Pablo A. Pastén

Culture dependent and independent analyses of bacterial communities involved in copper plumbing corrosion.

Aims:  This study used culture‐dependent and culture‐independent approaches to characterize bacterial communities in copper plumbing corrosion and to assess biofilm formation and copper resistance of heterotrophic bacteria isolated from copper pipes.

Natural attenuation process via microbial oxidation of arsenic in a high Andean watershed

Rivers in northern Chile have arsenic (As) concentrations at levels that are toxic for humans and other organisms. Microorganism-mediated redox reactions have a crucial role in the As cycle; the microbial oxidation of As (As(III) to As(V)) is a critical transformation because it favors the immobilization of As in the solid phase. We studied the role of microbial As oxidation for controlling the mobility of As in the extreme environment found in the Chilean Altiplano (i.e., > 4000 meters above sea level (masl) and < 310 mm annual rainfall), which are conditions that have rarely been studied. Our model system was the upper Azufre River sub-basin, where the natural attenuation of As from hydrothermal discharge (pH 4-6) was observed. As(III) was actively oxidized by a microbial consortium, leading to a significant decrease in the dissolved As concentrations and a corresponding increase in the sediments As concentration downstream of the hydrothermal source. In-situ oxidation experiments demonstrated that the As oxidation required biological activity, and microbiological molecular analysis confirmed the presence of As(III)-oxidizing groups (aroA-like genes) in the system. In addition, the pH measurements and solid phase analysis strongly suggested that the As removal mechanism involved adsorption or coprecipitation with Fe-oxyhydroxides. Taken together, these results indicate that the microorganism-mediated As oxidation contributed to the attenuation of As concentrations and the stabilization of As in the solid phase, therefore controlling the amount of As transported downstream. This study is the first to demonstrate the microbial oxidation of As in Altiplano basins and its relevance in the immobilization of As.

Differential arsenic binding in the sediments of two sites in Chile's lower Loa River basin.

Fluvial sediments from two lower Loa River basin sites in northern Chile were compared in order to probe the effects of vegetation and organic matter (OM) on As accumulation in fluvial environments. The two sites were the Sloman dam, which lacks macrophytes and has a low OM content (2.4%) in sediments, and the Quillagua Oasis, which is 23 km downstream from the Sloman site and has a higher OM (6.2%) in sediments and abundant aquatic plant life. The Quillagua site had preferential As enrichment with a co-occurrence pattern that differed from that of the Sloman site, which had a lower As concentration (1528 vs. 262 mg/kg d.w., respectively). At the Quillagua site, As concentration was strongly correlated with Mn and OM (r = 0.91 and 0.85, respectively); while at the Sloman site, As concentration in sediments was significantly correlated with Ca and Sr (r = 0.63 and 0.54, respectively). Sequential extraction analyses showed that the Sloman site had higher percentage of easily exchangeable As within the surface sediment (12%, 45 mg/kg d.w.) compared with the Quillagua site (3%, 40 mg/kg d.w.). These contrasting results suggest that both vegetation and OM control the immobilization and accumulation of As in the arid Loa River basin.

Potential accumulation of contaminated sediments in a reservoir of a high-Andean watershed: Morphodynamic connections with geochemical processes†

Rapid changes due to anthropic interventions in high-altitude environments, such as the Altiplano region in South America, require new approaches to understand the connections between physical and geochemical processes. Alterations of the water quality linked to the river morphology can affect the ecosystems and human development in the long term. The future construction of a reservoir in the Lluta River, located in northern Chile, will change the spatial distribution of arsenic-rich sediments, which can have significant effects on the lower parts of the watershed. In this investigation, we develop a coupled numerical model to predict and evaluate the interactions between morphodynamic changes in the Lluta reservoir, and conditions that can potentially desorb arsenic from the sediments. Assuming that contaminants are mobilized under anaerobic conditions, we calculate the oxygen concentration within the sediments to study the interactions of the delta progradation with the potential arsenic release. This work provides a framework for future studies aimed to analyze the complex connections between morphodynamics and water quality, when contaminant-rich sediments accumulate in a reservoir. The tool can also help to design effective risk management and remediation strategies in these extreme environments.

