Hydrochemical changes before and after earthquakes have been reported for over 50 years. However, few reports provide sufficient data for an association to be verified statistically. Also, no mechanism has been proposed to explain why hydrochemical changes are observed far from earthquake foci where associated strains are small (<10−8). Here we address these challenges based on time series of multiple hydrochemical parameters from two sites in northern Iceland. We report hydrochemical changes before and after M >5 earthquakes in 2002, 2012, and 2013. The longevity of the time series (10 and 16 years) permits statistical verification of coupling between hydrochemical changes and earthquakes. We used a Student t test to find significant hydrochemical changes and a binomial test to confirm association with earthquakes. Probable association was confirmed for preseismic changes based on five parameters (Na, Si, K, δ18O, and δ2H) and postseismic changes based on eight parameters (Ca, Na, Si, Cl, F, SO4, δ18O, and δ2H). Using concentration ratios and stable isotope values, we showed that (1) gradual preseismic changes were caused by source mixing, which resulted in a shift from equilibrium and triggered water‐rock interaction; (2) postseismic changes were caused by rapid source mixing; and (3) longer‐term hydrochemical changes were caused by source mixing and mineral growth. Because hydrochemical changes occur at small earthquake‐related strains, we attribute source mixing and water‐rock interaction to microscale fracturing. Because fracture density and size scale inversely, we infer that mixing of nearby sources and water‐rock interaction are feasible responses to small earthquake‐related strains.

Based on hydrochemical monitoring, petrological observations, and geochemical modeling, we identify a mechanism and estimate a time scale for fault healing after an earthquake. Hydrochemical monitoring of groundwater samples from an aquifer, which is at an approximate depth of 1200 m, was conducted over a period of 10 years. Groundwater samples have been taken from a borehole (HU-01) that crosses the Húsavík-Flatey Fault (HFF) near Húsavík town, northern Iceland. After 10 weeks of sampling, on 16 September 2002, an M 5.8 earthquake occurred on the Grimsey Lineament, which is approximately parallel to the HFF. This earthquake caused rupturing of a hydrological barrier resulting in an influx of groundwater from a second aquifer, which was recorded by 15-20% concentration increases for some cations and anions. This was followed by hydrochemical recovery. Based on petrological observations of tectonically exhumed fault rocks, we conclude that hydrochemical recovery recorded fault healing by precipitation of secondary minerals along fractures. Because hydrochemical recovery accelerated with time, we conclude that the growth rate of these minerals was controlled by reaction rates at mineral-water interfaces. Geochemical modeling confirmed that the secondary minerals which formed along fractures were saturated in the sampled groundwater. Fault healing and therefore hydrochemical recovery was periodically interrupted by refracturing events. Supported by field and petrographic evidence, we conclude that these events were caused by changes of fluid pressure probably coupled with earthquakes. These events became successively smaller as groundwater flux decreased with time. Despite refracturing, hydrochemical recovery reached completion 8-10 years after the earthquake.

Glendonites have been found worldwide in marine sediments from the neoproterozoic era to the Quaternary period. the precursor of glendonite, ikaite (caco 3 • 6H 2 o), is metastable and has only been observed in nature at temperatures <7 °C. Therefore, glendonites in the sedimentary record are commonly used as paleotemperature indicators. However, several laboratory experiments have shown that the mineral can nucleate at temperatures>7 °C. Here we investigate the nucleation range for ikaite as a function of temperature and pH. We found that ikaite precipitated at temperatures of at least 35 °C at pH 9.3 −10.3 from a mixture of natural seawater and sodium carbonate rich solution. At pH 9.3, we observed pseudomorphic replacement of ikaite by porous calcite during the duration of the experiment (c. 5 hours). These results imply that ikaite can form at relatively high temperatures but will then be rapidly replaced by a calcite pseudomorph. This finding challenges the use of glendonites as paleotemperature indicators. Calcium carbonate, one of the most common naturally occurring minerals, has an important role in the global carbon cycle. Calcite is the stable form of calcium carbonate at the Earth's surface. However, growth of calcite is often inhibited by a range of external factors 1-3. This explains why metastable hydrous and anhydrous carbonate minerals tend to form instead of calcite. A common example is the precipitation of aragonite instead of calcite in the oceans. The Mg/Ca ratio of the seawater controls this precipitation: when this ratio exceeds 2, aragonite is favoured because Mg acts as an inhibitor of calcite growth 1,4. Two hydrous forms of calcium carbonate occur instead of calcite under certain conditions: monohydrocalcite (CaCO 3 •H 2 O) and ikaite (CaCO 3 •6H 2 O). Monohydrocalcite (MHC) has been found as calcareous incrustations and the main form of calcium carbonate in Lake Issyk-Kul, Republic of Kyrgyzstan 5 and as beach rocks around two salt lakes 6. Experimental results and investigation of natural samples indicate that the formation of MHC requires high Mg/Ca ratios and a pH >8 in the solution from which it forms 6-8. The second hydrous form, ikaite, is more common than MHC despite the narrow temperature range of its stability. The mineral was first discovered as tufa columns in Ikka Fjord, SW Greenland 9,10. Ikaite has only been observed in nature at temperatures between −2 and 7 °C 11. At temperatures >7 °C, ikaite transforms to calcite and water pseudomorphically or by decomposition. In spite of the narrow temperature range of its stability, ikaite has been widely reported: in organic rich marine sediments 12-14 , in sea ice 15,16 , in speleothems 17 , as seasonal tufa columns in alkaline lakes 18 , as precipitates in sediments or on the shores of alkaline springs or lakes 19,20 , and as precipitates in riverbeds caused by anthropogenic pollution 21. In 1982, Suess et al. discovered authigenic ikaite crystals in marine sediments, and the resemblance of these crystals to the pseudomorph glend...

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