Ocean acidification triggered by Siberian Trap volcanism has been implicated as a kill18 mechanism for the Permo-Triassic mass extinction, but evidence for an acidification event 19 remains inconclusive. To address this, we present a high resolution seawater pH record across 20 this interval, utilizing boron isotope data combined with a quantitative modeling approach. In the 21 latest Permian, the alkalinity of the ocean increased, priming the Earth system with a low level of 22 atmospheric CO 2 and a high ocean buffering capacity. The first phase of extinction was 23 2 coincident with a slow injection of isotopically light carbon into the atmosphere-ocean, but the 24 ocean was well-buffered such that ocean pH remained stable. During the second extinction pulse, 25 however, a rapid and large injection of carbon overwhelmed the buffering capacity of the ocean,
26causing an abrupt and short-lived acidification event that drove the preferential loss of heavily 27 calcified marine biota. kyrs (2) and can be resolved into two distinct marine extinction pulses, with the respective kill 37 mechanisms appearing to be ecologically selective (3). The first occurred in the latest Permian 38 (Extinction Pulse 1; EP1) and was followed by an interval of temporary recovery before the 39 second pulse (EP2) which occurred in the earliest Triassic. The direct cause of the mass 40 extinction is widely debated with a diverse range of overlapping mechanisms proposed, 41 including widespread water column anoxia (4), euxinia (5), global warming (6) and ocean 42 acidification (7).
43Models of PTB ocean acidification suggest that a massive, and rapid, release of CO 2 from 44 Siberian Trap volcanism, acidified the ocean (7). Indirect evidence for acidification comes from 45 the interpretation of faunal turnover records (3, 8), potential dissolution surfaces (9) and Ca 46 3 isotope data (7). A rapid input of carbon is also potentially recorded in the negative carbon 47 isotope excursion (CIE) that characterizes the PTB (10, 11) . The interpretation of these records 48 is, however, debated (12), and of great importance to understanding the current threat of 49 anthropogenically-driven ocean acidification (11).
50Here, we test the ocean acidification hypothesis by presenting a novel proxy record of 51 ocean pH across the PTB, using the boron isotope composition of marine carbonates ( 11 additional counterbalancing alkalinity flux. This is consistent with independent proxy data (6).
129The alkalinity source may have been further increased through soil loss (26) carbon to the atmosphere, yet remarkably, the acidification event occurs after the decline in 13 C,
139when 13 C has rebounded somewhat and is essentially stable (Fig. 2).
140Unlike the first carbon injection, the lack of change in 13 C at this time rules out very 141 13 C-depleted carbon sources, because no counterbalancing strongly 13 C-enriched source exists.