The deep geological repository (DGR) concept consists of storing radioactive waste in metal canisters, surrounded by compacted bentonite, and placed deeply into a geological formation. Here, bentonite slurry microcosms with copper canisters, inoculated with bacterial consortium and amended with acetate, lactate and sulfate were set up to investigate their geochemical evolution over a year under anoxic conditions. The impact of microbial communities on the corrosion of the copper canisters in an early-stage (45 days) was also assessed. The amended bacterial consortium and electron donors/acceptor accelerated the microbial activity, while the heat-shocked process had a retarding effect. The microbial communities partially oxidize lactate to acetate, which is subsequently consumed when the lactate is depleted. Early-stage microbial communities showed that the bacterial consortium reduced microbial diversity with Pseudomonas and Stenotrophomonas dominating the community. However, sulfate-reducing bacteria such as Desulfocurvibacter, Anaerosolibacter, and Desulfosporosinus were enriched coupling oxidation of lactate/acetate with reduction of sulfates. The generated biogenic sulfides, which could mediate the conversion of copper oxides (possibly formed by trapped oxygen molecules on the bentonite or driven by the reduction of H2O) to copper sulfide (Cu2S), were identified by X-ray photoelectron spectroscopy (XPS). Overall, these findings shed light on the ideal geochemical conditions that would affect the stability of DGR barriers, emphasizing the impact of the SRB on the corrosion of the metal canisters, the gas generation, and the interaction with components of the bentonite.

Gaps in the United States Environmental Protection Agency (US EPA) Lead and Copper Rule (LCR) leave some consumers and their pets vulnerable to high cuprosolvency in drinking water. This study seeks to help proactive utilities who wish to mitigate cuprosolvency problems through the addition of orthophosphate corrosion inhibitors. The minimum doses of orthophosphate necessary to achieve acceptable cuprosolvency in relatively new copper pipe were estimated as a function of alkalinity via linear regressions for the 90th, 95th, and 100th percentile copper tube segments (R2 > 0.98, n = 4). Orthophosphate was very effective at reducing cuprosolvency in the short term but, in some cases, resulted in higher long-term copper concentrations than the corresponding condition without orthophosphate. Alternatives to predicting \"long-term\" results for copper tubes using simpler bench tests starting with fresh Cu(OH)2 solids showed promise but would require further vetting to overcome limitations such as maintaining water chemistry and orthophosphate residuals and to ensure comparability to results using copper tube.

Deep Geological Repositories (DGRs) consist of radioactive waste contained in corrosion-resistant canisters, surrounded by compacted bentonite clay, and buried few hundred meters in a stable geological formation. The effects of bentonite microbial communities on the long-term stability of the repository should be assessed. This study explores the impact of harsh conditions (60 °C, highly-compacted bentonite, low water activity), and acetate:lactate:sulfate addition, on the evolution of microbial communities, and their effect on the bentonite mineralogy, and corrosion of copper material under anoxic conditions. No bentonite illitization was observed in the treatments, confirming its mineralogical stability as an effective barrier for future DGR. Anoxic incubation at 60 °C reduced the microbial diversity, with Pseudomonas as the dominant genus. Culture-dependent methods showed survival and viability at 60 °C of moderate-thermophilic aerobic bacterial isolates (e.g., Aeribacillus). Despite the low presence of sulfate-reducing bacteria in the bentonite blocks, we proved their survival at 30 °C but not at 60 °C. Copper disk\'s surface remained visually unaltered. However, in the acetate:lactate:sulfate-treated samples, sulfide/sulfate signals were detected, along with microbial-related compounds. These findings offer new insights into the impact of high temperatures (60 °C) on the biogeochemical processes at the compacted bentonite/Cu canister interface post-repository closure.

Deep Geological Repository (DGR) is the preferred option for the final disposal of high-level radioactive waste. Microorganisms could affect the safety of the DGR by altering the mineralogical properties of the compacted bentonite or inducing the corrosion of the metal canisters. In this work, the impact of physicochemical parameters (bentonite dry density, heat shock, electron donors/acceptors) on the microbial activity, stability of compacted bentonite and corrosion of copper (Cu) discs was investigated after one-year anoxic incubation at 30 ºC. No-illitization in the bentonite was detected confirming its structural stability over 1 year under the experimental conditions. The microbial diversity analysis based on 16 S rRNA gene Next Generation Sequencing showed slight changes between the treatments with an increase of aerobic bacteria belonging to Micrococcaceae and Nocardioides in heat-shock tyndallized bentonites. The survival of sulfate-reducing bacteria (the main source of Cu anoxic corrosion) was demonstrated by the most probable number method. The detection of CuxS precipitates on the surface of Cu metal in the bentonite/Cu metal samples amended with acetate/lactate and sulfate, indicated an early stage of Cu corrosion. Overall, the outputs of this study help to better understand the predominant biogeochemical processes at the bentonite/Cu canister interface upon DGR closure.

The structure and composition of copper surfaces in aqueous solutions of benzotriazole (BTAH) and NaCl was investigated by sum frequency vibrational spectroscopy as a function of concentration and bias during cyclic voltammetry experiments. We found that the protection provided by the BTAH films formed at the copper surface is effective for negative bias voltages below the open circuit potential (OCP) but not at positive voltages where Cl- displaces BTAH. By measuring the Gibbs adsorption energy of BTAH and Cl-, we found that a particularly stable Cl- structure is formed around the OCP, suggesting that electronegative additives that move the OCP to higher negative values can improve BTAH protection, which we confirmed by the addition of a negatively charged sodium dodecyl sulfate surfactant.

