Application of phosphorus amendments reduces metal uptake and increases yield of Oryza saliva L. (rice) in Cd/Cu-contaminated paddy field.

To alleviate worldwide food safety issues caused by metal contamination, an easily available material is urgently needed for extensive application. In this study, calcium magnesium phosphate fertiliser (Pcm) was applied to a Cd/Cu co-contaminated paddy field in comparison with limestone and organic fertiliser. The results showed that only Pcm is effective in simultaneously reducing Cd uptake by 56.7% and Cu uptake by 36.2% in Oryza saliva L. (rice). The rice yield, reduced mainly by Cu, also increased by 30.1% with respect to the enhancement of soil pH, cation exchange capacity and availability of phosphorus, as well as the reduction in availabilities of Cd and Cu. Additionally, Pcm dramatically shaped the bacterial community structure, with Proteobacteria and Firmicutes predominant in the soils. The beneficial genera Exiguobacterium, Citrobacter, and Acinetobacter, which are vital for phosphate dissolution and Cd/Cu immobilisation, were also enriched. The results demonstrated that the application of Pcm at 0.4% (w:w) was able to enhance both crop quantity and quality in Cd/Cu co-contaminated paddy fields by reducing Cu/Cd availability, promoting rice yield, and reshaping bacterial community structures.

Effect of humic acid on bioreduction of facet-dependent hematite by Shewanella putrefaciens CN-32.

Interfacial reactions between iron (Fe) (hydr)oxide surfaces and the activity of bacteria during dissimilatory Fe reduction affect extracellular electron transfer. The presence of organic matter (OM) and exposed facets of Fe (hydr)oxides influence this process. However, the underlying interfacial mechanism of facet-dependent hematite and its toxicity toward microbes during bioreduction in the presence of OM remains unknown. Herein, humic acid (HA), as typical OM, was selected to investigate its effect on the bioreduction of hematite {100} and {001}. When HA concentration was increased from 0 to 500 mg L-1, the bioreduction rates increased from 0.02 h-1 to 0.04 h-1 for hematite {100} and from 0.026 h-1 to 0.05 h-1 for hematite {001}. Since hematite {001} owned lower resistance than hematite {100} irrespective of the HA concentration, and hematite {100} was less favorable for reduction. Microscopy-based analysis showed that more hematite {001} nanoparticles adhered to the cell surface and were bound more closely to the bacteria. Moreover, less cell damage was observed in the HA-hematite {001} treatments. As the reaction progressed, some bacterial cells died or were inactivated; confocal laser scanning microscopy showed that bacterial survival was higher in the HA-hematite {001} treatments than in the HA-hematite {100} treatments after bioreduction. Spectroscopic analysis revealed that facet-dependent binding was primarily realized by surface complexation of carboxyl functional groups with structural Fe atoms, and that the binding order of HA functional groups and hematite was affected by the exposed facets. The exposed facets of hematite could influence the electrochemical properties and activity of bacteria, as well as the binding of bacteria and Fe oxides in the presence of OM, thereby governing the extracellular electron transfer and concomitant bioreduction of Fe (hydr)oxides. These results provide new insights into the interfacial reactions between OM and facet-dependent Fe oxides in anoxic, OM-rich soil and sediment environments.

Synthesis and characterization of polymerizable MOFs for the preparation of MOF/polymer mixed matrix membranes.

Mixed-matrix membranes (MMMs) comprising polymer matrices and metal-organic frameworks (MOFs) provide efficient and economic CO2 separation. One major challenge is to construct continuous and defect-free MMMs due to poor MOF/polymer compatibility. Here, this protocol describes the step-by-step details for synthesis of desired linkers that allow the fabrication of new polymerizable MOFs containing vinyl groups (BUCT MOFs) and the preparation procedures of defect-free MMMs with enhanced MOF/polymer interfacial adhesion and boosted gas separation performances. For complete details on the use and execution of this profile, please refer to Chen et al. (2021).

Molecularly imprinted monoliths: Recent advances in the selective recognition of biomacromolecules related biomarkers.

