Applications of magnetic nanoparticles in surface-enhanced Raman scattering (SERS) detection of environmental pollutants

Environmental pollution, a major problem worldwide, poses considerable threat to human health and ecological environment. Efficient and reliable detection technologies, which focus on the appearance of emerging environmental and trace pollutants, are urgently needed. Surface-enhanced Raman scattering(SERS) has become an attractive analytical tool for sensing trace targets in environmental field because of its inherent molecular fingerprint specificity and high sensitivity. In this review, we focused on the recent developments in the integration of magnetic nanoparticles(MNPs) with SERS for facilitating sensitive detection of environmental pollutants. An overview and classification of different types of MNPs for SERS detection were initially provided, enabling us to categorize the huge amount of literature that was available in the interdisciplinary research field of MNPs based SERS technology. Then, the basic working principles and applications of MNPs in SERS detection were presented. Subsequently, the detection technologies integrating MNPs with SERS that eventually were used for the detection of various environmental pollutions were reviewed. Finally, the advantages of MNP-basedSERS detection technology for environmental pollutants were concluded, and the current challenges and future outlook of this technology in practical applications were highlighted. The application of the MNPsbasedSERS techniques for environmental analysis will be significantly advanced with the great progresses of the nanotechnologies, optics, and materials.     

The onset of surface-enhanced Raman scattering for single-particle detection of submicroplastics

Microplastics represent an emerging environmental problem worldwide, raising ecological and food safety concerns. Compared to microplastics, there is growing evidence of an even higher abundance of submicro- and nanoplastics in the environment, but a reliable monitoring method for detecting these smaller-sized plastics is lacking. Herein we presented the application of surface-enhanced Raman scattering (SERS) for this purpose. Particles of polystyrene (PS; 600 nm) were used as the probe analyte. Gold nanourchins (AuNU; 50 nm), i.e. urchin-shaped nanoparticles with irregular spikes around the core, were used as the SERS-active substrate. The effectiveness of SERS on PS was evaluated at a single-particle level with different numbers of AuNU in order to determine the minimum conditions required for the onset of the SERS effect. Our findings suggest that SERS of a single particle of PS can be induced by as few as 1–5 particles of AuNU, and that the use of excitation wavelength at 785 nm is appropriate to meet the red-shifted surface plasmon resonance of AuNU upon aggregation. These specifications provide additional information for the development of SERS-based tools for detecting plastic particles < 1 µm in food and environmental samples.     

Surface-enhanced Raman scattering for mixing state characterization of individual fine particles during a haze episode in Beijing, China

The nondestructive characterization of the mixing state of individual fine particles using the traditional single particle analysis technique remains a challenge. In this study, fine particles were collected during haze events under different pollution levels from September 5 to 11 2017 in Beijing, China. A nondestructive surface-enhanced Raman scattering (SERS) technique was employed to investigate the morphology, chemical composition, and mixing state of the multiple components in the individual fine particles. Optical image and SERS spectral analysis results show that soot existing in the form of opaque material was predominant during clear periods (PM_2.5 ≤ 75 µg/m³). During polluted periods (PM_2.5 > 75 µg/m³), opaque particles mixed with transparent particles (nitrates and sulfates) were generally observed. Direct classical least squares analysis further identified the relative abundances of the three major components of the single particles: soot (69.18%), nitrates (28.71%), and sulfates (2.11%). A negative correlation was observed between the abundance of soot and the mass concentration of PM_2.5. Furthermore, mapping analysis revealed that on hazy days, PM_2.5 existed as a core-shell structure with soot surrounded by nitrates and sulfates. This mixing state analysis method for individual PM_2.5 particles provides information regarding chemical composition and haze formation mechanisms, and has the potential to facilitate the formulation of haze prevention and control policies.     

表面增强拉曼散射技术鉴别大肠杆菌和志贺氏菌的研究

以整个大肠杆菌和志贺氏菌为研究对象,通过和纳米银颗粒混合制片,利用表面增强拉曼效应检测并区分大肠杆菌和志贺氏菌.结果表明,未与纳米银颗粒混合的大肠杆菌和志贺氏菌没有明显的拉曼信号,而与纳米银颗粒混合后有明显的拉曼信号,二者有明显的区别,且重现性良好,可为鉴别大肠杆菌和志贺氏菌病原体研究及实际应用提供依据.     

