Microbes play a prominent role in transforming arsenic to and from immobile forms in aquifers1. Much of this cycling involves inorganic forms of arsenic2, but microbes can also generate organic forms through methylation3, although this process is often considered insignificant in aquifers4, 5, 6, 7. Here we identify the presence of dimethylarsinate and other methylated arsenic species in an aquifer hosted in volcaniclastic sedimentary rocks. We find that dimethylarsinate is widespread in the aquifer and its concentration correlates strongly with arsenite concentration. We use laboratory incubation experiments and an aquifer injection test to show that aquifer microbes can produce dimethylarsinate at rates of about 0.1% of total dissolved arsenic per day, comparable to rates of dimethylarsinate production in surface environments. Based on these results, we estimate that globally, biomethylation in aquifers has the potential to transform 100 tons of inorganic arsenic to methylated arsenic species per year, compared with the 420–1,250 tons of inorganic arsenic that undergoes biomethylation in soils8. We therefore conclude that biomethylation could contribute significantly to aquifer arsenic cycling. Because biomethylation yields arsine and methylarsines, which are more volatile and prone to diffusion than other arsenic species, we further suggest that biomethylation may serve as a link between surface and subsurface arsenic cycling.
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