Multi-technique approach to assess the effects of microbial biofilms involved in copper plumbing corrosion

Microbially influenced corrosion (MIC) is recognized as an unusual and severe type of corrosion that causes costly failures around the world. A microbial biofilm could enhance the copper release from copper plumbing into the water by forming a reactive interface. The biofilm increases the corrosion rate, the mobility of labile copper from its matrix and the detachment of particles enriched with copper under variable shear stress due to flow conditions. MIC is currently considered as a series of interdependent processes occurring at the metal-liquid interface. The presence of a biofilm results in the following effects: (a) the formation of localized microenvironments with distinct pH, dissolved oxygen concentrations, and redox conditions; (b) sorption and desorption of labile copper bonded to organic compounds under changing water chemistry conditions; (c) change in morphology by deposition of solid corrosion by-products; (d) diffusive transport of reactive chemical species from or towards the metal surface; and (e) detachment of scale particles under flow conditions. Using a multi-technique approach that combines pipe and coupon experiments this paper reviews the effects of microbial biofilms on the corrosion of copper plumbing systems, and proposes an integrated conceptual model for this phenomenon supported by new experimental data.

Modeling MIC copper release from drinking water pipes.

Copper is used for household drinking water distribution systems given its physical and chemical properties that make it resistant to corrosion. However, there is evidence that, under certain conditions, it can corrode and release unsafe concentrations of copper to the water. Research on drinking water copper pipes has developed conceptual models that include several physical-chemical mechanisms. Nevertheless, there is still a necessity for the development of mathematical models of this phenomenon, which consider the interaction among physical-chemical processes at different spatial scales. We developed a conceptual and a mathematical model that reproduces the main processes in copper release from copper pipes subject to stagnation and flow cycles, and corrosion is associated with biofilm growth on the surface of the pipes. We discuss the influence of the reactive surface and the copper release curves observed. The modeling and experimental observations indicated that after 10h stagnation, the main concentration of copper is located close to the surface of the pipe. This copper is associated with the reactive surface, which acts as a reservoir of labile copper. Thus, for pipes with the presence of biofilm the complexation of copper with the biomass and the hydrodynamics are the main mechanisms for copper release.

Response of suspended sediment particle size distributions to changes in water chemistry at an Andean mountain stream confluence receiving arsenic rich acid drainage

Acid drainage is an important water quality issue in Andean watersheds, affecting the sustainability of urban, agricultural and industrial activities. Mixing zones receiving acid drainage are critical sites where changes in pH and chemical environment promotes the formation and dissolution of iron and aluminum oxy/hydroxides. These particles can significantly change the speciation of toxic metals and metalloids throughout drainage networks via sorption, desorption and settling processes. However, little is known about the behavior of particle size distributions (PSDs) in streams affected by acid drainage and their relationship to metal speciation. This work studied: (a) the PSDs for a wide range of mixing ratios found at a fluvial confluence affected by acid drainage, and (b) the response of PSDs and arsenic speciation to environmental changes found when the particles approach complete mixing conditions. The confluence between the Azufre River (pH ~ 2, high concentration of dissolved metals) and Caracarani River (pH = 8.6, low concentration of dissolved metals) was used as a representative model for study. Field measurements show a bimodal PSD with modal diameters of ~50 and 300 µm. At shorter distances from the junction the smaller modes with smaller particle volumes were dominant across the stream cross-sections. A systematic shift towards larger particle sizes and larger particle volumes occurred downstream. The analysis of laboratory PSDs for Azufre/Caracarani mixing ratios between 0.01 and 0.5 (pHs from 6.2 to 2.3) showed a bimodal trend with ~15 and 50 µm characteristic diameters; larger particles formed at higher pHs. When particle suspensions were transferred in laboratory experiments from very low pHs to full mixing conditions (pH ~ 2.8 and mixing ratio ~ 0.25) particle sizes varied, while the dissolved arsenic concentration decreased. The observed reaction kinetics were slow compared to the time scale of advective transport, creating opportunities for engineered controls for arsenic. This work contributes to a better understanding of the chemical-hydrodynamic interactions in watersheds affected by mining, and identifying opportunities to improve water quality at points of use. This article is protected by copyright. All rights reserved.

