Dolomite Ca,Mg(CO3)2 precipitation from supersaturated ionic solutions at Earth surface temperatures is considered kinetically inhibited because of the difficulties experienced in experimentally reproducing such a process. Nevertheless, recent dolomite is observed to form in hypersaline and alkaline environments. Such recent dolomite precipitation is commonly attributed to microbial mediation because dolomite has been demonstrated to form in vitro in microbial cultures. The mechanism of microbially mediated dolomite precipitation is, however, poorly understood and it remains unclear what role microbial mediation plays in natural environments. In the study presented here, simple geochemical methods were used to assess the limitations and controls of dolomite formation in Deep Springs Lake, a highly alkaline playa lake in eastern California showing ongoing dolomite authigenesis. The sediments of Deep Springs Lake consist of unlithified, clay-fraction dolomite ooze. Based on δ18O equilibria and textural observations, dolomite precipitates from oxygenated and agitated surface brine. The Na-SO4-dominated brine contains up to 500 mm dissolved inorganic carbon whereas Mg2+ and Ca2+ concentrations are ca 1 and 0·3 mm, respectively. Precipitation in the subsurface probably is not significant because of the lack of Ca2+ (below 0·01 mm). Under such highly alkaline conditions, the effect of microbial metabolism on supersaturation by pH and alkalinity increase is negligible. A putative microbial effect could, however, support dolomite nucleation or support crystal growth by overcoming a kinetic barrier. An essential limitation on crystal growth rates imposed by the low Ca2+ and Mg2+ concentrations could favour the thermodynamically more stable carbonate phase (which is dolomite) to precipitate. This mode of unlithified dolomite ooze formation showing δ13C values near to equilibrium with atmospheric CO2 (ca 3‰) contrasts the formation of isotopically light (organically derived), hard-lithified dolomite layers in the subsurface of some less alkaline environments. Inferred physicochemical controls on dolomite formation under highly alkaline conditions observed in Deep Springs Lake may shed light on conditions that favoured extensive dolomite formation in alkaline Precambrian oceans, as opposed to modern oceans where dolomites only form diagenetically in organic C-rich sediments.