Protocol for detecting micro(nano)plastics released from intravenous infusion products.

Approaches for detecting micro(nano)plastics (MNPs) released from intravenous infusion products (IVIPs) are vital for evaluating the safety of both IVIPs and their derived MNPs on human health, yet current understanding is limited. Here, we present a protocol for detecting polyvinyl chloride (PVC) MNPs by combining Raman spectroscopy, scanning electron microscopy equipped with energy-dispersive X-ray spectroscopy (SEM-EDS), and pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS). We describe steps for collecting, pretreating, and measuring PVC MNPs released from IVIPs. For complete details on the use and execution of this protocol, please refer to Li et al.1.

Advances in ultrasonic treatment of oily sludge: mechanisms, industrial applications, and integration with combined treatment technologies.

In the petroleum sector, the generation of oily sludge is an unavoidable byproduct, necessitating the development of efficient treatment strategies for both economic gain and the mitigation of negative environmental impacts. The intricate composition of oily sludge poses a formidable challenge, as existing treatment methodologies frequently fall short of achieving baseline disposal criteria. The processes of demulsification and dehydration are integral to diminishing the oil content and reclaiming valuable crude oil, thereby playing a critical role in the management of oily sludge. Among the myriad of treatment solutions, ultrasonic technology has emerged as a particularly effective physical method, celebrated for its diverse applications and lack of resultant secondary pollution. This comprehensive review delves into the underlying mechanisms and recent progress in the ultrasonic treatment of oily sludge, with a specific focus on its industrial implementations within China. Both isolated ultrasonic treatment and its combination with other technological approaches have proven successful in addressing oily sludge challenges. The adoption of industrial-scale systems that amalgamate ultrasound with multi-technological processes has shown marked enhancements in treatment efficacy. The fusion of ultrasonic technology with other cutting-edge methods holds considerable potential across a spectrum of applications. To fulfill the goals of resource recovery, reduction, and neutralization in oily sludge management, the industrial adoption and adept application of a variety of treatment technologies are imperative.

Deciphering Vanadium Speciation in Smelting Ash and Adaptive Responses of Soil Microorganisms.

Abundant smelting ash is discharged during pyrometallurgical vanadium (V) production. However, its associated V speciation and resultant ecological impact have remained elusive. In this study, V speciation in smelting ash and its influence on the metabolism of soil microorganisms were investigated. Smelting ashes from V smelters contained abundant V (19.6-115.9 mg/g). V(V) was the dominant species for soluble V, while solid V primarily existed in bioavailable forms. Previously unrevealed V nanoparticles (V-NPs) were prevalently detected, with a peak concentration of 1.3 × 1013 particles/g, a minimal size of 136.0 ± 0.6 nm, and primary constituents comprising FeVO4, VO2, and V2O5. Incubation experiments implied that smelting ash reshaped the soil microbial community. Metagenomic binning, gene transcription, and component quantification revealed that Microbacterium sp. and Tabrizicola sp. secreted extracellular polymeric substances through epsB and yhxB gene regulation for V-NPs aggregation to alleviate toxicity under aerobic operations. The V K-edge X-ray absorption near-edge structure (XANES) spectra suggested that VO2 NPs were oxidized to V2O5 NPs. In the anaerobic case, Comamonas sp. and Achromobacter sp. reduced V(V) to V(IV) for detoxification regulated by the napA gene. This study provides a deep understanding of the V speciation in smelting ash and microbial responses, inspiring promising bioremediation strategies to reduce its negative environmental impacts.

Nanoparticulate pollutants in the environment: Analytical methods, formation, and transformation.

The wide application of nanomaterials and plastic products generates a substantial number of nanoparticulate pollutants in the environment. Nanoparticulate pollutants are quite different from their bulk counterparts because of their unique physicochemical properties, which may pose a threat to environmental organisms and human beings. To accurately predict the environmental risks of nanoparticulate pollutants, great efforts have been devoted to developing reliable methods to define their occurrence and track their fate and transformation in the environment. Herein, we summarized representative studies on the preconcentration, separation, formation, and transformation of nanoparticulate pollutants in environmental samples. Finally, some perspectives on future research directions are proposed.

Direct entry of micro(nano)plastics into human blood circulatory system by intravenous infusion.