Corrosion of copper material in drinking water systems causes public health concerns and plumbing failures. This study investigated the early corrosion of new copper surfaces in situ using a novel technique: quartz crystal microbalance with dissipation (QCMD). The QCMD results showed that increasing the water pH from 6.5 to 9.0 and the addition of 6 mg/L orthophosphate at pH 6.5 and 9.0 slowed down the copper surface mass changes as indicated by the reduced changes in frequency (Δf5) at 51-89% and total copper release at 29-72%. The water pH 9.0 without orthophosphate was the most likely to induce localized corrosion relative to other conditions at pH 6.5 and pH 9.0 with orthophosphate. Based on the changes in dissipation values (ΔD5) from QCMD and the morphology, microstructure, and composition of the deposited copper corrosion byproducts, digital microscopy, field-emission scanning electron microscopy with energy dispersive spectroscopy, and X-ray photoelectron spectrometry analyses confirmed that the pH and orthophosphate inhibited copper corrosion with different mechanisms. QCMD provided sensitive, rapid, and continuous responses to mass and surface changes and can be useful for evaluating early water corrosivity to new copper.

Carbonaceous residues on copper pipes during the manufacturing process are known to be one of the main causes of pitting corrosion on copper pipes. This study examined the corrosion-inhibiting effect of benzotriazole (BTA) on C12200 copper pipes with carbonaceous film in synthetic tap water. In the absence of BTA, localized corrosion mechanisms due to galvanic corrosion, crevice corrosion, and oxygen-concentration cell were proposed in the boundary part of the carbonaceous film on the copper through X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) with energy dispersive spectrometer (EDS) analyses. Electrochemical tests showed that BTA inhibits corrosion by forming Cu-BTA complexes on all over the copper surface where carbonaceous film is present. BTA mitigates galvanic corrosion and crevice corrosion at the boundary of the carbonaceous film and suppresses the formation of oxygen-concentration cells through the formation of a Cu-BTA complex.

Exceptionally large crystals of posnjakite, Cu4SO4(OH)6(H2O), formed during corrosion of a Swagelock(tm) Snubber copper gasket within the MX1 beamline at the ANSTO-Melbourne, Australian Synchrotron. The crystal structure was solved using synchrotron radiation to R 1 = 0.029 and revealed a structure based upon [Cu4(OH)6(H2O)O] sheets, which contain Jahn-Teller-distorted Cu octa-hedra. The sulfate tetra-hedra are bonded to one side of the sheet via corner sharing and linked to successive sheets via extensive hydrogen bonds. The sulfate tetra-hedra are split and rotated, which enables additional hydrogen bonds.

Microbiologically influenced corrosion (MIC) of copper by Desulfovibrio vulgaris, a sulfate reducing bacterium (SRB), was investigated in anaerobic vials with a fixed broth volume of 40 mL but varied headspace volumes (10 mL, 85 mL 160 mL). It was found that the headspace volume variation had a very large effect on the dissolved [H2S] in the broth and the cell counts of planktonic and sessile cells, as well as Cu corrosion severity. A 16× smaller headspace led to a 1.6-fold increase in the dissolved [H2S], a 13-fold decrease in sessile SRB cell count, a 32-fold decrease in planktonic cell count and a 3.7-fold increase of Cu weight loss. SEM images revealed that different headspace volumes caused different corrosion patterns on the immersed coupons. With a lower headspace volume, pitting corrosion was observed, while with a higher headspace volume, intergranular corrosion was seen. The results confirmed that SRB MIC of Cu belongs to metabolite-MIC (M-MIC) by H2S, unlike SRB MIC of carbon steel that belongs to extracellular electron transfer-MIC (EET-MIC) that is directly correlated with sessile cell counts rather than dissolved [H2S]. .

Hypochlorous acid has been reported as the main oxidant agent responsible for the corrosion of copper plumbing systems in chlorinated water supplies. However, there is little information about chlorine consumption kinetics in a combined system (i.e., with dissolved oxygen (DO) and free chlorine), as well as its complete mass balance within a copper pipe during stagnation. The results of our experiments using copper pipes filled with synthetic drinking water, with a moderate alkalinity (pH = 7.2; dissolved inorganic carbon = 80 mg as CaCO3 /L), and tested under chlorine concentrations from 0 to 8 mg/L, show that chlorine depletion is associated with pipe wall reactions (i.e., copper oxidation and scale formation processes). Free chlorine was depleted after 4 h of stagnation and its kinetic constant depend on the initial concentration, probably due to diffusion processes. Surface analysis including scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and total reflection X-ray fluorescence (T-XRF) suggest chlorine precipitation, probably as CuCl. The obtained kinetics of chlorine and DO reduction would be critical for modeling and prediction of corrosion events of copper premise plumbing systems. In addition, our results indicate that the pipe\'s surface reactions due to corrosion induces a loss of free chlorine in the bulk water, decreasing chlorine added for disinfection and the subsequent effect on water quality.