Neonicotinoid insecticides (NNIs) are extensively used insecticides worldwide, yet the data on NNIs residues in the Yangtze River, China is scarce. Occurrence and distribution of six NNIs and a ...metabolite (desmethyl-acetamiprid) in surface water were investigated in the central Yangtze River, China at 20 sites from March to July and September 2015. Acetamiprid (ACE), imidacloprid (IMI) and thiamethoxam (THM) were the most frequently detected NNIs and IMI had a highest median concentration of 4.37 ng/L, followed by ACE (2.50 ng/L), THM (1.10 ng/L), nitenpyram (NTP; 0.34 ng/L), clothianidin (CLO; 0.10 ng/L), and thiacloprid (THCP; 0.02 ng/L). Significantly higher concentrations and detection frequencies of NNIs were observed in the summer than in the spring, which may be explained by the heavier precipitation in summer. Spatial variation with higher levels among the lower sites than the upper sites may be related with the agriculture land use. NNI contamination presented a low risk to aquatic life according to the risk quotient method, while IMI had potential risk to aquatic life according to the threshold of IMI (8.3 ng/L) in freshwater recommended in Netherland. Using the relative potency factors method for chronic cumulative risk assessment for NNIs, potential exposure to NNIs through water ingestion are three orders of magnitude lower than the recommended relative chronic reference dose. Ongoing environmental monitoring of NNIs is needed due to the increase use of NNIs in China.
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•Six typical NNIs were found in the central Yangtze River, and ACE, IMI and THM were the highest.•DM-ACE was found in surface water for the first time.•Higher NNIs levels were found in the summer than in the spring, with the highest observed in June.•Spatial variations of neonicotinoid contamination were observed.•Potential risk of NNIs to aquatic ecosystem and human were assessed.
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•Lignin-based activated carbons were prepared by chemical activation with FeCl3.•The best-activated carbon described a high 1500 m2⋅g−1 specific surface area.•Maximum acetaminophen ...adsorption capacity at 655 mg·g−1.•Maximum acetamiprid adsorption capacity at 765 mg·g−1.•Both target compounds adsorbed in two layers on the activated carbon surface.
Lignin has been employed as a precursor to synthesize activated carbons with the aim of lignin-biomass revalorization. The properties of these activated carbons were compared, and the best adsorbent was employed to remove two emerging pollutants from water, acetaminophen and acetamiprid. The adsorption mechanisms of pharmaceutical and pesticide compounds were analyzed, modeled and interpreted via statistical physics models. In particular, adsorption kinetics and isotherms of acetaminophen and acetamiprid at temperatures between 20 and 60 °C were quantified experimentally. Equilibrium data were fitted to different statistical physics-based isotherm models to establish the corresponding adsorption mechanism. A double layer adsorption model with one type of functional group was the best to correlate and explain the removal of these organic molecules. Steric parameters for the adsorption of these organic compounds were also calculated thus determining that their adsorption was multi-molecular. At tested operating conditions, acetaminophen adsorption was endothermic, while acetamiprid removal was exothermic. Physical adsorption forces were expected to be responsible for the removal of both compounds. This study reports new insights on the adsorption mechanisms of relevant emerging pollutants commonly found in water worldwide.
Traditional DNA walkers face enormous challenges due to limited biostability and reaction kinetics. Herein, we designed a self-driven close-looped DNAzyme walker (cl-DW) with high structural ...biostability and catalytic activity that enabled rapid electrochemiluminescence (ECL) detection of pesticide residue acetamiprid. Specifically, cl-DW exhibited increasing ability to resist nuclease degradation with a 570-fold longer half-degradation time than that of the single-stranded DNAzyme walker (ss-DW) due to the protected DNA terminal. Furthermore, cl-DW achieved high catalytic activity with a 4.3-fold faster reaction kinetic than that of ss-DW due to the circularized nanostructure of an available catalytic domain. Consequently, we utilized cl-DW as a signal amplifier and tin-based sulfide (SnS2) nanoflowers as ECL emitters to construct an ECL aptasensor, which realized the sensitive detection of acetamiprid with a limit of detection of 0.85 nM. This work provides a reliable approach to exploring DNA walkers with high catalytic activity and better biostability for molecular monitoring.