Au nanoring arrays as surface enhanced Raman spectroscopy substrate for chemical component study of individual atmospheric aerosol particle

Monolayer-ordered gold nanoring arrays were prepared by ion-sputtering method and used as surface enhanced Raman spectroscopy (SERS) substrates to test the individual atmospheric aerosols particle. Compared to other methods used for testing atmospheric aerosols particles, the collection and subsequent detection in our work is performed directly on the gold nanoring SERS substrate without any treatment of the analyte. The SERS performance can be tuned by changing the depth of the gold nanoring cavity as originating from coupling of dipolar modes at the inner and outer surfaces of the nanorings. The electric field exhibits uniform enhancement and polarization in the ordered Au nanoring substrate, which can improve the accuracy for detecting atmospheric aerosol particles. Combined with Raman mapping, the information about chemical composition of individual atmospheric aerosols particle and distribution of specific components can be presented visually. The results show the potential of SERS in enabling improved analysis of aerosol particle chemical composition, mixing state, and other related physicochemical properties.     

Insight into the interaction between trimethoprim and soluble microbial products produced from biological wastewater treatment processes

Soluble microbial products (SMPs),dissolved organic matter excreted by activated sludge,can interact with antibiotics in wastewater and natural water bodies.Interactions between SMPs and antibiotics can influence antibiotic migration,transformation,and toxicity but the mechanisms involved in such interactions are not fully understood.In this study,integrated spectroscopy approaches were used to investigate the mechanisms involved in interactions between SMPs and a representative antibiotic,trime...     

Nickel phosphide on Ni foam as anode and peroxymonosulfate as the chemical oxidizer for effective direct urea fuel cell

The direct urea fuel cell (DUFC) is a low cost and competitive approach for contemporaneous urine or urea-contaminated wastewater treatment and electricity generation. However, the lack of efficient urea oxidation reaction (UOR) electrocatalysts and suitable electron acceptors remains a challenge for practical applications. Here, we developed a DUFC system using Ni₂[email protected] foam as the anode and peroxymonosulfate (PMS) as the chemical oxidizers. The Ni₂[email protected] foam anode showed a high oxidation activity for UOR with an onset potential of 0.30 V vs. Ag/AgCl and Tafel slope of 34.4 mV/dec. PMS with high theoretical potential improved the cell voltage to 1.43 V. A power density of DUFC up to 4.91 mW/cm² was achieved using PMS at room temperature, which was approximately twice as high as using H₂O₂ (2.38 mW/cm²). Ni^II/Ni^III was the redox active species on the Ni₂P anode in the DUFC process, and Ni^II was electrochemically oxidized to Ni^III, which reverted to Ni^II by urea reduction. When real human urine was used as the fuel, a power density of 4.46 mW/cm² can be achieved at room temperature. This DUFC with high cell performance showed potential application in urea wastewater treatment.     

Variability of fuel consumption and CO2 emissions of a gasoline passenger car under multiple in-laboratory and on-road testing conditions

An increasing divergence regarding fuel consumption(and/or CO₂ emissions) between realworld and type-approval values for light-duty gasoline vehicles(LDGVs) has posed severe challenges to mitigating greenhouse gases(GHGs) and achieving carbon emissions peak and neutrality. To address this divergence issue, laboratory test cycles with more real-featured and transient traffic patterns have been developed recently, for example, the China Lightduty Vehicle Test Cycle for Passenger cars(CL...     

A porous biochar supported nanoscale zero-valent iron material highly efficient for the simultaneous remediation of cadmium and lead contaminated soil

Risk associated with heavy metals in soil has been received widespread attention.In this study,a porous biochar supported nanoscale zero-valent iron（BC-nZVI） was applied to immobilize cadmium（Cd） and lead（Pb） in clayey soil.Experiment results indicated that the immobilization of Cd or Pb by BC-nZVI process was better than that of BC or nZVI process,and about 80% of heavy metals immobilization was obtained in BC-nZVI process.Addition of BC-nZVI could increase soil pH and organic matter（SOM）.Cd or...     