Understanding the pathways of human exposure to micro(nano)plastics (MNPs) is crucial for assessing their health impacts. Intravenous infusion can induce MNPs direct entry into the human blood, posing serious risks on human health, but remains unclear. Herein, we developed comprehensive analytical methods to detect polyvinyl chloride (PVC) MNPs down to 20 nm, and found about 0.52 µg equal to 105-1011 particles of PVC-MNPs released from intravenous infusion products (IVIPs) during each intravenous infusion of 250 mL injection. The released amounts of MNPs from IVIPs were dependent on the plastic materials, and the injection volume and composition. These findings indicated that the released MNPs should be directly introduced into the human blood circulatory system, causing serious impacts on human health. Our study reveals a previously ignored but important pathway of human exposure to MNPs, and calls for further research on the potential risks of these MNPs on human health.

Quantitation of Atmospheric Suspended Polystyrene Nanoplastics by Active Sampling Prior to Pyrolysis-Gas Chromatography-Mass Spectrometry.

Plastic has been demonstrated to release nanoplastics (NPs) into the atmosphere under sunlight irradiation, posing a continuous health risk to the respiratory system. However, due to lack of reliable quantification methods, the occurrence and distribution of NPs in the atmosphere remain unclear. Polystyrene (PS) micro- and nanoplastics (MNPs) represent a crucial component of atmospheric MNPs. In this study, we proposed a simple and robust method for determining the concentration of atmospheric PS NPs using pyrolysis-gas chromatography-mass spectrometry (Py-GC/MS). Following active sampling, the filter membrane is directly ground and introduced into the Py-GC/MS system to quantify PS NPs. The proposed method demonstrates excellent reproducibility and high sensitivity, with a detection limit as low as down to 15 pg/m3 for PS NPs. By using this method, the occurrence of PS NPs in both indoor and outdoor atmospheres has been confirmed. Furthermore, the results showed that the abundance of outdoor PS NPs was significantly higher than that of indoor samples, and there was no significant difference in NP vertical distribution within a height of 28.6 m. This method can be applied for the routine monitoring of atmospheric PS NPs and for evaluating their risk to human health.

Extraction of Common Small Microplastics and Nanoplastics Embedded in Environmental Solid Matrices by Tetramethylammonium Hydroxide Digestion and Dichloromethane Dissolution for Py-GC-MS Determination.

Determination of microplastics and nanoplastics (MNPs), especially small MPs and NPs (<150 µm), in solid environmental matrices is a challenging task due to the formation of stable aggregates between MNPs and natural colloids. Herein, a novel method for extracting small MPs and NPs embedded in soils/sediments/sludges has been developed by combining tetramethylammonium hydroxide (TMAH) digestion with dichloromethane (DCM) dissolution. The solid samples were digested with TMAH, and the collected precipitate was washed with anhydrous ethanol to eliminate the natural organic matter. Then, the MNPs in precipitate were extracted by dissolving in DCM under ultrasonic conditions. Under the optimized digestion and extraction conditions, the factors including sizes and concentrations of MNPs showed insignificant effects on the extraction process. The feasibility of this sample preparation method was verified by the satisfactory spiked recoveries (79.6-91.4%) of polystyrene, polyethylene, polypropylene, poly(methyl methacrylate), polyvinyl chloride, and polyethylene terephthalate MNPs in soil/sediment/sludge samples. The proposed sample preparation method was coupled with pyrolysis gas chromatography-mass spectrometry to determine trace small MPs and NPs with a relatively low detection limit of 2.3-29.2 µg/g. Notably, commonly used MNPs were successfully detected at levels of 4.6-51.4 µg/g in 6 soil/sediment/sludge samples. This proposed method is promising for evaluating small solid-embedded MNP pollution.

Spatial distribution of polystyrene nanoplastics and small microplastics in the Bohai Sea, China.