Biomarkers are significant indicators to assist the early diagnosis of diseases and assess the therapeutic response. However, due to the low abundance of biomarkers in complex biological fluids, it is highly desirable to explore efficient techniques to attain their selective recognition and capture before the detection. Molecularly imprinted monoliths integrate the high selectivity of imprinted polymers and the rapid convective mass transport of monoliths, and as a result, are promising candidates to achieve the specific enrichment of biomarkers from complex samples. This review summarizes the various imprinting approaches for the preparation of molecularly imprinted monoliths. The state-of-art advances as an effective platform for applications in the selective capture of biomacromolecules related biomarkers were also outlined.

Field study on the soil bacterial associations to combined contamination with heavy metals and organic contaminants.

The understanding of soil microbial associations to combined contamination would substantially benefit the restoration of damaged ecosystems, which is currently limited at the field scale. In this study, we investigated the soil bacterial associations to combined contamination with metals (Cd, Cu, Hg, Pb, and Zn), polyaromatic hydrocarbons (PAHs), and polybrominated diphenyl ethers (PBDEs). Samples were collected from field sites under five land-use patterns with electronic waste recycling. Results showed that the contents of Cd (0.22-12.86 mg/kg), Cu (17-14,136 mg/kg), Pb (4.6-77,014 mg/kg), Hg (0.28-22 mg/kg), Zn (26-42,495 mg/kg), PAHs (4.6-1753 µg/kg), and PBDEs (1.9-1079 µg/kg) varied significantly across sites. We observed positive correlations between catalase activity and heavy metals, indicative of a resistance response to the oxidative stress induced by metals. Furthermore, the bacterial community diversity was found to be determined primarily by PBDEs, whereas acenaphthylene, available phosphorus, and 2,2',3,3',4,5,6-heptabrominated diphenyl ether (BDE-183) were the three major drivers affecting community composition. The co-occurrence network constructed for bacterial communities exposed to combined contamination was non-random with scale-free, small-world and modularity features. We further proposed functional roles of the modules including stress resistance, hydrocarbon degradation, and nutrient cycling. Overall, the findings of redundancy analysis, variation partition analysis and the co-occurrence network indicated that soil bacterial community under combined contamination cooperated to survive. Members including Rhodoplanes and Nitrospira were capable of degrading PAHs and PBDEs in various pathways, while others, including Acinetobacter, Citrobacter, and Pseudomonas, reduced the metal toxicity to the community. Our findings provide new insights into the responses of soil bacteria, particularly in terms of inter-specific relationships, under combined contamination at the field scale.

Enantioselective Analysis and Degradation Studies of Four Stereoisomers of Difenoconazole in Citrus by Chiral Liquid Chromatography-Tandem Mass Spectrometry.

Four difenoconazole stereoisomers were well separated on a Superchiral S-OX column. The absolute configurations of the four stereoisomers of difenoconazole eluted in an orderly fashion with the chiral column were confirmed as (2S,4S), (2S,4R), (2R,4R), and (2R,4S)-difenoconazole, respectively, by single-crystal X-ray diffraction. For the first time, a simple and efficient trace detection method for the determination of residues of the four stereoisomers of difenoconazole in a plant sample by HPLC-MS/MS was developed. The mean recoveries were 78.23-104.38% with RSDs of 0.33-9.95%. The limits of detection for the four difenoconazole enantiomers were 0.0002-0.0004 mg/kg, and the limits of quantitation were 0.0044-0.011 mg/kg in citrus leaves and whole fruits. There was no obvious enantioselectivity upon degradation of the four stereoisomers in citrus leaves and whole fruits in Hunan and Guizhou. In Guangzhou, the rate of degradation of (2R,4R)-difenoconazole was the slowest among the four stereoisomers of difenoconazole.

Bagging and non-bagging treatment on the dissipation and residue of four mixed application pesticides on banana fruit.

