Targeted extraction of pesticide from agricultural run-off using novel molecularly imprinted polymeric pendants

Compared with nutrient levels and habitat degradation, the importance of agricultural pesticides in surface water may have been underestimated due to a lack of comprehensive quantitative analysis. Increasing pesticide contamination results in decreasing regional aquatic biodiversity, i.e., macroinvertebrate family richness is reduced by ∼30% at pesticide concentrations equaling the legally accepted regulatory threshold levels (RTLs). This study provides a comprehensive metaanalysis of 838 peer-reviewed studies (>2,500 sites in 73 countries) that evaluates, for the first time to our knowledge on a global scale, the exposure of surface waters to particularly toxic agricultural insecticides. We tested whether measured insecticide concentrations (MICs; i.e., quantified insecticide concentrations) exceed their RTLs and how risks depend on insecticide development over time and stringency of environmental regulation. Our analysis reveals that MICs occur rarely (i.e., an estimated 97.4% of analyses conducted found no MICs) and there is a complete lack of scientific monitoring data for ∼90% of global cropland. Most importantly, of the 11,300 MICs, 52.4% (5,915 cases; 68.5% of the sites) exceeded the RTL for either surface water (RTLSW) or sediments. Thus, the biological integrity of global water resources is at a substantial risk. RTLSW exceedances depend on the catchment size, sampling regime, and sampling date; are significantly higher for newer-generation insecticides (i.e., pyrethroids); and are high even in countries with stringent environmental regulations. These results suggest the need for worldwide improvements to current pesticide regulations and agricultural pesticide application practices and for intensified research efforts on the presence and effects of pesticides under real-world conditions.

Though many efforts have been devoted to the adsorptive removal of hazardous materials of organophosphorus pesticides (OPs), it is still highly desirable to develop novel adsorbents with high adsorption capacities. In the current work, the removal of two representative OPs, glyphosate (GP) and glufosinate (GF), was investigated by the exceptionally stable Zr-based MOFs of UiO-67. The abundant Zr-OH groups, resulting from the missing-linker induced terminal hydroxyl groups and the inherent bridging ones in Zr-O clusters of UiO-67 particles, served as natural anchorages for efficient GP and GF capture in relation with their high affinity toward phosphoric groups in OPs. The correlation between the most significant parameters such as contact time, OPs concentration, adsorbent dose, pH, as well as ionic strength with the adsorption capacities was optimized, and the effects of these parameters on the removal efficiency of GP and GF from the polluted aqueous solution were investigated. The adsorption of GP on UiO-67 was faster than that of GF, and a pseudo-second-order rate equation effectively described the uptake kinetics. The Langmuir model exhibited a better fit to adsorption isotherm than the Freundlich model. Thanks to the strong affinity and adequate pore size, the adsorption capacities in UiO-67 approached as high as 3.18 mmol (537 mg) g(-1) for GP and 1.98 mmol (360 mg) g(-1) for GF, which were much higher than those of many other reported adsorbents. The excellent adsorption characteristics of the current adsorbents toward OPs were preserved in a wide pH window and high concentration of the background electrolytes. These prefigured the promising potentials of UiO-67 as novel adsorbent for the efficient removal of OPs from aqueous solution.