Micro- and nano-plastic (MNP) pollution has attracted public concerns. Currently, most environmental researches focus on large microplastics (MPs), while small MNPs that have great impacts on marine ecosystems are rarely reported. Understanding the pollution levels and distribution patterns of small MNPs could help assess their potential impacts on the ecosystem. Polystyrene (PS) MNPs were often used as models to assess their toxicity, hence, we collected 21 sites in a Chinese sea area (the Bohai Sea) to analyze their pollution level and horizontal distribution in surface water samples, and vertical distributions in five sites with the water depth >25 m. Samples were filtered by glass membranes (1 µm) to trap MPs, which were frozen, ground, dried, and detected by pyrolysis-gas chromatography-mass spectrometry (pyGC-MS); while the nanoplastics (NPs) in the filtrate were captured with alkylated ferroferric oxide (Fe3O4) to form aggregates, which were separated by glass membrane (300 nm) filtration for pyGC-MS determination. Small PS MPs (1-100 µm) and NPs (<1 µm) were detected in 18 samples with the mass concentrations ranging from <0.015 to 0.41 µg/L, indicating that PS MNPs are widely present in Bohai Sea. Our study contributes to understanding the pollution levels and distribution patterns of MNPs (<100 µm) in the marine system and provides valuable data for their further risk assessment.

Coating zirconium oxide-nanocomposite with humic acid for recovery of mercury and chromium in hazardous waste of chemical oxygen demand test.

Hazardous waste of chemical oxygen demand (COD) test (HWCOD) is one of the most common laboratory wastewaters, containing large amounts of H2SO4 and highly toxic Cr3+ and Hg2+. Current treatment methods suffered from incomplete removal of Cr3+ and high-cost. Herein, a humic acid-coated zirconium oxide-resin nanocomposite (HA-HZO-201) was fabricated for efficient recovery of Cr3+ and Hg2+ in HWCOD. The synthesized HA-HZO-201 shows excellent tolerance to wide pH range (1-5) and high salinity (3.5 mol/L NaCl), as well as adsorption capacity for Cr3+ (37.5 mg/g) and Hg2+ (121.3 mg/g). After treating with HA-HZO-201 by using a fixed-bed adsorption procedure, the final Cr3+ and Hg2+ concentrations in HWCOD decreased to 0.28 and 0.02 mg/L, respectively. In addition, the HA-HZO-201 can be regenerated by desorption and recovery of Cr3+ and Hg2+ using HNO3 and thiourea as eluents, respectively. After 5 cycles of adsorption/desorption, the removal efficiencies still reach up to 86.0% for Cr3+ and 89.7% for Hg2+, indicating an excellent regeneration of HA-HZO-201. We hope this work open new opportunities for treatment of HWCOD with high-efficiency and low-cost.

Swelling-Induced Fragmentation and Polymer Leakage of Nanoplastics in Seawater.

Nanoplastics (NPs) have been successively detected in different environmental matrixes and have aroused great concern worldwide. However, the fate of NPs in real environments such as seawater remains unclear, impeding their environmental risk assessment. Herein, multiple techniques were employed to monitor the particle number concentration, size, and morphology evolution of polystyrene NPs in seawater under simulated sunlight over a time course of 29 days. Aggregation was found to be a continuous process that occurred constantly and was markedly promoted by light irradiation. Moreover, the occurrence of NP swelling, fragmentation, and polymer leaching was evidenced by both transmission electron microscopy and scanning electron microscopy techniques. The statistical results of different transformation types suggested that swelling induces fragmentation and polymer leakage and that light irradiation plays a positive but not decisive role in this transformation. The observation of fragmentation and polymer leakage of poly(methyl methacrylate) and poly(vinyl chloride) NPs suggests that these transformation processes are general for NPs of different polymer types. Facilitated by the increase of surface functional groups, the ions in seawater could penetrate into NPs and then stretch the polymer structure, leading to the swelling phenomenon and other transformations.

Evaluating the Occurrence of Polystyrene Nanoparticles in Environmental Waters by Agglomeration with Alkylated Ferroferric Oxide Followed by Micropore Membrane Filtration Collection and Py-GC/MS Analysis.

Although nanoplastics (NPs) are recognized as emerging anthropogenic particulate pollutants, the occurrence of NPs in the environment is rarely reported, partly due to the lack of sensitive methods for the concentration and detection of NPs. Herein, we present an efficient method for enriching NPs of different compositions and various sizes. Alkylated ferroferric oxide (Fe3O4) particles were prepared as adsorbents for highly efficient capture of NPs in environmental waters, and the formed large Fe3O4-NP agglomerates were separated by membrane filtration. Detection limits of 0.02-0.03 µg/L were obtained for polystyrene (PS) and poly(methyl methacrylate) (PMMA) NPs by detection with pyrolysis-gas chromatography-mass spectrometry (Py-GC/MS). When analyzing real water samples from different sources, it is remarkable that PS NPs were detected in 11 out of 15 samples with concentrations ranging from <0.07 to 0.73 µg/L, while PMMA were not detected. The wide detection of PS NPs in our study confirms the previous speculation that NPs may be ubiquitous in the environmental waters. The accurate quantification of PS NPs in environmental waters make it possible to monitor the pollution status of NPs in aquatic systems and evaluate their potential risks.

