A review of bio-based materials for oil spill treatment.

Being cost-effective, synthetic materials were initially used abundantly for the removal of oil. Gradually, however, awareness of the use of dispersants like Corexit, which makes water resources more toxic than oil, has changed the scenario for the treatment of spilled oil. The removal of spilled oil from water resources is still a very topical issue. An eco-friendly and sustainable approach towards the environment has introduced many low-cost, non-toxic and biodegradable materials along with different biomasses to make micro-to nano-sized materials, membranes, sponges/aerogel, etc. for the removal and recovery of oil from water resources. Additionally, the reusability of these materials after the recovery of oils has added one more step towards sustainability. This review comprises the work conducted by various researchers in the field of the removal and recovery of spilled oils using various biomasses and polymers, either in the form of sorbents or separators.

Carboxymethyl Chitosan and Its Hydrophobically Modified Derivative as pH-Switchable Emulsifiers.

The emulsification properties of carboxymethyl chitosan (CMChi) and hydrophobically modified carboxymethyl chitosan (h-CMChi) were studied as a function of pH and dodecane/water ratio. The pH was varied between 6-10, and the oil/water ratio between 0.1-2.0. In CMChi solution, the emulsion stability increased as the pH was lowered from 10 to 7, and the phase inversion was shifted from oil/water ratio 1.0 to 1.8, respectively. The system behaved differently in pH 6 due to the aggregation of CMChi and the formation of nanoparticles (∼200-300 nm). No phase inversion was observed and the maximum amount of emulsified oil was reached at oil/water ratio 1.2. The h-CMChi showed similar behavior as a function of pH but, due to hydrophobic modification, the phase inversion was shifted to higher values in pH 7-10. In pH 6, the behavior was similar, but the maximum amount of emulsified oil was higher compared to CMChi. The amount of adsorbed particles correlated with the emulsified amount of oil. Reversible emulsification of dodecane was demonstrated by pH adjustment using CMChi and h-CMChi solutions. The formed emulsions were gel-like, suggesting particle-particle interaction.

One-pot synthesis of trifunctional chitosan-EDTA-ß-cyclodextrin polymer for simultaneous removal of metals and organic micropollutants.

The global contamination of water resources with inorganic and organic micropollutants, such as metals and pharmaceuticals, poses a critical threat to the environment and human health. Herein, we report on a bio-derived chitosan-EDTA-ß-cyclodextrin (CS-ED-CD) trifunctional adsorbent fabricated via a facile and green one-pot synthesis method using EDTA as a cross-linker, for the adsorption of toxic metals and organic micropollutants from wastewater. In this system, chitosan chain is considered as the backbone, and the immobilized cyclodextrin cavities capture the organic compounds via host-guest inclusion complexation, while EDTA-groups complex metals. The thoroughly characterized CS-ED-CD was employed for batch adsorption experiments. The adsorbent displayed a monolayer adsorption capacity of 0.803, 1.258 mmol g-1 for Pb(II) and Cd(II) respectively, while a heterogeneous sorption capacity of 0.177, 0.142, 0.203, 0.149 mmol g-1 for bisphenol-S, ciprofloxacin, procaine, and imipramine, respectively. The adsorption mechanism was verified by FT-IR and elemental mapping. Importantly, the adsorbent perform is effective in the simultaneous removal of metals and organic pollutants at environmentally relevant concentrations. All these findings demonstrate the promise of CS-ED-CD for practical applications in the treatment of micropollutants. This work adds a new insight to design and preparation of efficient trifunctional adsorbents from sustainable materials for water purification.

The pH sensitive properties of carboxymethyl chitosan nanoparticles cross-linked with calcium ions.

In environmental applications the applied materials are required to be non-toxic and biodegradable. Carboxymethyl chitosan nanoparticles cross-linked with Ca2+ ions (CMC-Ca) fulfill these requirements, and they are also renewable. These nanoparticles were applied to oil-spill treatment in our previous study and here we focused on enhancing their properties. It was found that while the divalent Ca2+ ions are crucial for the formation of the CMC-Ca, the attractive interaction between NH3+ and COO- groups contributed significantly to the formation and stability of the CMC-Ca. The stability decreased as a function of pH due to the deprotonation of the amino groups. Therefore, the nanoparticles were found to be fundamentally pH sensitive in solution, if the pH deviated from the pH (7-9) that was used in the synthesis of the nanoparticles. The pH sensitive CMC-Ca synthesized in pH 7 and 8 were most stable in the studied conditions and could find applications in oil-spill treatment or controlled-release of substances.