Is sorption technology fit for the removal of persistent and mobile organic contaminants from water?

Persistent, Mobile, and Toxic (PMT) and very persistent and very mobile (vPvM) substances are a growing threat to water security and safety. Many of these substances are distinctively different from other more traditional contaminants in terms of their charge, polarity, and aromaticity. This results in distinctively different sorption affinities towards traditional sorbents such as activated carbon. Additionally, an increasing awareness on the environmental impact and carbon footprint of sorption technologies puts some of the more energy-intensive practices in water treatment into question. Commonly used approaches may thus need to be readjusted to become fit for purpose to remove some of the more challenging PMT and vPvM substances, including for example short chained per- and polyfluoroalkyl substances (PFAS). We here critically review the interactions that drive sorption of organic compounds to activated carbon and related sorbent materials and identify opportunities and limitations of tailoring activated carbon for PMT and vPvM removal. Other less traditional sorbent materials, including ion exchange resins, modified cyclodextrins, zeolites and metal-organic frameworks are then discussed for potential alternative or complementary use in water treatment scenarios. Sorbent regeneration approaches are evaluated in terms of their potential, considering reusability, potential for on-site regeneration, and potential for local production. In this context, we also discuss the benefits of coupling sorption to destructive technologies or to other separation technologies. Finally, we sketch out possible future trends in the evolution of sorption technologies for PMT and vPvM removal from water.

Efficient removal of trifluoroacetic acid from water using surface-modified activated carbon and electro-assisted desorption.

Trifluoroacetic acid (TFA) is a very persistent, very mobile substance (vPvM) with potential toxicity, and causes increasing environmental concerns worldwide. Conventional wastewater treatment strategies are inefficient for selective TFA removal in the presence of inorganic anions. Here we show that surface defunctionalized activated carbon felt (DeACF) carrying anion exchange sites exhibits an outstanding adsorption efficiency towards TFA thanks to introduced electrostatic attraction and enhanced interactions between hydrophobic carbon surface and CF3 moieties (qmax = 30 mg/g, Kd = (840 ± 80) L/kg at cTFA = 3.4 mg/L in tap water). Flow-cell experiments demonstrated a strongly favored TFA uptake by DeACF from tap water over Cl- and SO42- but a remarkable co-adsorption of the inorganic water contaminant NO3-. Electro-assisted TFA desorption using 10 mM Na2SO4 as electrolyte and oxidized ACF as anode showed high recoveries of ≥ 87% at low cell voltages (< 1.1 V). Despite an initial decrease in TFA adsorption capacity (by 33%) caused by partial surface oxidation of DeACF after the 1st ad-/desorption cycle, the system stability was fully maintained over the next 4 cycles. Such electro-assisted 'trap&release' approach for TFA removal can be exploited for on-site regenerable adsorption units and as a pre-concentration step combined with degradation technologies.

Experimental studies on combined production of CH4 and safe long-term storage of CO2 in the form of solid hydrate in sediment.

The production of the confirmed enormous resources of CH4 trapped in permafrost and deep ocean sediments in the form of hydrates has been hampered by the lack of an extraction procedure that is both effective and environmentally sensitive. This research explores experimentally the dynamic rate limiting steps in the dissociation of methane hydrates and the formation of CO2 hydrates in a sediment matrix. The use of CO2 injection and substitution for hydrate extraction takes advantage of novel thermodynamics and also provides a safe storage option for greenhouse gas. This experimental work incorporates a high-pressure facility dedicated for CH4 hydrates exchange with CO2 that replicates creation of natural gas hydrate from incoming gas below water in the pore space. The hydrate formation/exchange chamber follows the state-of-art hydrate science and is equipped with sensors distributed in several sections: the top section for gas release, a CH4 hydrate section, and a subsequent injection of CO2 from the bottom section, which also mimics hydrate dissociation towards incoming seawater through fracture systems connected from the seafloor. Four experimental conditions were examined. They comprise pure CO2 injection, and 10, 20, and 30 mole% N2 added to the CO2. We observed an increase in CH4 release from pure CO2 injection to 10 mole% N2 addition. A significant extra release of CH4 occurred by stepping up to 20 mole% N2 addition but no significant change was observed from 20 to 30 mole% N2 addition. Maximum conversion in this study is 34 mole% of CO2, and 2 mole% N2 taking the place of methane hydrate in large and small cavities. The results also show that effective substitution for hydrate production cannot rely on pure carbon dioxide injection.