BACKGROUND: Bananas are vulnerable to disease and insect pests after producing fruit. In order to increase the yield and produce high-quality fruit, the insecticides and fungicides are mixed and applied 2-3 times on banana, then the fruit is bagged. Buprofezin, imidacloprid, difenoconazole, and pyraclostrobin are widely used on banana. However, there is a lack of research on the effect of fruit bagging on pesticide dissipation and residues on bananas. RESULTS: A versatile liquid chromatography-tandem mass spectrometry method with modified QuEChERS sample preparation has been developed for the determination of buprofezin, imidacloprid, difenoconazole, and pyraclostrobin in bananas. The recovery of four pesticides was satisfactory (74.96-98.63%) with reasonable relative standard deviation (≤ 8.78%). In Hainan and Guangzhou, the half-lives of the four pesticides were 4.68-13.9 and 5.63-20.4 days in non-bagged and bagged bananas, respectively. The significance analysis of the half-lives in the two sites showed that the dissipation rates of the three pesticides (imidacloprid, difenoconazole, pyraclostrobin) on whole bananas were significantly decreased by the effect of bagging (P < 0.05). However, there was no significant difference in the degradation of half-life of buprofezin under bagging and without bagging (P > 0.05). CONCLUSION: The high vapor pressure and the non-systemic property cause buprofezin to evaporate and dissipate the fastest among the four studied pesticides. The ultimate residues of four pesticides in bananas are lower than the maximum residue limits in China after three times of mixed applications under bagging or non-bagging. The results provide scientific data for evaluating the safety of four pesticides in banana bagging. © 2020 Society of Chemical Industry.

Cadmium threshold for acidic and multi-metal contaminated soil according to Oryza sativa L. Cadmium accumulation: Influential factors and prediction model.

Cadmium (Cd) contamination in soil-rice systems has become a global public concern. However, influencing factors and the contamination threshold of Cd in soils remain largely unknown owing to soil heterogeneity, which limits our ability to assess the risk to human health and to draft appropriate environmental policies. In this study, we selected the soil-rice system of Longtang and Shijiao town in southern China, which was characterized by multi-metal acidic soil contamination due to improper electronic waste recycling activities, as a case to analyze the influence of different soil properties on the Cd threshold in the soil and Cd accumulation in rice. The results showed that soil organic matter (SOM) was the main factor regulating Cd accumulation in the soil-rice system. Moreover, compared with the total Cd concentration, the DTPA-extractable Cd concentration in the soil was a better predictor of Cd transportation in the soil-rice system. According to the prediction model, when SOM was < 35 g kg-1, the CdDTPA threshold was 0.16 mg kg-1 with a 95% likelihood of Cdrice accumulation above the Chinese food standard limit (0.2 mg kg-1). Conversely, when SOM was ≥ 35 g kg-1, the CdDTPA threshold was only 0.03 mg kg-1. This study of the influence of SOM on Cd accumulation in a soil-rice system confirms that SOM is a crucial parameter for better and safer rice production, especially in multi-metal contaminated acidic soils.

Alkaline amendments improve the health of soils degraded by metal contamination and acidification: Crop performance and soil bacterial community responses.

Soil degradation due to heavy metal contamination and acidification has negative effects on soil health and crop growth. Many previous studies have tried to improve the growth of crops and decrease their metal uptake. The recovery of soil health, however, has rarely been focused in soil remediation. In this study, a pot trial was conducted with lettuce (Lactuca sativa L.) growing in heavy metal contaminated and acidic soils, to examine the effects of alkaline amendments (limestone, LS; calcium magnesium phosphate fertilizer, Pcm) and organic amendments (cow manure compost, CMC; biochar, BC) on the growth of lettuce and on the availability of heavy metals, enzyme activities, and bacterial community structures in the soils. The results showed that, in comparison with the CMC and BC treatments, LS and Pcm were more effective at improving lettuce growth and reducing metal concentrations in shoots. Urease and catalase activities in LS and Pcm amended soils were consistently higher than in those with CMC and BC. Additionally, the alkaline amendments dramatically improved the bacterial diversity and shaped more favorable bacterial community structures. Proteobacteria and Gemmatimonadetes were predominant in soils amended with alkaline treatments. The beneficial bacterial genera Gemmatimonas and f_Gemmatimonadaceae, which are vital for phosphate dissolution, microbial nitrogen metabolism, and soil respiration, were also enriched. The results suggest that alkaline amendments were superior to organic amendments, and thus may be useful for the future recovery of soil functions and health under heavy metal contamination and low pH.