•An electrochemiluminescence aptasensor was designed for acetamiprid detection.•Spatial folding effect enhanced catalytic activity of close-looped DNAzyme walker.•Close-looped DNAzyme walker had improved structural biostability.•This method had satisfactory results for practical application of small molecule.
Neonicotinoid insecticides specifically target insect subtypes of nicotinic acetylcholine receptors. Acetamiprid (ACE: C10H11ClN4), the neonicotinoid insecticide, is used to control crop insect pests ...worldwide. It is a nitrile, monochloropyridine, and carboxamidine that is highly soluble and accessible to waterways. There, it causes neurotoxic and oxidative perturbance to non-target organisms. The unionid mussel Chamabradia rubens is a common Northern River Nile suspension feeder. The current study aimed to assess ACE filtration from waters by C. rubens, and whether this biological power can reduce ACE effects on fish. Removal of ACE by C. rubens was assessed using LC-MS/MS. Zebrafish Danio rerio adults were exposed to different sublethal doses of ACE in the presence or absence of C. rubens in their aquaria. The results showed that mussels could remove significant ACE amounts from water, where it accumulated mostly in the digestive gland. The presence of C.rubens in zebrafish aquaria having ACE was accompanied by significant upregulation of antioxidant enzyme gene transcripts and total H2O2 scavenging, in contrast to mussel-free ACE-exposed groups. Meanwhile, liver triglycerides rose 5-6-fold in response to ACE in the “Fish-Only” groups, indicating an ACE-induced hepatotoxicity. Also, Insulin-like growth factor 1 (igf1) and fish body mass increased more in “Fish + Mussel” groups than in the “Fish-Only” ones. In aggregate, these findings suggest that the Nile mussel could reduce the oxidative stress and metabolic changes induced in fish by ACE. This can contribute valuable environmental and economic benefits upon the use of this mussel as a biofilter.
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•The neonicotinoid insecticide acetamiprid induces oxidative stress in zebrafish.•Nile clam Chambardia rubens removes significant amounts of acetamiprid in waters.•C. rubens in zebrafish aquaria alleviated acetamiprid-induced toxicity.•C. rubens was proven as a successful biofilter against acetamiprid adverse impacts.
Metal-organic framework play an important role in developing novel detection techniques. Herein, an ultrathin two-dimensional (2D) metal-organic framework nanosheet (Cu-TCPP) assembled microflower ...was successfully synthesized and applied for ultrasensitive detection. The high detection performance of Cu-TCPP microflower was attributed to high-capacity aptamer adsorption and specific desorption resulting from numerous approachable active sites, and its ultrathin nanosheets microflower-like structure. Moreover, the Cu-TCPP microflower had overcame the disadvantages of 2D MOF nanosheets which tended to agglomerate. Moreover, it exhibited excellent fluorescence quenching performance as a donor for fluorescence resonance energy transfer. Acetamiprid, a new chloronicotinic neurotoxic insecticide was used as the model analyte. The ultrasensitive sensor was developed by combining the Cu-TCPP microflower with deoxyribonuclease Ⅰ signal enhanced fluorescence. When acetamiprid was present, the fluorescent labeled aptamer probe was selectively bound to acetamiprid and desorbed from the Cu-TCPP microflower, resulting in fluorescence recovery. Subsequently, DNase Ⅰ was used to cleave the DNA strands of the aptamer probe, and acetamiprid was released to participate in a new cycle. The detection limit of the assay was as low as 5.56 pg/mL with a linear range 50.00 pg/mL∼5.00 μg/mL, and it was a universal platform to detect other analytes.
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•The Cu-TCPP microflower was synthetized with superior active sites and FRET performance.•The Cu-TCPP microflower and DNase I assisted amplification was combined for ultrasensitive aptasensor.•The aptasensor for sensitive and selective detection of acetamiprid with LOD 5.56 pg/mL and linear range 50 ∼ 5,000,000 pg/mL.