Adsorption of polar and ionic organic compounds on activated carbon: Surface chemistry matters.

Persistent and mobile organic compounds (PMOCs) are often detected micropollutants in the water cycle, thereby challenging the conventional wastewater and drinking water treatment techniques. Carbon-based adsorbents are often less effective or even unable to remove this class of pollutants. Understanding of PMOC adsorption mechanisms is urgently needed for advanced treatment of PMOC-contaminated water. Here, we investigated the effect of surface modifications of activated carbon felts (ACFs) on the adsorption of six selected PMOCs carrying polar or ionic groups. Among three ACFs, defunctionalized ACF bearing net positive surface charge at neutral pH provides the most versatile sorption efficiency for all studied PMOC types representing neutral, anionic and cationic compounds. Ion exchange capacity giving quantitative information of sorbent surface charges at specified pH is recognized as a frequently underestimated key property for evaluating adsorbents aiming at PMOC adsorption. A most recently developed prediction tool for Freundlich parameters in PMOC adsorption was applied and the prediction results are compared to the experimental data. The comparison demonstrates the so far underestimated importance of the sorbent surface chemistry for PMOC adsorption affinity and capacity. PMOC adsorption mechanisms were additionally investigated by adsorption experiments at various temperatures, pH values and electrolyte concentrations. Exothermic sorption was observed for all sorbate-sorbent pairs. Adsorption is improved for ionic PMOCs on AC carrying sites of the same charge (positive or negative) at increased electrolyte concentration, while not affected for neutral PMOCs unless strong electron donor-acceptor yet weak non-Coulombic interactions exist. Our findings will allow for better design and targeted application of activated carbon-based sorbents in water treatment facilities.

Mechanistic insights into fast adsorption of perfluoroalkyl substances on carbonate-layered double hydroxides.

Layered double hydroxide (LDH) with the metal composition of Cu(II)Mg(II)Fe(III) was prepared as an adsorbent for fast adsorption of perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA). 84% of PFOS and 48% of PFOA in relation to the equilibrium state were adsorbed in the first minutes of contact with 0.1 g/L of suspended µm-sized LDH particles. The adsorption mechanisms of PFOS and PFOA on the CuMgFe-LDH were interpreted. Hydrophobic interactions were primarily responsible for the adsorption of these compounds in accordance with the different adsorption affinities of long-chain (C8, Kd = 105 L/kg) and short-chain (C4, Kd = 102 L/kg) perfluorinated carboxylic acids. PFOA adsorption on CuMgFe-LDH was strongly suppressed under alkaline conditions while PFOS uptake was only slightly affected in the pH range from 4.3 to 10.7, indicating a significant role of electrostatic interactions for PFOA adsorption. The adsorption of PFOS and PFOA was rather insensitive to competition by monovalent anions. The previously reported 'memory effect' of calcined CuMgFe-LDH for sorption of organic anions was not confirmed in the present study. Spent CuMgFe-LDH could be easily regenerated by extraction with 50 vol% methanol in water within 1 h and maintained a high PFOS removal in subsequent usage cycles.

What is specific in adsorption of perfluoroalkyl acids on carbon materials?