Monitoring the Cd2+ release from Cd-containing quantum dots in simulated body fluids by size exclusion chromatography coupled with ICP-MS.

Quantification of Cd2+ release from Cd-containing quantum dots (QDs) is of fundamental importance to elucidate its toxicity to organisms, but remains a great challenge due to the lack of appropriate analytical method. Herein, a facile method based on size exclusion chromatography (SEC) combined with inductively coupled plasma mass spectrometry (ICP-MS) was developed for separating and quantifying the QDs and counterpart ions. By using the mixture of sodium dodecyl sulfate (SDS) and ethylenediaminetetraacetic acid tetrasodium salt (EDTA) as the mobile phase, the defect of QD and ion adsorption onto the SEC column was overcome, thus realizing the accurate quantification of ionic species. Besides, the concentration of QDs was achieved through subtracting the ion concentration from the total concentration. Selecting CdSe@ZnS as the typical QDs, the Cd2+ release process in four typical simulated body fluids, namely, simulated gastric fluid, simulated sweat, Gamble's solution, and artificial lysosomal fluid, was monitored using the developed SEC-ICP-MS method. The media pH is identified as the decisive factor which controls the dissolution of ZnS shells and also the Cd2+ release kinetics and final concentration. Our results suggest that the oral pathway for QD uptake poses the biggest risk to human health.

Total Organic Carbon as a Quantitative Index of Micro- and Nano-Plastic Pollution.

The global pollution of micro- and nano-plastics (MNPs) calls for monitoring methods. As diverse mixtures of various sizes, morphologies, and chemical compositions in the environment, MNPs are currently quantified based on mass or number concentrations. Here, we show total organic carbon (TOC) as an index for quantifying the pollution of total MNPs in environmental waters. Two parallel water samples are respectively filtered with a carbon-free glass fiber membrane. Then, one membrane with the collected particulate substances is treated by potassium peroxodisulfate oxidation and Fenton digestion in sequence for quantifying the sum of MNPs and particulate black carbon (PBC) as TOCMNP&PBC using a TOC analyzer, another membrane is treated by sulfonation and Fenton digestion for quantifying PBC as TOCPBC, and the TOC of MNPs is calculated by subtracting TOCPBC from TOCMNP&PBC. The feasibility of our method is demonstrated by determination of various MNPs of representative plastic types and sizes (0.5-100 µm) in tap, river, and sea water samples, with low detection limits (∼7 µg C L-1) and high spiked recoveries (83.7-114%). TOC is a powerful index for routine monitoring of MNP pollution.

Digestive Elimination of Coexisting Microplastics for Determination of Particulate Black Carbon in Environmental Waters.

Determination of particulate black carbon (PBC) in the environment is of great importance but faces a new challenge due to the increasing occurrence of coexisting microplastics (MPs), which are an emerging contaminant with properties very similar to those of PBC and cannot be discriminated in the chemical digestion procedure of the reported PBC analysis method. Herein, a comprehensive method has been developed for accurately determining PBC by digestive elimination of the coexisting MPs and other non-black carbon organic matter. Water samples were filtered with a glass fiber membrane (0.3 µm pore size), and the collected substances with the membrane were subjected to sulfonation with chlorosulfonic acid and Fenton digestion in sequence and then to the total organic carbon analyzer for quantification of PBC. Under the optimized conditions, MPs of various sizes and polymer types were efficiently eliminated (>91.0%), whereas various PBC samples were undigested with recoveries over 91.7% except for the relatively low recovery of 65.6% for the PBC prepared at a low pyrolysis temperature of 400 °C. The feasibility of the proposed method was verified by analysis of real water samples with a spike recovery of 88.6-100.2%. We anticipate that this work will pave an avenue for reliable determination of PBC in the presence of MPs.

