±30/ Wedraogo-Dumazet, 1983, Jarezo, 1987; Colin,
1/95). There was no correlation between conduc- 1988). This imbalance can be large and might have
tivity and the amount of rainwater collected. two possible causes. The ®rst is the lack of NH4
The pH of rain samples ranged between 4.29 measurements, which can cause a signi®cant cation
(PSM1) and 6.2 (PSM4). The mean value was de®cit. Jarezo (1987) and Colin (1988) have shown
5.22 2 0.65. Pristine rainwater is moderately acidic for marine and inland rains collected in France that
with a theoretical value of 5.7 (Berner-Kay and this species can make up 40% of the total cations.
Berner, 1987). The higher values reported here The second is that lack of measurements of both
could be the result of dissolution of windblown H3PO4 and organic species (acetate, formate, humic
dust with a high CaCO3 content, but the high pH acid . . .) may induce an anion de®cit. The observed
value does not correspond with the high HCO3 con- imbalance for anions or cations is, therefore, not a
centration. Rainwater can also have a pH below 5.7 re¯ection on the quality of the data set but, de
due to the presence of natural H2SO4, weak organic facto, the charge balance cannot be calculated.
acids, or anthropogenic emission of H2SO4 and/or The 87Sr/86Sr ratios ranged between 0.709198
HNO3. In this study, 9 values were lower and 4
(PSM7) and 0.713143 (PSM 8). The ratio increased
greater than 5.7.
and decreased several times between PSM1 (end of
Concentrations of several elements varied greatly
winter) and PSM5 (summer) from 0.7112 to 0.7093.
during the sampling period. Five ions were clearly
predominant. Ca and Na were the most abundant The isotope ratio was then relatively constant
cations with a mean weighted concentration of 17.7 during the summer (PSM5, 6 and 7: 0.7094, 0.7093,
and 13.99 mmoles/l, respectively. Ca content varied 0.7092). The greatest increase was observed between
80-fold (1 mmole/l in PSM9 to 78.8 mmole/l in PSM7 and PSM8 (beginning of autumn) from
PSM5). Sodium content varied 100-fold (0.43 0.7092 to 0.7131. 87Sr/86Sr ratios then decreased
mmole/l in PSM9 to 43 mmole/l in PSM13). between PSM8 and PSM11 (winter) from 0.7131 to
Magnesium was the least abundant of the major 0.7095, increased in PSM12 (0.71077) and ®nally
cations with a mean weighted content of 2.8 mmole/ decreased in PSM 13 (winter, 0.70925)
Chemistry of rainwater in the French Massif Central 945
DISCUSSION
(Hofmann et al., 1977; Church et al., 1984) or in commonly observed. PSM 13 has a low Cl/Na
the upper continental crust (Losno et al., 1991). ratio, which translates to a marine Cl value of
The Na/Al ratio of the upper continental crust is around 220%. The non marine input of Cl could
approximately 0.42 (Taylor and McLennan, 1985; come from various sources of pollution including
Condie, 1993), and the ratio for shales is 0.11 automobiles, coal combustion, incinerators and fer-
(Condie, 1993). The dierence between these values tilizers.
is the result of continental weathering. As soils are Sulphate from sea salt (Table 3) ranges from less
the main source of terrestrial material in aerosols, than 1% (PSM6 and 9) to 19.4% (PSM13). Excess
the crustal source must be representative of soils. SO4 in rain over unpolluted land in Amazonia has
Hofmann et al. (1977) and Church et al. (1984) been estimated at around 5 mmol/l (Stallard and
have shown that shales are more representative of Edmond, 1981). Excess SO4 over land commonly
average soils than the rocks of the upper continen- ranges from 10 to more than 100 mmol/l and high
tal crust. Therefore, the correction of crustal Na values can be related to pollution (mainly due to
with Al has been applied using shales as a terrestrial burning of fossil fuel, Berner-Kay and Berner,
dust reference. Sodium in rainwater samples can be 1987). In the rain collected in the Massif Central,
considered to originate from sea salt when Al < 0.5 4.1 mmol/l to 49 mmol/l of excess sulfate was
ppb. If Yt=0 in equation (1), the sea salt and ter- measured. Two samples have SO4 values similar to
restrial contributions can be obtained using those measured over unpolluted areas (PSM 9 and
equation (2). When Al is dierent from 0, part of 12). PSM1 (31/3/94±22/4/94) had the highest SO4
the Na is derived from a terrestrial source and ter- content (48.7 mmol/l) and PSM5 (16/6/94±28/7/94)
restrial Na is calculated with equation (3), using a also had a high value (46.8 mmol/l). In the spring,
Na/Al ratio of 0.11. excess SO4 was between 15 and 25 mmol/l. SO4
The correction of terrestrial Na with Al shows increased during the early summer and generally
that less than 1% of Na was of terrestrial origin, decreased after October.
