Rhamnolipids-based bio-supramolecular solvents as green and sustainable media for extraction of pyrethroid insecticides in water and food matrices.

A novel bio-supramolecular solvent (bio-SUPRAS) based on rhamnolipids (RLs) was designed for efficient extraction of pyrethroid insecticides in water and food matrices. Benefiting from RLs as amphiphiles equipped with the attractive properties of bio-degradable, low toxicity and high stability, bio-SUPRAS was spontaneously generated through salt induced coagulation. The bio-SUPRAS was characterized by cryo-scanning electron microscope and main factors influencing the extraction performance were investigated in detail. Under the optimized conditions, the method was found to have desirable limits of detection (5∼10 µg l-1), good precision (RSDs<16.9 %) and satisfactory recovery (75.2 %∼94.3 %). More importantly, the extraction mechanism was studied by density functional theory systematically. Following greenness assessment, the technique was successfully used for enrichment of pyrethroid pesticides in real samples before HPLC-UV analysis. Thus, the method showed the outstanding merits of eco-efficient, green, time-saving, and had favorable application prospect to remove trace analytes from intricate sample matrices.

Switchable deep eutectic solvent as green and efficient media for liquid-phase microextraction of phenoxyacetic acid herbicides in water and food matrices.

In this work, a switchable deep eutectic solvent (SDES) based on fatty acid and polyetheramine ion pair was prepared for liquid-phase microextraction (LPME) of phenoxyacetic acid herbicides in drinking water, beverage and honey matrices. The as-synthesized SDES equipped with an interesting characteristic of fast and reversible polarity switching, achieving homogeneous extraction and rapid bi-phase separation simultaneously. Several key parameters affecting the extraction performance were investigated comprehensively by Box-Behnken design. Under the optimal conditions, the method exhibited excellent linearity (15-4000 µg L-1), low detection limits (3-5 µg L-1), desirable precision (RSD < 8.1 %), and satisfactory recovery (72.6-98.7 %). More importantly, the introduction of SDES can simplify the pre-treatment procedure, shorten extraction time (4 min), and avoid the usage of traditional organic solvent during the whole extraction process. In addition, the switching mechanism of SDES was characterized by FT-IR and 1H NMR, and the forming mechanism of SDES was investigated using density-functional theory. The green of the method was estimated using the analytical ecological scale, the analytical green calculator, and the green analytical procedure index. The cytotoxicity of SDES was investigated and the result displayed that toxicity of the SDES was very low with the EC50 > 500 mg/L. Therefore, the proposed method was green and efficient and revealed considerable application prospects for the extraction of trace analytes from complex materials.

An effervescence-assisted switchable deep eutectic solvent based liquid-phase microextraction of triazole fungicides in drinking water and beverage.

A new effervescence-assisted switchable deep eutectic solvent-based liquid phase microextraction (EA-SDES-LPME) combined with HPLC-UV was developed for determination of common triazole fungicides in drinking water and beverages, including myclobutanil, flusilazole, hexaconazole and bitertanol. The alternative extraction solvent was prepared with hexafluoroisopropanol and dipropylamine with the merits of time-saving, easy to collect and cost-effectiveness. The SDES can be reversibly switched between hydrophilic and hydrophobic states by pH adjustment. The homogeneous extraction was achieved under the hydrophilic form of SDES, and the bi-phase separation was obtained easily by adjusting pH value to restore the original hydrophobicity. Moreover, the characterization of SDES was investigated by FTIR and 1H NMR. The main variables affecting extraction efficiency were optimized in detail. Under the optimal conditions, the proposed method shows desirable precision (RSDs less than 18.5%) and acceptable recovery (72.6-95.4%). The lower limits of detection and limits of quantitation were found to be in the range of 1-2 µg L-1 and 5-10 µg L-1, respectively. The formation mechanism of SDES and the extraction mechanism for target analytes were investigated by density functional theory. The proposed methodology was simplicity, sensitive, time-saving and successfully applied to determine triazole fungicides in drinking water and beverages, making it an alternative technique for the analysis of trace analytes with satisfactory sensitivity.

Comparison of Fourteen Reference Evapotranspiration Models With Lysimeter Measurements at a Site in the Humid Alpine Meadow, Northeastern Qinghai-Tibetan Plateau.