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•A cauliflower-like super-hydrophobic SERS substrate by two-step laser processing.•The enhancement factor of the SERS substrate reaches 5.9 × 109 for R6G.•The detection limit of the ...SERS substrates for acetamiprid is as low as 10-5 g/L.
Residues of organic pesticides continue to accumulate in the human body through the food chain, posing a serious threat to health. Therefore, the efficient and sensitive detection of pesticide residues is crucial. Surface-enhanced Raman scattering (SERS), as a powerful spectroscopic technique, holds great potential for the trace detection of pesticides. In this study, a cauliflower-like SERS substrate fabricated via a two-step laser processing is proposed for highly sensitive detection of acetamiprid. The cauliflower-like structure features a large surface area, providing numerous hotspots and abundant adsorption sites for the target molecules. Furthermore, the rich micro/nano structures on the surface confer super-hydrophobicity properties to the substrate, effectively enriching the analyte and greatly enhancing the SERS performance. As a result, the cauliflower-like super-hydrophobic substrate demonstrates a detection limit as 10-15 M for the typical dye analyte (R6G), with an enhancement factor of 2.6 × 108. Additionally, the substrate exhibits excellent signal reproducibility with a relative standard deviation of 8.33 %. In practical pesticide detection, the detection limit for acetamiprid on orange is 10-4 g/L, significantly surpassing the national standard. In conclusion, the cauliflower-like super-hydrophobic substrate enhances the sensitivity, uniformity, reproducibility, and reliability of SERS signals in detection process, showing tremendous potential in the field of food safety.
Effective monitoring of pesticide residues in food and environmental samples is of high importance as these chemical residues undergo ongoing eco- and bio-accumulation, compromising the health of ...humans and animals alike. Several sensor platforms are being developed for the detection of pesticide residues in a range of sample matrices. A relatively new sensor platform that has gained enormous attention is based on the natural enzyme-mimicking catalytic activity of nanomaterials, more commonly referred to as nanozyme activity. In this review, we provide a critical overview of the recent advances in nanozyme-based sensing strategies for the detection of pesticides. The review highlights the salient features and the working principle of various nanozyme-based sensors, their integration with molecular recognition elements (MREs) to improve target specificity, and associated limitations that must be overcome to turn nanozyme sensors into mainstream analytical tools. The review further provides a critical outlook of nanozyme-based sensors for pesticide detection. The last section of the review outlines the steps that must be taken to realise the full potential of nanozyme-based sensors.
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•This review provides a critical overview of nanozyme sensors for the detection of pesticides.•The review highlights the breath of sensors developed using nanozymes.•Opportunities and challenges for future growth is summarized.
In an effort to achieve high sensitive and selective detection of pesticide residues, numerous nanomaterial-based aptasensors are currently being developed for acetamiprid analysis. Recently, ...aptamers as a potent alternative of antibodies are used in biosensing platforms. There is tremendous interest in utilizing of nanomaterial as basic building blocks and signaling elements in aptasensors. The nanomaterials have the unique optical and electrical properties. The combination of nanomaterial and aptamer technology has opened a new window in pesticide residues monitoring. In this review, recent advances and applications of optical and electrochemical nanomaterial-based aptasensors for the detection and quantitative determination of acetamiprid in details have been discussed.
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•Acetamiprid is an insecticide that can generate potential health risk of humans.•Aptamers have attracted as a novel sensing elements.•Nanomaterials have become one of the most interesting sensing materials.•Recent development in the nano-aptasensing of acetamiprid was reviewed.
Toxicology studies suggest that neonicotinoids may be associated with adiposity development via thyroid hormone disruption and increased oxidative stress. Prior epidemiological studies report mixed ...results for the association between neonicotinoids and adiposity measures.
To examine the association between detectable concentrations of parent neonicotinoids (imidacloprid, acetamiprid, clothianidin) and neonicotinoid metabolites (5-hydroxy-imidacloprid, N-desmethyl-acetamiprid) with adiposity measures among US adults, and whether sex modifies the associations for neonicotinoid metabolites with adiposity.