Counting Nanoplastics in Environmental Waters by Single Particle Inductively Coupled Plasma Mass Spectroscopy after Cloud-Point Extraction and In Situ Labeling of Gold Nanoparticles.

The globally raising concern for nanoplastics (NPs) pollution calls for analytical methods for investigating their occurrence, fates, and effects. Counting NPs with sizes down to 50 nm in real environmental waters remains a great challenge. Herein, we developed a full method from sample pretreatment to quantitative detection for NPs in environmental waters. Various NPs of common plastic types and sizes (50-1200 nm) were successfully labeled by in situ growth of gold nanoparticles and counted by single particle inductively coupled plasma mass spectrometry. Sucrose density gradient centrifugation enables the isolation of gold-labeled NPs from homogeneously nucleated Au nanoparticles, enhancing the particle number detection limit to 4.6 × 108 NPs/L for 269 nm spherical polystyrene NPs. For real environmental water samples, the pretreatment of acid digestion with a mixture of 5 mM HNO3 and 40 mM HF eliminates the coexisting inorganic nanoparticles, while the following dual cloud-point extraction efficiently isolates NPs from various matrices and thus improves the Au-labeling efficiency. The high spiked recoveries (72.9%-92.8%) of NPs in different waters demonstrated the applicability of this method in different scenarios.

Sequential Isolation of Microplastics and Nanoplastics in Environmental Waters by Membrane Filtration, Followed by Cloud-Point Extraction.

Respective detection of microplastics (MPs) and nanoplastics (NPs) is of great importance for their different environmental behaviors and toxicities. Using spherical polystyrene (PS) and poly(methyl methacrylate) (PMMA) plastics as models, the efficiency for sequential isolation of MPs and NPs by membrane filtration and cloud-point extraction was evaluated. After filtering through a glass membrane (1 µm pore size), over 90.7% of MPs were trapped on the membrane, whereas above 93.0% of NPs remained in the filtrate. The collected MPs together with the glass membrane were frozen in liquid nitrogen, ground, and suspended in water (1 mL) and subjected to pyrolysis-gas chromatography-mass spectrometry (Py-GC/MS) determination. The NPs in the filtrate were concentrated by cloud-point extraction, heated at 190 °C to degrade the extractant, and then determined by Py-GC/MS. For MPs and NPs spiked in pure water, the method detection limits are in the range of 0.05-1.9 µg/L. The proposed method is applied to analyze four real water samples, with the detection of 1.6-7.6 µg/L PS MPs and 0.6 µg/L PMMA MPs in three samples, and spiked recoveries of 75.0-102% for MPs and 67.8-87.2% for NPs. Our method offers a novel sample pretreatment approach for the respective determination of MPs and NPs.

Supplementation of Bacillus sp. DU-106 reduces hypercholesterolemia and ameliorates gut dysbiosis in high-fat diet rats.

Gut microbiota modulation by a probiotic is a novel therapy for hypercholesterolemia mitigation. This study initially investigated the potential hypocholesterolemic effect of Bacillus sp. DU-106 in hypercholesterolemic rats and explored its potential relation with gut microbiota. Sprague-Dawley rats received a high-fat diet, or a high-fat diet supplemented with 7.5 × 109 and 1.5 × 1010 CFU/kg bw/day Bacillus sp. DU-106 (low-dose and high-dose groups). At the end of 9 weeks, Bacillus sp. DU-106 treatment significantly decreased the body weight, liver index, and total cholesterol. 16S rRNA sequencing showed that Bacillus sp. DU-106 intervention significantly increased bacterial richness and particularly increased the genus abundance of Turicibacter, Acinetobacter, Brevundimonas, and Bacillus and significantly decreased the abundance of Ralstonia. Metabolomic data further indicated that the supplementation of Bacillus sp. DU-106 remarkably changed the gut metabolic profiles of hypercholesterolemic rats and, in particular, elevated the metabolites of indole-3-acetate, methylsuccinic acid, creatine, glutamic acid, threonine, lysine, ascorbic acid, and pyridoxamine. Spearman's correlation analysis showed the close relation between the different genera and metabolites. In conclusion, Bacillus sp. DU-106 supplement ameliorated high-fat diet-induced hypercholesterolemia and showed potential probiotic benefits for the intestine. KEY POINTS: • A novel potential probiotic Bacillus sp. DU-106 ameliorated hypercholesterolemia in rats. • Bacillus sp. DU-106 supplement regulated gut microbiome structure and richness. • Bacillus sp. DU-106 supplement changed metabolic profiles in high-fat diet rats. • Significant correlations were observed between differential genera and metabolites.