Evapotranspiration is a key component in the terrestrial water cycle, and accurate evapotranspiration estimates are critical for water irrigation management. Although many applicable evapotranspiration models have been developed, they are largely focused on low-altitude regions, with less attention given to alpine ecosystems. In this study, we evaluated the performance of fourteen reference evapotranspiration (ET0) models by comparison with large weight lysimeter measurements. Specifically, we used the Bowen ratio energy balance method (BREB), three combination models, seven radiation-based models, and three temperature-based models based on data from June 2017 to December 2018 in a humid alpine meadow in the northeastern Qinghai-Tibetan Plateau. The daily actual evapotranspiration (ETa) data were obtained using large weighing lysimeters located in an alpine Kobresia meadow. We found that the performance of the fourteen ET0 models, ranked on the basis of their root mean square error (RMSE), decreased in the following order: BREB > Priestley-Taylor (PT) > DeBruin-Keijman (DK) > 1963 Penman > FAO-24 Penman > FAO-56 Penman-Monteith > IRMAK1 > Makkink (1957) > Makkink (1967) > Makkink > IRMAK2 > Hargreaves (HAR) > Hargreaves1 (HAR1) > Hargreaves2 (HAR2). For the combination models, the FAO-24 Penman model yielded the highest correlation (0.77), followed by 1963 Penman (0.75) and FAO-56 PM (0.76). For radiation-based models, PT and DK obtained the highest correlation (0.80), followed by Makkink (1967) (0.69), Makkink (1957) (0.69), IRMAK1 (0.66), and IRMAK2 (0.62). For temperature-based models, the HAR model yielded the highest correlation (0.62), HAR1, and HAR2 obtained the same correlation (0.59). Overall, the BREB performed best, with RMSEs of 0.98, followed by combination models (ranging from 1.19 to 1.27 mm day-1 and averaging 1.22 mm day-1), radiation-based models (ranging from 1.02 to 1.42 mm day-1 and averaging 1.27 mm day-1), and temperature-based models (ranging from 1.47 to 1.48 mm day-1 and averaging 1.47 mm day-1). Furthermore, all models tended to underestimate the measured ETa during periods of high evaporative demand (i.e., growing season) and overestimated measured ETa during low evaporative demand (i.e., nongrowing season). Our results provide new insights into the accurate assessment of evapotranspiration in humid alpine meadows in the northeastern Qinghai-Tibetan Plateau.

Soil Moisture Variations in Response to Precipitation Across Different Vegetation Types on the Northeastern Qinghai-Tibet Plateau.

An understanding of soil moisture conditions is crucial for hydrological modeling and hydrological processes. However, few studies have compared the differences between the dynamics of soil moisture content and soil moisture response to precipitation infiltration under different types of vegetation on the Qinghai-Tibet Plateau (QTP). In this study, a soil moisture sensor was used for continuous volumetric soil moisture measurements during 2015 and 2016, with the aim of exploring variations in soil moisture and its response to precipitation infiltration across two vegetation types (alpine meadow and alpine shrub). Our results showed that temporal variations in soil moisture at the surface (0-20 cm) and middle soil layers (40-60 cm) were consistent with precipitation patterns for both vegetation types. However, there was a clear lag in the soil moisture response to precipitation for the deep soil layers (80-100 cm). Soil moisture content was found to be significantly positively related to precipitation and negatively related to air temperature. Aboveground biomass was significantly negatively associated with the surface soil moisture content (0-20 cm) during the growing season. Statistically significant differences were observed between the soil water content of the surface, middle, and deep soil layers for the two vegetation types (p < 0.05). Soil moisture (19.81%) in the surface soil layer was significantly lower than that in the deep soil layer (24.75%) for alpine shrubs, and the opposite trend was observed for alpine meadows. The maximum infiltration depth of alpine shrubs was greater than that of alpine meadows under extremely high-precipitation events, which indicates that alpine shrubs might be less susceptible to surface runoff under extreme precipitation events. Furthermore, low precipitation amounts did not affect precipitation infiltration for either vegetation type, whereas the infiltration depth increased with precipitation for both vegetation types. Our results suggest that a series of small precipitation events may not have the same effect on soil moisture as a single large precipitation event that produces the equivalent total rainfall.

Corrigendum: Comparison of 14 reference evapotranspiration with lysimeter measurements at a site in the humid alpine meadow, northeastern Qinghai-Tibetan Plateau.

[This corrects the article DOI: 10.3389/fpls.2022.854196.].