National Health and Nutrition Examination Survey (NHANES) 2015–2016 data was utilized to estimate covariate-adjusted associations between detectable neonicotinoids and fat mass index (FMI), lean mass index (LMI), waist circumference, body fat percentage, and body mass index (BMI) using multiple linear regression. We estimated incidence rate ratios (IRRs) for overweight or obese status with detectable neonicotinoid concentrations using Poisson's modified regression. Sampling strategies were accounted for in the regression models.
Detectable levels of acetamiprid were associated with a decrease in FMI (β = −3.17 kg/m2, 95% CI -4.79, −1.54), LMI (β = −3.17 kg/m2, 95% CI -5.17, −1.17), body fat percentage (β = −4.41, 95% CI -8.20, −0.62), waist circumference (β = −9.80 cm, 95% CI -19.08, −0.51), and BMI (β = −3.88kg/m2, 95% CI -7.25, −0.51) among adults. In contrast, detectable levels of 5-hydroxy-imidacloprid were associated with greater rates of being overweight/obese (IRR = 1.11, 95% CI 1.04, 1.18)) and increased LMI (β = 0.67 kg/m2, 95% CI 0.04, 1.29). Sex modified the association between N-desmethyl-acetamiprid and LMI (pint = 0.075) with a positive association among males (β = 1.14 kg/m2, 95% CI 0.38, 1.90), and an insignificant inverse association in females. Sex also modified the association for N-desmethyl-acetamiprid with FMI (pint = 0.095) and body fat percentage (pint = 0.072), with suggestive evidence showing positive associations for males and inverse associations for females.
Detectable concentrations of acetamiprid were inversely associated with adiposity, while there were mixed findings for 5-hydroxy-imidacloprid. Findings suggest sex differences, though results are not clear with regard to the directionality of the association by sex.
•Neonicotinoid compounds may be associated with the pathogenesis of adiposity.•Acetamiprid was inversely associated with all the adiposity measures examined.•5-hydroxy-imidacloprid was positively associated with being overweight/obese.•Sex differences were seen with N-desmethyl-acetamiprid and some adiposity measures.
Neonicotinoid insecticides (NNIs) are a relatively new class of insecticides, and carbendazim (CBDZ) is a representative antifungal biocide. The occurrence of them in indoor dust was not documented ...in China. In this study, 336 indoor dust samples were collected from 3 cities, including Taiyuan (October 2016), Wuhan (October 2016 and 2018), and Shenzhen (February 2019), located in North, Central, and South China, for determination of the residues of six NNIs, two of their metabolites, and CBDZ. Acetamiprid (ACE), imidacloprid (IMI), and CBDZ were found to be the major target analytes in dust samples from all selected cities with detection frequencies of 98.8%, 99.7%, and 95.2%, respectively. At least one target NNI was detected for all of the dust samples, with the median concentration of 25.8 ng/g for the imidacloprid-equivalent total neonicotinoids (IMIeq: generated by the relative potency factor method), and the median for CBDZ was 35.8 ng/g. Higher levels of several NNIs and CBDZ were found in urban areas of Taiyuan and Wuhan than those in rural areas. A significant increase of the NNI residues was observed in dust of Wuhan from 2016 to 2018 (while not significant for CBDZ). Finally, the estimated daily intake (EDI) of IMIeq and CBDZ for infants and toddlers were higher than that found in other age groups through dust ingestion, which indicated that infants and toddlers may be susceptible to current residue of NNIs and CBDZ in indoor dust, and dust ingestion of NNIs might be <1% of that reported for dietary intakes in China. This is the first study to report the residue levels of NNIs and CBDZ in dust samples from indoor environment in China.
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•IMI and ACE were the most frequently detected target NNIs.•DNT, THCP, DM-ACE and 5-OH-IMI were firstly reported in indoor dust.•An increasing trend of NNIs was observed in Wuhan from 2016 to 2018.•The highest concentrations of IMIeq and CBDZ were found in Wuhan in 2018 and Shenzhen, respectively.•This is the first study about NNIs and CBDZ in indoor dust from China.