In Situ Surface-Enhanced Raman Spectroscopic Evidence on the Origin of Selectivity in CO2 Electrocatalytic Reduction.

The electrocatalytic reduction of CO2 (CO2ER) to liquid fuels is important for solving fossil fuel depletion. However, insufficient insight into the reaction mechanisms renders a lack of effective regulation of liquid product selectivity. Here, in situ surface-enhanced Raman spectroscopy (SERS) empowered by 13C/12C isotope exchange is applied to probing the CO2ER process on nanoporous silver (np-Ag). Direct spectroscopic evidence of the preliminary intermediates, *COOH and *OCO-, indicates that CO2 is coordinated to the catalyst via diverse adsorption modes. Further, the relative Raman intensities of the above intermediates vary notably on np-Ag modified by Cu or Pd, and the liquid product selectivity also changes accordingly. Combined with density functional theory calculations, this study demonstrates that the CO2 adsorption configuration is a critical factor governing the reaction selectivity. Meanwhile, *COOH and *OCO- are key targets in the initial stage regulating liquid product selectivity, which could facilitate future selective catalyst design.

Coexposed nanoparticulate Ag alleviates the acute toxicity induced by ionic Ag+in vivo.

Health concerns of silver nanoparticles (AgNPs) emerged with the increase of their industrial and biomedical application and thus human exposure. The highly dynamic properties of AgNPs lead to coexposure to nanoparticulate and ionic silver, and the combined effects of different Ag species might alter their individual toxicity. Herein, the toxicity of AgNPs combined with ionic Ag+ toward the rat was investigated after intravenous (i.v.) exposure to either AgNPs (5 mg/kg), Ag+ (5 mg/kg), or a mixture of Ag+ and AgNPs (5 mg/kg for both). Comparable results by histopathological and biochemical studies revealed that the exposure to individual AgNPs causes no apparent toxicity in rats, while Ag+ ions at the same dose induced marked acute toxicity. More importantly, while there was a negligible combined effect on the Ag accumulation, the less toxic AgNPs ameliorated Ag+ induced toxicity to rat organs after coexposure to the mixture of Ag+ and AgNPs, which might result from the complexation of Ag+ with the thiols like metallothioneins. Therefore, the combined toxicity of particulate and ionic Ag was complicated by their individual toxicities and also their interaction with intracellular detoxification biomolecules, regardless of differences in Ag accumulation. Although further investigations are still needed for the potential toxic mechanisms of the coexposed AgNPs and Ag+, considerations of the combined toxicity of different Ag species will reflect more accurate assessments of their health impacts.

Speciation Analysis of the Uptake and Biodistribution of Nanoparticulate and Ionic Silver in Escherichia coli.

A new method was developed to determine the nanoparticulate and ionic silver (Ag) species in bacteria (Escherichia coli, E. coli). By removal of the cell wall with lysozyme, the cell surface-adsorbed Ag species were separated from the intracellular Ag species, which were extracted by tetramethylammonium hydroxide and determined by size-exclusion chromatography coupled with inductively coupled plasma mass spectrometry (SEC-ICP-MS). The detection limit is 3 ng/107 CFU/mL (where CFU is colony-forming unit) for both silver nanoparticles (AgNPs) and ionic Ag(I) species. The cell wall-adsorbed Ag was calculated by subtracting the contents of the intra- and extracellular Ag from the total exposure dose of Ag, and therefore the biodistribution of Ag species was profiled. We then applied this strategy to quantitatively analyze extra- and intracellular Ag species in E. coli after respective exposure to Ag+ and 10 and 30 nm AgNPs at different effective concentrations (EC10, EC50, and EC90). Results showed that the intracellular and cell wall-bound Ag account for 5.98-15.21% and 25.13-64.43% of the exposed dose, respectively, and AgNPs could transform into complexed or free Ag+. Our method opens new avenues for the quantitative analysis of the uptake and biodistribution of nanoparticles and their transformation species in bacteria.