A new aerobic chemolithoautotrophic arsenic oxidizing microorganism isolated from a high Andean watershed

Biological arsenic oxidation has been suggested as a key biogeochemical process that controls the mobilization and fate of this metalloid in aqueous environments. To the best of our knowledge, only four aerobic chemolithoautotrophic arsenite-oxidizing (CAO) bacteria have been shown to grow via direct arsenic oxidation and to have the essential genes for chemolithoautotrophic arsenite oxidation. In this study, a new CAO bacterium was isolated from a high Andean watershed evidencing natural dissolved arsenic attenuation. The bacterial isolate, designated TS-1, is closely related to the Ancylobacter genus, in the Alphaproteobacteria class. Results showed that TS-1 has genes for arsenite oxidation and carbon fixation. The dependence of bacterial growth from arsenite oxidation was demonstrated. In addition, a mathematical model was suggested and the kinetic parameters were obtained by simultaneously fitting the biomass growth, arsenite depletion curves, and arsenate production. This research increases the knowledge of chemolithoautotrophic arsenic oxidizing microorganisms and its potential role as a driver for natural arsenic attenuation.

Enhancement of particle aggregation in the presence of organic matter during neutralization of acid drainage in a stream confluence and its effect on arsenic immobilization

Acid drainage (AD) is an important environmental concern that impacts water quality. The formation of reactive Fe and Al oxyhydroxides during the neutralization of AD at river confluences is a natural attenuation process. Although it is known that organic matter (OM) can affect the aggregation of Fe and Al oxyhydroxides and the sorption of As onto their surfaces, the role of OM during the neutralization of AD at river confluences has not been studied. Field and experimental approaches were used to understand this role, using the Azufre River (pH 2) - Caracarani River (pH 8.6) confluence (northern Chile) as model system. Field measurements of organic carbon revealed a 10-15% loss of OM downstream the confluence, which was attributed to associations with Fe and Al oxyhydroxides that settle in the river bed. Laboratory mixtures of AD water with synthetic Caracarani waters under varying conditions of pH, concentration and type of OM revealed that OM promoted the aggregation of Fe oxyhydroxides without reducing As sorption, enhancing the removal of As at slightly acidic conditions (pH ∼4.5). At acidic conditions (pH ∼3), aggregation of OM - metal complexes at high OM concentrations could become the main removal mechanism. One type of OM promoted bimodal particle size distributions with larger mean sizes, possibly increasing the settling velocity of aggregates. This work contributes to a better understanding of the role of OM in AD affected basins, showing that the presence of OM during processes of neutralization of AD can enhance the removal of toxic elements.

Water Quality: Trends and Challenges

The complex dynamics of the interactions between natural factors (geology, hydrology, biogeochemistry) and human factors (mining, agriculture, urban space, infrastructure) underlie a diverse range of challenges related to water quality throughout Chile. Water quality in Northern Chile is characterized by high local concentrations of dissolved salts, metals, and metalloids in surface and groundwater. Salts and metals show decreasing concentrations towards Central Chile due to higher water discharge; yet still local enrichments are observed in some tributaries (notably copper). Reservoirs and lakes in Central Chile show mesotrophic and eutrophic conditions with chronic episodes of algal blooms and fish kills from the high influx of nutrients linked mainly to diffuse pollution from agriculture and urban wastewater discharges without tertiary treatment. Water quality in Southern Chile is characterized in general by low dissolved salts concentrations and oligotrophic to oligo-mesotrophic conditions, with local exceptions in streams and bodies of water that receive industrial and treated urban wastewater discharges or that are used for fish farming. Several challenges to water policy arise when considering water quality issues: (i) integrated management approach to water quality; (ii) a more comprehensive and dense monitoring network; (iii) protection and improvement of the trophic state of Chilean lakes and reservoirs; (iv) promote the use of more sustainable treatment alternatives like enhanced natural attenuation and constructed wetlands.