Carbon nanomaterial functionalization with pesticide-detoxifying carboxylesterase.

Four carbon materials, spent coffee-ground biochar, carbon black, short CNTs, and nitrogen-doped few-layer graphene (N-graphene) were tested for their functionalization with a commercial carboxylesterase. Their robustness to variations in time and key physicochemical parameters (temperature and pH) was analysed. In general, carbon nanomaterials showed better performance than biochar, both in terms of binding capacity and resilience in harsh conditions, at statistically significant levels. Among the tested materials, functionalized N-graphene also showed the highest level of inhibition of carboxylesterase by pesticide exposure. Therefore, N-graphene was selected for biotechnological application of pesticide scavenging toxicity in T. thermophila, a ciliate bioindicator of water quality. While immobilization of the enzyme was not effective in the case of carbaryl, a methyl carbamate, in the case of the organophosphorus dichlorvos, a 1- or 30-min contact time with a water solution containing 5 times the LC100 - 0.5 mM - allowed 50% and 100% rescue of ciliate survival, respectively. These results suggest that functionalization with carboxylesterase may be of additional benefit compared to bare carbon in water clean-up procedures, especially for highly hydrophilic pesticides such as dichlorvos.

Ecotoxicological effects of silver nanoparticles in marine mussels.

As the production of silver nanoparticles (AgNPs) is becoming more prevalent, it is becoming increasingly necessary to understand the toxicological effects they can have on different ecosystems. In the marine bioindicator species M. galloprovincialis Lam we predicted toxicity and bioaccumulation of 5 nm alkane-coated and 50 nm uncoated silver nanoparticles (AgNPs) along with silver nitrate as a function of the actual dose level. We generated a time persistence model of silver in seawater and used the Area Under the Curve (AUC) as independent variable in the hazard assessment. This approach allowed us to evaluate unbiased ecotoxicological endpoints for acute (survival) and chronic toxicity (byssal adhesion). Logistic regression analysis rendered an overall LC5096h values of 0.81 ± 0.07 mg h L-1 irrespectively of the silver form. By contrast, for byssal adhesion regression analysis revealed a much higher toxicological potential of silver nitrate vs AgNPs with EC5024h values respectively of 0.0024 ± 0.0009 vs 0.053 ± 0.016 and 0.063 (no computable error for 50 nm AgNP) mg h L-1, undoubtedly confirming a prevalence of ionic silver effects over AgNPs. Bioaccumulation was more efficient for silver nitrate >5 nm AgNP >50 nm AgNP reflecting a parallel with the preferential uptake route / target organ. Finally, we derived Risk Quotient (RQs) for acute and chronic effects of nanosilver in shellfish and showed that the RQs are far from the Level of Concern (LoC) at current estimated environmental concentrations (EECs). This information can ultimately help researchers, policy makers, and industry professionals decide how to safely regulate and/or dispose of AgNPs.