Processes controlling δ7Li in rivers illuminated by study of streams and groundwaters draining basalts

- Li isotope fractionation occurs during suspended load transport in rivers.
- Subsurfaces residence times, reflected in seasonal changes, strongly influences riverine δ7Li.
- Li isotopes do not correlate with other indicators of weathering intensity.
- δ7Li and Li/Na in dissolved loads of rivers reflect water-rock interaction.
- Li isotopes are powerful tracers of continental weathering.

We evaluate the factors influencing the abundance, [Li], and isotopic composition of riverine Li delivered to the oceans through analyses and modeling of [Li] and δ7Li in streams and groundwaters draining a single continental lithology, the Columbia River Basalts (CRBs). The streams were sampled in different climate zones that lie east (dry), and west (wet) of the Cascades Mountains, and during two different seasons (summer and late winter) in order to evaluate climatic and seasonal influences on Li isotopes in rivers. Dissolved Li (δLidis7=+9.3 to +30.4) is systematically heavier than that of fresh or weathered CRBs (−4.7 to +6.0, Liu et al., 2013), suspended loads (−5.9 to −0.3), and shallow groundwaters (+6.7 to +9.4), consistent with previous studies showing that Li isotope fractionation is affected by equilibration between stream water and secondary minerals. However, the lack of correlation between δ7Lidis and climate zone, the uniform secondary minerals and bedrock, coupled with the highly variable (>20‰) δLidis7 indicate that other factors exert a strong control on δ7Lidis. In particular, the heavier Li in streams compared to the shallow groundwaters that feed them indicates that continued isotopic fractionation between stream water and suspended and/or bed loads has a major influence on riverine δ7Li. Seasonal δ7Li variation is observed only for streams west of the Cascades, where the difference in precipitation rate between the dry and wet seasons is greatest. Reactive transport model simulations reveal that riverine δ7Li is strongly controlled by subsurface residence times and the Li isotope fractionation occurring within rivers. The latter explains why there is no positive correlation between δ7Li and traditional weathering proxies such as Si or normalized Si in rivers, as riverine Li isotope fractionation drives δ7Li to higher values during transport, whereas the concentrations of major cations and anions are diluted. The varying residence time for groundwaters feeding the western streams in summer (long residence times, higher δ7Li, greater weathering) and winter (short residence times, lower δ7Li, less weathering) explains the observed seasonal variations. A global, negative correlation between δ7Li and Li/Na for streams and rivers draining basaltic catchments reflects the overall transport time, hence the amount of silicate weathering. Based on our results, the increase of δ7Li in seawater during the Cenozoic is unlikely related to changing climate, but may reflect mountain building giving rise to increased silicate weathering.