This study aims to analyze the individual and combined chemical attacks of sulfate and chloride ions on cementitious materials and assess the efficiency of some selected additives (fly ash, blast furnace slag, and metakaolin) in countering this combined attack. This research is conducted in the context of construction in marine environments, where reinforced concrete structures are often subject to significant challenges due to early exposure to sulfate and chloride ions. This early exposure results in concrete expansion, cracking, and, ultimately, the corrosion of steel reinforcements. Nevertheless, the interaction between sulfate ions, chloride ions, and the cementitious matrix remains poorly understood. Previous research has drawn conflicting conclusions, with some suggesting that sulfate ions mitigate chloride attacks, while others have come to the opposite conclusion. During this study, experimental investigations were conducted by immersing powders obtained from crushed ordinary Portland cement (CEM I) paste specimens, as well as binary, ternary, and quaternary blends, in sulfate, chloride, and sulfate–chloride solutions over the course of 25 days at an early age. Results from different characterization techniques (thermogravimetric analysis, Fourier Transform Infrared spectroscopy, Raman spectroscopy, etc.) indicate that chloride ions delay the formation of ettringite, while the presence of sulfate ions accelerates the chloride attack by limiting the formation of Friedel’s salt. The Mercury Intrusion Porosimetry test confirmed these results by showing a pronounced increase in specimens’ porosity after exposure to solely sulfate after 25 days, compared to the ones exposed to both sulfate and chloride ions. Furthermore, the incorporation of multiple additives, particularly in ternary and quaternary blends, demonstrates the enhanced durability of the studied samples. This was confirmed by a Fourier Transform Infrared spectroscopy analysis, which indicated a delayed ettringite formation in these mixtures. This delay was further affirmed by the complete depletion of sulfate ions in the sulfate solutions upon contact with powders derived from the 100% CEM I paste.

Placed in a sulfate-rich environment, concrete reacts with sulfate ions, influencing the long-term durability of reinforced concrete (RC) structures. This external sulfate attack (ESA) degrades the cement paste through complex and coupled physicochemical mechanisms that can lead to severe mechanical damage. In common practice, RC structures are generally exposed to sulfate at an early age. This early exposition can affect ESA mechanisms that are generally studied on pre-cured specimens. Moreover, current efforts for sustainable concrete construction focus on replacing clinker with supplementary cementitious materials, requiring a 90-day curing period, which contradicts real-life scenarios. Considering all these factors, the objective of this study is to explore ESA effects at an early age on cement-blended paste samples using various low-carbon formulations. The characterization techniques used demonstrated that the reference mix (100% CEM I) exhibits the weakest resistance to sulfate, leading to complete deterioration after 90 weeks of exposure. This is evident through the highest mass gain, expansion, cracking, formation of ettringite and gypsum, and sulfate consumption from the attacking solution. Conversely, the ternary mix, consisting of CEM I, slag, and metakaolin, demonstrates the highest resistance throughout the entire 120 weeks of exposure. All the blended pastes performed well in the sulfate environment despite being exposed at an early age. It can be recommended to substitute clinker with a limited quantity of metakaolin, along with blast furnace slag, as it is the most effective substitute for clinker, outperforming other combinations.

Surfactants based on polyfluoroalkyl ethers are commonly used in fire-fighting foams on airport platforms, including for training sessions. Because of their persistence into the environment, their toxicity and their bioaccumulation, abnormal amounts can be found in ground and surface water following the operations of airport platforms. As with many other anthropogenic, organic compounds, some concerns are raised about their biodegradation. That is why the Organization for Economic Co-operation and Development (OECD) 301 F protocol was implemented to monitor the oxygen consumption during the biodegradation of a commercial fire-fighting foam. However, a Raman spectroscopic monitoring of the process was also attached to this experimental procedure to evaluate to what extent a polyfluoroalkyl ether disappeared from the environmental matrix. Our approach relies on the use of chemometrics, such as Principal Component Analysis (PCA) and Partial Least Squares (PLS), in order to monitor the kinetics of the biodegradation reaction of one fire-fighting foam, Tridol S3B, containing a polyfluoroalkyl ether. This study provided a better appreciation of the partial biodegradation of some polyfluoroalkyl ethers by coupling Raman spectroscopy and chemometrics. This will ultimately facilitate the design of future purification and remediation devices for airport platforms.

The addition of water is used to past by internal post-curing of hardening cement. Hydration and curing of cementitious are widely identified by non-destructive ¹ H nuclear magnetic resonance (NMR) measurements of transverse relaxation time and self-diffusion. However, those non-destructive analytical methodologies do not give a truly chemical characterization of the cement matrix during the hydration and curing process. Indeed, the NMR studies only the water dynamics of hydrating cement with internal post-curing. Recent research indicated chemometrics coupled with Raman spectroscopy allows for a better understanding of chemical processes. Recent advances in computing gave industries and research centers the opportunity to generate cost effective data. In this work, an original method is presented, which uses both a data analysis and a non-invasive, non-destructive Raman monitoring of the hydration reaction of a Portland cement. Data was then analyzed by means of chemometrics methods (principal components analysis (PCA), independent components analysis (ICA), and multivariate curve resolution-alternated least-squares (MCR-ALS) with SIMPLe-to-use Interactive Self-modelling Mixture Analysi (SIMPLISMA) and Orthogonal Projection Approach (OP initialization). Results were compared to the ones obtained with thermogravimetric analysis of this cement paste. Besides the consistency of results from both analytical measurements, chemometrics coupled to Raman spectroscopy accurately revealed the details of the setting without any samples collection. The acquisition frequency allowed a proper identification of the occurrence of each of the various phases involved in the hydration and setting process.