The origins and behaviour of carbon in a major semi-arid river, the Murray River, Australia, as constrained by carbon isotopes and hydrochemistry

Research highlights: → δ13C and concentrations of DIC in Murray River controlled by mineralisation of organic carbon and evasion. → Murray River is source of atmospheric CO2. → In-river processing of carbon results in difficulties in determining carbon sources. - Abstract: δ13C values of dissolved inorganic C (DIC), dissolved organic C (DOC), and particulate organic C (POC) together with δ18O and δ2H values of water, δ34S values of dissolved SO4, and major ion concentrations were measured in the Murray River and its tributaries between November 2005 and April 2007 to constrain the origins and behaviour of riverine C. δ13CDIC values in the Murray River vary between -9.5 and -4.7 per mille with a range of <3 per mille within any sampling round. δ13CDIC values of the tributaries are -11.0 per mille to -5.1 per mille. DIC concentrations of the Murray River increase from ∼25 mg/L in the middle and upper reaches of the river to 45-55 mg/L in the lower reaches. However, the mass ratio of DIC as a proportion of the total dissolved solids (TDS) decreases from ∼0.6-0.7 in the headwaters to ∼0.2-0.3 in the lower reaches of the river, with similar downstream changes in DIC/Cl ratios. This precludes simple evaporative concentration of DIC and is interpreted as the river evading CO2; this interpretation is consistent with pCO2 values that are in the range 550-11,200 ppm volume (ppmv), which are far higher than those in equilibrium with the atmosphere (∼360 ppmv). The δ13CDIC values are similar to those that would be produced by the weathering of marine limestone (δ13C ∼ 0 per mille). However, the lack of marine limestones cropping out in the Murray-Darling Basin and the relatively uniform δ13CDIC values of the Murray River (even in upland reaches where the dominant rock types are metamorphosed silicates and granites) make this unlikely. Rather the high pCO2 values and δ13CDIC values are best explained by a combination of mineralisation of low δ13C organic C and evasion to the atmosphere. The rate of these two processes may attain near steady state and control both DIC concentrations and δ13C values.