except for PSM10 where terrestrial Na is close to Nitrate in rain comes from both human activities
2.6%. If the upper continental crust is used as the (like fuel combustion) and chemical reactions in the
terrestrial dust reference, there is an input of from atmosphere (Berner-Kay and Berner, 1987), the lar-
0.2% to 3% (except for PSM10 where terrestrial gest source of NO3 in rain being the production of
Na is close to 9.8%). This shows the small contri- N oxides during fossil fuel combustion. In rainwater
bution of the terrestrial component in the Na con- collected in the Massif Central, the positive trend
tent. The proportions of sea salt and terrestrial end between excess SO4 and total NO3 re¯ects the input
members were therefore calculated using equation of pollutants from fossil fuel combustion over the
(1) and equation (2) with Na as marine reference. studied period (Fig. 3). Chlorine input from the pol-
The X/Na ratios for X = Cl, SO4, Ca, Mg, K, Sr lutant sources cannot be linked to that of SO4 and
were determined according to the composition of NO3 as indicated by the lack of correlation between
sea water given by Berner-Kay and Berner (1987). SO4 and NO3, and Cl (not shown).
Results are given in Table 3 in percentage of the Marine Ca values were low (<1.4%) for almost
marine source. the whole data set (PSM2-7, 9, 10, 12; Table 3),
The proportion of Cl coming from sea salt ran- similar to results reported by Berner-Kay and
ged from 3.6% in PSM 9 to 100% in PSM 2 and Berner (1987). In PSM 11 and 13, 4±6% of Ca was
PSM 8 (Table 3). Values between 33 and 60% are of marine origin, and 7 and 9.5% of Ca was of
Table 3. Results expressed in % of Cl, SO4, Ca, Na, Mg, K and Sr of the marine contribution in rain samples. Samples
with an asterisk have Na corrected using Al for crustal inputs
Sample
reference
87
PSM Sr/86Sr t Cl m SO4 m Km Na m Ca m Mg m Sr m
1 0.71027 93.2% 4.6% 21.0% 100% 7.0% 100.0% 22.5%
2 0.71126 100.0% 1.6% 3.3% 100% 1.2% 33.5% 3.9%
3 0.70950 64.3% 1.5% 3.4% 100% 1.1% 26.2% 4.3%
4 0.71048 62.9% 2.8% 2.8% 100% 1.4% 50.2% 5.1%
5* 0.70927 72.7% 2.4% 1.8% 97% 0.5% 51.6% 3.0%
6* 0.70945 32.4% 0.8% 3.1% 98% 0.6% 64.7% 4.4%
7 0.70920 59.9% 2.8% 4.2% 100% 0.6% 26.6% 3.0%
8 0.71625 99.9% 7.2% 7.5% 100% 9.5% 79.7% 43.9%
9* 0.71229 3.6% 0.6% 0.1% 96% 0.1% 3.8% 1.0%
10* 0.71141 52.9% 1.0% 3.4% 90% 0.8% 10.2% 3.8%
11* 0.70967 84.3% 8.9% 39.3% 99% 4.2% 44.0% 31.3%
12* 0.71092 71.8% 8.5% 62% 100% 1.2% 17.0% 8.5%
13 0.70930 220.4% 19.3% 41.2% 99% 5.7% 100.0% 40.5%
Chemistry of rainwater in the French Massif Central 947
cate rocks (Faure, 1986). Thus, the 87Sr/86Sr ratio congruent dissolution of carbonate rocks, the
87
of silicate dust depends on the age and Rb/Sr ratio Sr/86Sr ratio of river water is the same as that of
of the parent rocks. the rocks. Leaching experiments with double dis-
The isotopic composition of Sr in dusts can be tilled water of soils from silicate watersheds have
estimated by studying 87Sr/86Sr ratios of river shown that soluble Sr in soils and Sr in the dis-
water. On a carbonate watershed, because of the solved load in rivers, also have similar isotope
Fig. 4. Schematic geological map of France and location map of the dierent crustal components con-
sidered in this work (1-6)
Chemistry of rainwater in the French Massif Central 949
ratios (NeÂgrel, 1992). Strontium can be given o by study of rivers draining only one carbonate facies:
vegetation in a manner similar to that described by Lower Jurassic (LJ), Upper Jurassic (UJ), Lower
Crozat (1979), Clairac et al. (1988) and Artaxo and Cretaceous (LC), Upper Cretaceous (UC), Tertiary
Maenhaut (1990) for K. Vegetation extracts cations (T) in the Paris Basin (Table 4, and numbers 2, 3, 4
from soil waters, and Graustein and Armstrong in Fig. 4) provided 87Sr/86Sr ratios indicating the
(1983) and Graustein (1981) have shown that water possible sources of dusts (NeÂgrel et al., 1989). Two
in soils and plants have identical 87Sr/86Sr ratios, ®elds were identi®ed. The ®rst included the Lower
which are higher than that of Sr in the dissolved Jurassic, the Lower Cretaceous, and the Tertiary
load in rivers. Strontium can also be linked with with 87Sr/86Sr ratios ranging between 0.7086 and
anthropogenic emissions and fertilizers (more than 0.7094. The second included the Upper Jurassic and
1500 ppm Sr). the Upper Cretaceous with 87Sr/86Sr ratios of
0.7081 to 0.7084.
