Adsorption of the disinfectant benzalkonium chloride on montmorillonite. Synergistic effect in mixture of molecules with different chain lengths.

The biocide benzalkonium chloride (BAC) is a mix of cationic alkylbenzyldimethylammonium surfactants having different alkyl chain lengths. A comparative study of adsorption on the phyllosilicate clay montmorillonite of two of these surfactants, with alkyl chains having respectively 12 C atoms (BAC-12) and 14 C atoms (BAC-14), and a mixture of both surfactants is presented in this work. Adsorption isotherms were performed for individual surfactants and for a 1:1 mixture BAC-12+BAC-14. The adsorption was investigated in an ample concentration range that covers almost seven orders of magnitude in concentrations (from 1 nM to 10 mM), range that includes environmentally relevant concentrations. Quantification of BAC was performed by HPLC-UV and LC-MS and the results were completed with powder X-Ray diffraction. The adsorption of both surfactants leads to adsorption isotherms with two well differentiated steps. The first step corresponds almost exclusively to a cation exchange process, and the binding constant is very similar for both surfactants. The second step of the isotherms is observed at higher concentrations and adsorption is mainly driven by lateral interactions between surfactant molecules. The binding constant of this step is larger for BAC-14 than for BAC-12. Adsorption from a BAC-12+BAC-14 mixture shows a synergistic behaviour, possibly due to a better packing arrangement in the interlayer. Calculations show that in natural systems silicate clays are major sorbents of BAC at low concentrations whereas binding to humic acid is predominant at high concentrations.

Biomedicine in the environment: sorption of the cyclotide kalata B2 to montmorillonite, goethite, and humic acid.

Cyclotides are bioactive, stable mini-proteins produced in high amounts in Violaceae and Rubiaceae with promising pharmaceutical and agrochemical applications. Environmental issues must be addressed before large-scale plant cultivation of cyclotides for pharmaceutical or pesticidal purposes can commence. The objective of the present study was to investigate sorption of the cyclotide kalata B2 (kB2), because knowledge of cyclotide biogeochemistry will aid our understanding of environmental fate. The octanol-water partitioning coefficient was determined to be 2.8 ± 0.6 (log K(OW) = 0.4 ± 0.1). Sorption of kB2 by montmorillonite, goethite, and humic acid was investigated at different concentrations and under varying acidity and reached equilibrium within minutes. The kB2 sorption at a solution concentration of 0.2 mg/L to montmorillonite was high (120 mg/g) compared to humic acid (0.60 mg/g) and goethite (0.03 mg/g). Kalata B2 intercalated the interlayer space of montmorillonite. The sorption isotherm for humic acid was linear up to a solution concentration of 0.8 mg/L and concave for montmorillonite and goethite up to an equilibrium solution concentration of 1.5 mg/L. Sorption to goethite was unaffected by pH, but sorption to montmorillonite and humic acid at pH near the isoelectric point (pI) was threefold the sorption when pH > the isoelectric point, suggesting that electrostatic interaction/repulsion between kB2 and sorbents play an important role. The strong sorption to montmorillonite reduces exposure to below toxic threshold values. In addition, the transport risk of soluble cyclotides is reduced, but particle-bound cyclotides may be transported to recipient aquatic sediments with the associated risk of adversely affecting sediment-dwelling organisms.

Biomedicine in the environment: cyclotides constitute potent natural toxins in plants and soil bacteria.

Bioactive compounds produced by plants are easily transferred to soil and water and may cause adverse ecosystem effects. Cyclotides are gene-encoded, circular, cystine-rich mini-proteins produced in Violaceae and Rubiaceae in high amounts. Based on their biological activity and stability, cyclotides have promising pharmaceutical and agricultural applications. We report the toxicity of the cyclotides: kalata B1, kalata B2, and cycloviolacin O2 extracted from plants to green algae (Pseudokirchneriella subcapitata), duckweed (Lemna minor L.), lettuce (Lactuca sativa L.), and bacteria extracted from soil measured as [³H]leucine incorporation. Quantification by liquid chromatography-mass spectrometry demonstrated up to 98% loss of cyclotides from aqueous solutions because of sorption to test vials. Sorption was prevented by adding bovine serum albumin (BSA) to the aqueous media. Cyclotides were toxic to all test organisms with EC50 values of 12 through 140 µM (algae), 9 through 40 µM (duckweed), 4 through 54 µM (lettuce), and 7 through 26 µM (bacteria). Cycloviolacin O2 was the most potent cyclotide in all assays examined. This report is the first to document toxic effects of cyclotides in plants and soil bacteria and to demonstrate that cyclotides are as toxic as commonly used herbicides and biocides. Hence, cyclotides may adversely affect soil and aquatic environments, which needs to be taken into account in future risk assessment of cropping systems for production of these highly bioactive compounds.

Degradation kinetics of ptaquiloside in soil and soil solution.

Ptaquiloside (PTA) is a carcinogenic norsesquiterpene glycoside produced in bracken (Pteridium aquilinum (L.) Kuhn), a widespread, aggressive weed. Transfer of PTA to soil and soil solution eventually may contaminate groundwater and surface water. Degradation rates of PTA were quantified in soil and soil solutions in sandy and clayey soils subjected to high natural PTA loads from bracken stands. Degradation kinetics in moist soil could be fitted with the sum of a fast and a slow first-order reaction; the fast reaction contributed 20 to 50% of the total degradation of PTA. The fast reaction was similar in all horizons, with the rate constant k(1F) ranging between 0.23 and 1.5/h. The slow degradation, with the rate constant k(1S) ranging between 0.00067 and 0.029/ h, was more than twice as fast in topsoils compared to subsoils, which is attributable to higher microbial activity in topsoils. Experiments with sterile controls confirmed that nonmicrobial degradation processes constituted more than 90% of the fast degradation and 50% of the slow degradation. The lower nonmicrobial degradation rate observed in the clayey compared with the sandy soil is attributed to a stabilizing effect of PTA by clay silicates. Ptaquiloside appeared to be stable in all soil solutions, in which no degradation was observed within a period of 28 d, in strong contrast to previous studies of hydrolysis rates in artificial aqueous electrolytes. The present study predicts that the risk of PTA leaching is controlled mainly by the residence time of pore water in soil, soil microbial activity, and content of organic matter and clay silicates.