『Abstract
Seasonal changes in river chemistry offer the potential to assess
how weathering processes respond to changing meteorological parameters
and ultimately how chemical weathering might respond to climatic
parameters. Systematic seasonal variations in magnesium isotope
ratios (the 26Mg/24Mg ratio expressed as
δ26Mg in per mil units) are reported in stream waters
from a mono-lithological granitic, weathering-limited, first order
catchment from the Swiss Alps (Damma glacier). Rain, ground, and
pore-waters, in addition to plants, rocks, mineral separates and
soil are also reported. The concentration response of the river
waters is attenuated compared to the large changes in discharge.
However, the systematic trends in the isotope data imply that
either the source of the Mg changes in a systematic manner, or
that the process by which Mg is released into solution changes
as a function of discharge.
The two first order observations in the data that need to be
explained are 1) the systematic enrichment in 24Mg
in the stream waters compared to the granitic rocks they drain
and 2) a systematic increase in δ26Mg in the waters
during the summer melt season. Both observations (which are similar
to many other rivers draining silicate rock) can either be accounted
for by 1) conservative mixing between at least two different sources
of Mg (in addition to precipitation inputs), or 2) process related
fractionation. If the stream water compositions can be rationalised
by multi-component mixing, there is at least one unidentified
component with a δ26Mg<-1.2‰. This is considered unlikely.
Multiple physicochemical processes could fractionate Mg isotope
ratios such as 1) preferential leaching of 24Mg, 2)
exchange of Mg onto (or from) mineral surfaces and into interlayer
sites of clays, 3) uptake by plants, and 4) 26Mg could
be preferentially retained during the formation of secondary phases,
such as clays, amorphous phases or oxides. These processes are
not mutually exclusive and distinguishing between them at a field
scale is not trivial, but significant biological uptake is improbable
at this site. Unless there is a non-identified external input
of Mg, 26Mg must be accumulating in solid phase residues
in the catchment because of at least one physicochemical process.
Such processes are likely well described, at least in the first
order by a Rayleigh distillation model. Simple calculations illustrate
how much 26Mg would accumulate in the catchment per
unit time. In the first order, the isotopic enrichments in the
solids are so small that they would not be detectable for the
time-scales that are relevant to this field site, in spite of
the marked impact on the water chemistry. The seasonal signal
detected by mg isotope ratios is promising for using them (with
a better understanding of fractionation mechanisms) to quantify
how specific weathering processes impact upon both export fluxes,
and retention of elements within catchments.
Keywords: River geochemistry; Magnesium; Mg isotopes; Chemical
weathering』
1. Introduction
2. Study area and sample collection
3. Analytical procedure
4. Results
4.1. Correcting for precipitation inputs
5. Seasonal variations in stream water δ26Mg and causal
mechanisms
5.1. Conservative mixing as a control of stream water δ26Mg
5.2. Ion exchange as a control on mg isotopes?
5.3. Biological forcing of seasonal mg isotope variations
5.4. Preferential release of 24Mg during dissolution
5.5. Formation of secondary minerals and mg isotope variations
5.6. Implications and semi-quantitative constraints on seasonal
variations
6. Conclusions and perspectives
Acknowledgements
References