Various activated carbon products show wide variability in adsorption performance towards perfluoroalkyl acids (PFAAs) and predictive tools are largely missing. In order to gain a better understanding on the adsorption mechanisms of PFAAs, perfluorooctanoic acid (PFOA) was compared with its fluorine-free analogon octanoic acid (OCA) as well as phenanthrene (nonionic) in terms of their response towards changes in carbon surface chemistry. For this approach, a commercial activated carbon felt (ACF) with high content of acidic surface groups was modified by amino-functionalisation as well as thermal defunctionalisation in H2 (yielding DeCACF). While improvement by amino-functionalisation was moderate, defunctionalisation drastically enhanced adsorption of PFOA and other PFAAs. In comparison, OCA and phenanthrene were much less affected. Electrostatic interactions and charge compensation provided by positively charged surface sites (quantified by their anion exchange capacity) are obviously more crucial for PFAAs than for common organic acids (such as the tested OCA). A possible reason is their exceptionally strong acidity with pKa < 1. Nevertheless, at the best modified ACF material (DeCACF) the sorption coefficients (Kd) for PFOA and perfluorooctylsulfonic acid (PFOS) at environmentally relevant concentrations reach the range of 107 L/kg which is outstanding. DeCACF provides a surface with overall low polarity (low O-content), low density of acidic sites causing electrostatic repulsion, but nevertheless a sufficient density of charge-balancing sites for organic anions. The results of the present study contribute to an optimized selection of adsorbents for PFAA adsorption from water considering also various salt matrices and the presence of natural organic matter.

Hydrate Nucleation, Growth, and Induction.

The first stage of any phase transition is a dynamic coupling of transport processes and thermodynamic changes. The free energy change of the phase transition must be negative and large enough to also overcome the penalty work needed for giving space to the new phase. The transition from an unstable situation over to a stable growth is called nucleation. Hydrate formation nucleation can occur along a variety of different routes. Heterogeneous formation on the interface between gas (or liquid) and water is the most commonly studied. A hydrate can also form homogeneously from dissolved hydrate formers in water, and the hydrate can nucleate toward mineral surfaces in natural sediments or a pipeline (rust). A hydrate particle's critical size is the particle size needed to enter a region of stable growth. These critical sizes and the associated nucleation times are nanoscale processes. The dynamics of the subsequent stable growth can be very slow due to transport limitations of hydrate-forming molecules and water across hydrate films. Induction times can be defined as the time needed to reach a visible hydrate. In the open literature, these induction times are frequently misinterpreted as nucleation times. Additional misunderstandings relate to the first and second laws of thermodynamics and the number of independent thermodynamics variables. It is not possible to reach thermodynamic equilibrium in systems where hydrates form in a pipeline or in sediments. Finally, there are common misconceptions that only one type of hydrate will form. In a non-equilibrium situation, several hydrates will form, depending on which phases the hydrate formers and water come from. In this paper, we utilize a simple nucleation theory to illustrate nucleation and growth of some simple hydrates in order to illustrate the non-equilibrium nature of hydrates and the fast nucleation times. To illustrate this, we apply thermodynamic conditions for a real pipeline transporting natural gas from Norway to Germany. This specific example also serves as a case for illustration of the possible impact of rusty pipeline surfaces in kicking out water from the gas. Specifically, we argue that the tolerance limit for water concentration according to current industrial hydrate risk practice might overestimate the tolerance by a factor of 20 as compared to tolerance concentration based on adsorption on rust.

Methanol as a hydrate inhibitor and hydrate activator.

During their transport to processing plants, produced hydrocarbon streams are always accompanied by water appearing as a separate phase in contact with the hydrocarbons. Dramatic temperature and pressure changes during processing can lead to condensation of water and possibly hazardous formation of ice and hydrates. Historically, methanol has been the dominating chemical agent added to prevent the formation of solid water phases. In this work, the technique of molecular dynamics simulation has been utilized to investigate and illustrate the impact of methanol as a surfactant in a water-methane system. We have found that adding 5% of methanol boosted the diffusion of methane through the interface by more than 40% compared to the reference system. The amount of methane accumulated in the aqueous phase was also significantly higher. This effect will likely also result in a significant increase in homogeneous and heterogeneous hydrate formation in these regions in the case of the methanol-stimulated system, and thus necessitate the application of classical nucleation theory. In particular, our analysis emphasised the fact that several different hydrates may form in this scenario. In case of the homogeneous hydrate formation, there will theoretically exist an infinite number of hydrate phases corresponding to concentrations spanning the range between methane's solubility and its hydrate stability limit.