The fate of tetrathionate during the development of a biofilm in biogenic sulfuric acid attack on different cementitious materials.

The biodeterioration of cement-based materials in sewer environments occurs because of the production of sulfuric acid from the biochemical oxidation of H2S by sulfur-oxidizing bacteria (SOB). In the perspective of determining the possible reaction pathways for the sulfur cycle in such conditions, hydrated cementitious binders were exposed to an accelerated laboratory test (BAC test) to reproduce a biochemical attack similar to the one occurring in the sewer networks. Tetrathionate was used as a reduced sulfur source to naturally develop sulfur-oxidizing activities on the surfaces of materials. The transformation of tetrathionate was investigated on materials made from different binders: Portland cement, calcium aluminate cement, calcium sulfoaluminate cement and alkali-activated slag. The pH and the concentration of the different sulfur species were monitored in the leached solutions during 3 months of exposure. The results showed that the formation of different polythionates was independent of the nature of the material. The main parameter controlling the phenomena was the evolution of the pH of the leached solutions. Moreover, tetrathionate disproportionation was detected with the formation of more reduced forms of sulfur compounds (pentathionate, hexathionate and elemental sulfur) along with thiosulfate and sulfate. The experimental findings allowed numerical models to be developed to estimate the amount of sulfur compounds as a function of the pH evolution. In addition, biomass samples were collected from the exposed surface and from the deteriorated layers to identify the microbial populations. No clear influence of the cementitious materials on the selected populations was detected, confirming the previous results concerning the impact of the materials on the selected reaction pathways for tetrathionate transformation.

Laboratory Test to Evaluate the Resistance of Cementitious Materials to Biodeterioration in Sewer Network Conditions.

The biodeterioration of cementitious materials in sewer networks has become a major economic, ecological, and public health issue. Establishing a suitable standardized test is essential if sustainable construction materials are to be developed and qualified for sewerage environments. Since purely chemical tests are proven to not be representative of the actual deterioration phenomena in real sewer conditions, a biological test-named the Biogenic Acid Concrete (BAC) test-was developed at the University of Toulouse to reproduce the biological reactions involved in the process of concrete biodeterioration in sewers. The test consists in trickling a solution containing a safe reduced sulfur source onto the surface of cementitious substrates previously covered with a high diversity microbial consortium. In these conditions, a sulfur-oxidizing metabolism naturally develops in the biofilm and leads to the production of biogenic sulfuric acid on the surface of the material. The representativeness of the test in terms of deterioration mechanisms has been validated in previous studies. A wide range of cementitious materials have been exposed to the biodeterioration test during half a decade. On the basis of this large database and the expertise gained, the purpose of this paper is (i) to propose a simple and robust performance criterion for the test (standardized leached calcium as a function of sulfate produced by the biofilm), and (ii) to demonstrate the repeatability, reproducibility, and discriminability of the test method. In only a 3-month period, the test was able to highlight the differences in the performances of common cement-based materials (CEM I, CEM III, and CEM V) and special calcium aluminate cement (CAC) binders with different nature of aggregates (natural silica and synthetic calcium aluminate). The proposed performance indicator (relative standardized leached calcium) allowed the materials to be classified according to their resistance to biogenic acid attack in sewer conditions. The repeatability of the test was confirmed using three different specimens of the same material within the same experiment and the reproducibility of the results was demonstrated by standardizing the results using a reference material from 5 different test campaigns. Furthermore, developing post-testing processing and calculation methods constituted a first step toward a standardized test protocol.