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Modern microbial mats and microbialites are described from basaltic sea caves on the island of Kauai, HI. The mats grow on the ceilings and walls in the photic zone of several open caves where fresh water seeps out of the rock. Scanning (SEM) and transmission electron microscopy (TEM) showed that the active mats are dominated by filamentous and nonfilamentous cyanobacteria in the surface layers and heterotrophic bacteria in deeper layers. Energy dispersive X-ray analysis revealed that copious amounts of extracellular polymeric substances (EPS) are rich in Mg, Si, O, and Ca, likely concentrated from solution. Petrographic microscopy and electron microprobe analysis of the mineralized microbialites showed textures reminiscent of stromatolitic laminations, consisting mainly of alternating calcium carbonate (calcite and aragonite) and magnesium-rich silicate (kerolite). Thin coatings rich in magnesite, hydromagnesite and monohydrocalcite surround the microbialites on the rock surfaces and are likely inorganic in origin. Within the mats, minerals tend to form and concentrate within, or around, dense matrices of EPS. Microenvironments with geochemical conditions favorable for mineral crystallization likely develop in the mats as a result of the mucilaginous extracellular material and the development of bacterial microcolonies. In addition, copious amounts of extracellular polymers bind ions from solution and provide nucleation sites for mineral crystallization and growth. This combination of biological and inorganic processes can explain the occurrence of the secondary minerals in these caves, as well as the stromatolitic textures of the microbialites.