Efficient removal of Cr(VI) by a 3D Z-scheme TiO2-ZnxCd1-xS graphene aerogel via synergy of adsorption and photocatalysis under visible light

Efficient and robust photocatalysts for environmental pollutants removal with outstanding stability have great significance. Herein, we report a kind of three dimensional (3D) photocatalyst presented as Z-scheme heterojunction, which combining TiO 2 and Zn x Cd 1- x S with graphene aerogel to contrast TiO 2 -Zn x Cd 1- x S graphene aerogel (TSGA, x = 0.5) through a moderate hydrothermal process. The as-prepared Z-scheme TSGA was used to remove aqueous Cr(VI) via a synergistic effect of adsorption and visible light photocatalysis. The adsorption equilibrium can be reached about 40 min, then after about 30 min irradiation under visiblelight (wavelength ( λ) > 420 nm) the removal rate of Cr(VI) almost reached 100%, which is much better than the performance of pristine TiO 2 and Zn 0.5 Cd 0.5 S, as well as TiO 2 graphene aerogel (TGA) and Zn 0.5 Cd 0.5 S graphene aerogel (SGA). The virulent Cr(VI) was reduced to Cr(III) with hypotoxicity after photocatalysis on TSGA, meanwhile the as-synthesized TSGA presented a good stability and reusability. The reduced graphene oxide (rGO) sheets between TiO 2 and Zn 0.5 Cd 0.5 S played a role as charge transfer mediator, promoting the photoinduced electrons transfer and photocatalysis ability of TSGA was enhanced significantly. Hence,such photocatalyst exhibits a potential application on removing heavy metals with high efficiency and stability from polluted aqueous environment.     

Sorption kinetics of parent and substituted PAHs for low-density polyethylene (LDPE): Determining their partition coefficients between LDPE and water (KLDPE) for passive sampling

Low-density polyethylene(LDPE) has been widely used as a sorbent for passive sampling of hydrophobic organic contaminants(HOCs) in aquatic environments.However,it has seen only limited application in passive sampling for measurement of freely dissolved concentrations of parent and substituted PAHs(SPAHs),which are known to be toxic,mutagenic and carcinogenic.Here,the 16 priority PAHs and some typical PAHs were selected as target compounds and were simultaneously determined by gas chromatography–...     

Enhanced biodegradation of chlorobenzene via combined Fe3+ and Zn2+ based on rhamnolipid solubilisation

Biotrickling filters (BTFs) for hydrophobic chlorobenzene (CB) purification are limited by mass transfer and biodegradation. The CB mass transfer rate could be improved by 150 mg/L rhamnolipids. This study evaluated the combined use of Fe³⁺ and Zn²⁺ to enhance biodegradation in a BTF over 35 day. The effects of these trace elements were analysed under different inlet concentrations (250, 600, 900, and 1200 mg/L) and empty bed residence times (EBRTs; 60, 45, and 32 sec). Batch experiments showed that the promoting effects of Fe³⁺/Zn²⁺ on microbial growth and metabolism were highest for 3 mg/L Fe³⁺ and 2 mg/L Zn²⁺, followed by 2 mg/L Zn²⁺, and lowest at 3 mg/L Fe³⁺. Compared to BTF in the absence of Fe³⁺ and Zn²⁺, the average CB elimination capacity and removal efficiency in the presence of Fe³⁺ and Zn²⁺ increased from 61.54 to 65.79 g/(m³?hr) and from 80.93% to 89.37%, respectively, at an EBRT of 60 sec. The average removal efficiency at EBRTs of 60, 45, and 32 sec increased by 2.89%, 5.63%, and 11.61%, respectively. The chemical composition (proteins (PN), polysaccharides (PS)) and functional groups of the biofilm were analysed at 60, 81, and 95 day. Fe³⁺ and Zn²⁺ significantly enhanced PN and PS secretion, which may have promoted CB adsorption and biodegradation. High-throughput sequencing revealed the promoting effect of Fe³⁺ and Zn²⁺ on bacterial populations. The combination of Fe³⁺ and Zn²⁺ with rhamnolipids was an efficient method for improving CB biodegradation in BTFs.     

Assessment and prediction of the effect of ageing on the adsorption of nonylphenol in black carbon-sediment systems

Black carbon (BC) is a promising sediment amendment, as proven by its considerable adsorption capacity for hydrophobic organic pollutants and accessibility, but its reliability when used for the removal of pollutants in natural sediments still needs to be evaluated. For example, the ageing process, resulting in changing of surface physicochemical properties of BC, will decrease the adsorption capacity and performance of BC when applied to sediment pollution control. In this study, how the ageing process and BC proportion affect the adsorption capacity of BC-sediment systems was modelled and quantitatively investigated to predict their adsorption capacity under different ageing times and BC additions. The results showed that the ageing process decreased the adsorption capacity of both BC-sediment systems, due to the blockage of the non-linear adsorption sites of BC. The adsorption capacity of rice straw black carbon (RC)-sediment systems was higher than that of fly ash black carbon (FC)-sediment systems, indicating that RC is more efficient than FC for nonylphenol (NP) pollution control in sediment. The newly established model for the prediction of adsorption capacity fits the experimental data appropriately and yields acceptable predictions, especially when based on parameters from the Freundlich model. However, to fully reflect the influence of the ageing process on BC-sediment systems and make more precise predictions, it is recommended that future work considering more factors and conditions, such as modelling of the correlation between the adsorption capacity and the pore volume or specific surface area of BC, be applied to build an accurate and sound model.     

