Unveiling the secret of ancient Maya masons: Biomimetic lime plasters with plant extracts.

Ancient Maya produced some of the most durable lime plasters on Earth, yet how this was achieved remains a secret. Here, we show that ancient Maya plasters from Copan (Honduras) include organics and have a calcite cement with meso-to-nanostructural features matching those of calcite biominerals (e.g., shells). To test the hypothesis that the organics could play a similar toughening role as (bio)macromolecules in calcium carbonate biominerals, we prepared plaster replicas adding polysaccharide-rich bark extracts from Copan's local trees following an ancient Maya building tradition. We show that the replicas display similar features as the organics-containing ancient Maya plasters and demonstrate that, as in biominerals, in both cases, their calcite cement includes inter- and intracrystalline organics that impart a marked plastic behavior and enhanced toughness while increasing weathering resistance. Apparently, the lime technology developed by ancient Maya, and likely other ancient civilizations that used natural organic additives to prepare lime plasters, fortuitously exploited a biomimetic route for improving carbonate binders performance.

Interplay between arsenic and selenium biomineralization in Shewanella sp. O23S.

Bacteria play crucial roles in the biogeochemical cycle of arsenic (As) and selenium (Se) as these elements are metabolized via detoxification, energy generation (anaerobic respiration) and biosynthesis (e.g. selenocysteine) strategies. To date, arsenic and selenium biomineralization in bacteria were studied separately. In this study, the anaerobic metabolism of As and Se in Shewanella sp. O23S was investigated separately and mixed, with an emphasis put on the biomineralization products of this process. Multiple analytical techniques including ICP-MS, TEM-EDS, XRD, Micro-Raman, spectrophotometry and surface charge (zeta potential) were employed. Shewanella sp. O23S is capable of reducing selenate (SeO42-) and selenite (SeO32-) to red Se(-S)0, and arsenate (AsO43-) to arsenite (AsO33-). The release of H2S from cysteine led to the precipitation of AsS minerals: nanorod AsS and granular As2S3. When As and Se oxyanions were mixed, both As-S and Se(-S)0 biominerals were synthesized. All biominerals were extracellular, amorphous and presented a negative surface charge (-24 to -38 mV). Kinetic analysis indicated the following reduction yields: SeO32- (90%), AsO43- (60%), and SeO42- (<10%). The mix of SeO32- with AsO43- led to a decrease in As removal to 30%, while Se reduction yield was unaffected (88%). Interestingly, SeO42- incubated with AsO43- boosted the Se removal (71%). The exclusive extracellular formation of As and Se biominerals might indicate an extracellular respiratory process characteristic of various Shewanella species and strains. This is the first study documenting a complex interplay between As and Se oxyanions: selenite decreased arsenate reduction, whereas arsenate stimulated selenate reduction. Further investigation needs to clarify whether Shewanella sp. O23S employs multi-substrate respiratory enzymes or separate, high affinity enzymes for As and Se oxyanion respiration.

Bacterial Diversity Evolution in Maya Plaster and Stone Following a Bio-Conservation Treatment.

To overcome the limitations of traditional conservation treatments used for protection and consolidation of stone and lime mortars and plasters, mostly based on polymers or alkoxysilanes, a novel treatment based on the activation of indigenous carbonatogenic bacteria has been recently proposed and applied both in the laboratory and in situ. Despite very positive results, little is known regarding its effect on the evolution of the indigenous bacterial communities, specially under hot and humid tropical conditions where proliferation of microorganisms is favored, as it is the case of the Maya area. Here, we studied changes in bacterial diversity of severely degraded tuff stone and lime plaster at the archeological Maya site of Copan (Honduras) after treatment with the patented sterile M-3P nutritional solution. High-throughput sequencing by Illumina MiSeq technology shows significant changes in the bacterial population of the treated stones, enhancing the development of Arthrobacter, Micrococcaceae, Nocardioides, Fictibacillus, and Streptomyces, and, in one case, Rubrobacter (carved stone blocks at Structure 18). In the lime plaster, Arthrobacter, Fictibacillus, Bacillus, Agrococcus, and Microbacterium dominated after treatment. Most of these detected genera have been shown to promote calcium carbonate biomineralization, thus implying that the novel bio-conservation treatment would be effective. Remarkably, the treatment induced the reduction or complete disappearance of deleterious acid-producing bacteria such as Marmoricola or the phylum Acidobacteria. The outcome of this study demonstrates that such a bio-conservation treatment can safely and effectively be applied on temples, sculptures and stuccos of the Maya area and, likely, in other hot and humid environments.

Sequestration of selenium on calcite surfaces revealed by nanoscale imaging.

Calcite, a widespread natural mineral at the Earth's surface, is well-known for its capacity to sequester various elements within its structure. Among these elements, selenium is important because of its high toxicity in natural systems and for human health. In the form of selenite (Se((IV))), selenium can be incorporated into calcite during growth. Our in situ atomic force microscopy observations of calcite surfaces during contact with selenium-bearing solutions demonstrate that another process of selenium trapping can occur under conditions in which calcite dissolves. Upon the injection of solutions containing selenium in two states of oxidation (either Se((IV)) or Se((VI))), precipitates were observed forming while calcite was still dissolving. In the presence of selenate (Se((VI))), the precipitates formed remained small during the observation period. When injecting selenite (Se((IV))), the precipitates grew significantly and were identified as CaSeO3·H2O, based on SEM observations, Raman spectroscopy, and thermodynamic calculations. An interpretation is proposed where the dissolution of calcite increases the calcium concentration in a thin boundary layer in contact with the surface, allowing the precipitation of a selenium phase. This process of dissolution-precipitation provides a new mechanism for selenium sequestration and extends the range of thermodynamic conditions under which such a process is efficient.