The second end member was related to dust emis-
The terrestrial end member: nature and origin of the sions from silicate terrains (clay minerals, mica,
possible terrestrial sources in rainwater, Sr isotopes feldspar) from the Massif Central called the local
constraints silicate source (LSS, Table 4, and sampling site 5 in
Fig. 4) and from other granitic areas, here called
The sea-salt corrected chemical composition of remote silicate source (RSS, Table 4, and number 6
rainwater in the Massif Central indicates various in the Fig. 4) bordering the Massif Central
terrestrial components, but no single origin can be (Margeride, Morvan, Lozere). The Sr isotope ratios
considered. Numerous sources, both local and of this silicate end member can be approached
remote, natural and anthropogenic, must be con- through the dissolved load of rivers draining silicate
sidered. One of the terrestrial components can be basement (granite, gneiss and basalt bedrock) in the
related to calcic particles from soil or limestone Massif Central and in remote granitic watersheds.
dusts. This input of carbonate particles to the at- For granite and gneiss basements, the 87Sr/86Sr
mosphere could originate from Tertiary deposits ratios range between 0.7135 and 0.717 (NeÂgrel et
(Miocene and Oligocene marls and limestones) near al., 1988, 1989; Seimbille et al., 1991; NeÂgrel and
the sampling site and is called the local carbonate Deschamps, 1996; Table 4) and for basaltic base-
source (LCS) (Fig. 4). The 87Sr/86Sr ratio of springs ment the 87Sr/86Sr ratios range between 0.703 and
draining these rocks and soils is 0.71102 (Table 4, 0.705 (NeÂgrel and Deschamps, 1996).
and ®rst sampling site in Fig. 4). The last end member is made up of anthropo-
The Massif Central is bordered to the N, SW and genic input (Berner-Kay and Berner, 1987), such as
SE by marine deposits of the Paris Basin (Jurassic fertilizers with an 87Sr/86Sr ratio ranging between
to Oligocene), the Aquitaine Basin, and the Rhone 0.7079 and 0.7087 (NeÂgrel and Deschamps, 1996).
River valley (BRGM, 1980), respectively. These No data exist on Sr concentrations or isotope com-
deposits might represent a remote source of carbon- positions of other possible pollutants (automobile
ate particles in the rain samples, here called remote exhaust, coal combustion, incinerators).
carbonate source (RCS), the two principal sources Figure 5 shows the distribution of the terrestrial
87
being the Paris and Aquitaine basins (Fig. 4). The Sr/86Sr ratios in the 13 rain samples in the classic
Table 4. 87Sr/86Sr ratios for the possible terrestrial components in rainwaters collected in the Massif Central encompass-
ing the local carbonate source LCS, the remote carbonate source RCS with carbonate facies from Lower Jurassic (LJ),
Upper Jurassic (UJ), Lower Cretaceous (LC), Upper Cretaceous (UC), Tertiary (T) estimated through the dissolved load
of rivers draining this type of basement. The local silicate source (LSS, granitic, gneissic and basaltic bedrocks) and the
remote silicate source RSS bordering the Massif Central (Margeride, Morvan, Lozere) estimated through river draining
silicate basements and lastly by anthropogenic inputs (F) by fertilizers and carbonate amendments.
87
Identi®cation Type Key code Sr/86Sr
Sedimentary bedrocks LCS
Tertiary 0.71120
Sedimentary bedrocks RCS
Tertiary T 0.70895
Upper Cretaceous U.C 0.70810
Lower Cretaceous L.C 0.70940
Upper Jurassic U.J 0.70845
Lower Jurassic L.J 0.70860
Silicated Basements LSS/RSS
Basalts 0.703±0.705
Granites/gneiss 0.7135±0.717
Anthropogenic Inputs
Fertilizers (n = 3) F 0.7079±0.70832
Carbonate amendments F 0.7087
950 P. Negrel and S. Roy
Clairac B., Delmas R., Cros B., Cachier H., Buat-Menard Lacaux J. P. and Warburton J. A. (1980) The disposition
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