Distributions of chlorinated paraffins and the effects on soil microbial community structure in a production plant brownfield site.

The distributions of chlorinated paraffins (CPs) in soils and their ecological effects attract much attention, while site-scale data are still scarce. In this study, a comprehensive investigation was performed to understand the CP distributions at a CP production plant brownfield site, as well as their effects on soil microbial community. Short-, medium- and long-chain CPs (SCCPs, MCCPs, LCCPs) were detected in most samples with total contents ranging ND-5,090, ND-6,670, and ND-1450 ng g-1 (dw), respectively. A CP-hotspot was observed 10 m beneath the synthesis workshop, indicating the downward migration of CPs. The consistence of soil SCCP congener profiles with commercial product CP-52 suggested the leakage of CP products as the contamination source. Besides CPs, petroleum hydrocarbons (PHC) contamination also occurred beneath the synthesis workshop. Soil microbial community composition and diversity were significantly influenced by SCCPs (p < 0.05) despite their lower contents compared to other concerned contaminants. Microbial network analysis indicated nonrandom co-occurrence patterns, with Acinetobacter, Brevibacterium, Corynebacterium, Microbacterium, Stenotrophomonas, and Variibacter as the keystone genera. Genera from the same module showed significant ecological links (p < 0.05) and were involved in the degradation of PHCs and chlorinated organic contaminants. This study provides the first phylogenetic look at the microbial communities in CP contaminated soils, indicating that the long-term exposure to CPs and PHCs may lead to microbial group assemblages with the potential for degradation.

Determination of nitenpyram dissipation and residue in kiwifruit by LC-MS/MS.

To investigate the presence of nitenpyram in kiwifruit, a field experiment was conducted in six kiwifruit producing regions in China. A modified quick, easy, cheap, effective, rugged and safe method (QuEChERS) method based on liquid chromatography-tandem mass spectrometry (LC-MS/MS) was developed for the determination of nitenpyram in kiwifruit. Quantitative detection was performed by LC-MS/MS in multiple reaction monitoring (MRM) mode under positive-ion electrospray ionisation. The proposed method is linear and accurate in the range of 0.005 to 4.5 µg/mL. The recovery of nitenpyram was satisfactory (71.96-96.67%) with reasonable RSDs (9.83 %) for 0.01-4.5 mg/kg spiked levels. The limit of quantification (LOQ) was 0.01 mg/kg for nitenpyram. Nitenpyram degraded rapidly in kiwifruit with a half-life <4 days. Residues of nitenpyram were <0.01 - 0.54 mg/kg in kiwifruit 7, 14 and 21 days after spraying at six sites.

Effects of mineral oil spray additives on the distribution and dissipation kinetics of pyraclostrobin and azoxystrobin in banana leaves, fruits, and soil.

Using LC-MS/MS, a rapid and sensitive method for the simultaneous determination of pyraclostrobin and azoxystrobin residues in banana matrices (leaf and whole banana) and soil was established. The samples were extracted using acetonitrile and purified through C18 dispersive solid-phase extraction. The average recovery of the analytes in various matrices was in the range of 77.3%-103.9% with an RSD range of 0.9%-9.5%. The initial deposition amounts of pyraclostrobin and azoxystrobin at 2 h in the banana leaves of the mineral oil group were 1.43 and 1.31 times in Guangxi, and 2.10 and 1.81 times in Hainan for the water group, whereas those in the soil of the water group were 3.45 and 3.03 times in Guangxi, and 2.14 and 3.48 times in Hainan for the mineral oil group. The half-lives in the leaves and soil of the mineral oil group were not remarkably different from those of the water group. The terminal residue of the analytes on the whole banana was <0.02 mg/kg at 14 days after application from the two sites. The results of this work may indicate and promote the safety of using pyraclostrobin and azoxystrobin in banana production, especially with mineral oil spray adjuvants.