A review of electrokinetically enhanced bioremediation technologies for PHs

Since the early 1980’s there have been several different strategies designed and applied to the remediation of subsurface environment including physical, chemical and biological approaches.They have had varying degrees of success in remediating contaminants from subsurface soils and groundwater.The objective of this review is to examine the range of technologies for the remediation of contaminants, particularly petroleum hydrocarbons, in subsurfaces with a specific focus on bioremediation and el...     

Molecular toxicity and defense mechanisms induced by silver nanoparticles in Drosophila melanogaster

The widely use of silver nanoparticles (AgNPs) as antimicrobial agents gives rise to potential environmental risks. AgNPs exposure have been reported to cause toxicity in animals. Nevertheless, the known mechanisms of AgNPs toxicity are still limited. In this study, we systematically investigated the toxicity of AgNPs exposure using Drosophila melanogaster. We show here that AgNPs significantly decreased Drosophila fecundity, the third-instar larvae weight and rates of pupation and eclosion in a dose-dependent manner. AgNPs reduced fat body cell viability in MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) assays. AgNPs caused DNA damage in hemocytes and S2 cells. Interestingly, the mRNA levels of the entire metallothionein gene family were increased under AgNPs exposure as determined by RNA-seq analysis and validated by qRT-PCR, indicating that Drosophila responded to the metal toxicity of AgNPs by producing metallothioneins for detoxification. These findings provide a better understanding of the mechanisms of AgNPs toxicity and may provide clues to effect on other organisms, including humans.     

Thermal behaviors, combustion mechanisms, evolved gasses, and ash analysis of spent potlining for a hazardous waste management

An unavoidable but reusable waste so as to enhance a more circular waste utilization has been spent potlining (SPL) generated by the aluminum industry. The combustion mechanisms, evolved gasses, and ash properties of SPL were characterized dynamically in response to the elevated temperature and heating rates. Differential scanning calorimetric (DSC) results indicated an exothermic reaction behavior probably able to meet the energy needs of various industrial applications. The reaction mechanisms for the SPL combustion were best described using the 1.5-, 3- and 2.5-order reaction models. Fluoride volatilization rate of the flue gas was estimated at 2.24%. The SPL combustion emitted CO₂, HNCO, NO, and NO₂ but SO_x. The joint optimization of remaining mass, derivative thermogravimetry, and derivative DSC was achieved with the optimal temperature and heating rate combination of 783.5°C, and 5 °C/min, respectively. Interaction between temperature and heating rate exerted the strongest and weakest impact on DSC and remaining mass, respectively. The fluorine mainly as the formation of substantial NaF and CaF₂ in the residual ash. Besides, the composition and effect of environment of residual solid were evaluated. The ash slagging tendency and its mineral deposition mechanisms were elucidated in terms of turning SPL waste into a benign input to a circular waste utilization.     

Effect of dissolved oxygen on methane production from bottom sediment in a eutrophic stratified lake

Clarifying the role of sulfate and dissolved oxygen (DO) in methane production may allow for precise and accurate modeling of methane emissions in eutrophic lakes. We conducted field observations of sulfate, methane, and DO concentrations in Lake Abashiri, a typical brackish and eutrophic lake in a cold region, to develop a DO-based method for quantitively estimating methane production in a eutrophic lake and analyzed the results. We found that sulfate concentrations decreased rapidly from 900.0 mg/L in water overlying the sediments to nearly 0.0 mg/L in the bottom sediment. Methane production was almost uniform across sediment depths of 0.05 to 0.25 m, ranging from 1400 to 1800 µmol/m²/day. Also, methane production was found to be a function of DO concentrations in water overlying the bottom and could be modeled by a logistic function: constant production at 1,400 µmol/m²/day for DO concentrations of 0.0 to 3.0 mg/L, rapidly decreasing to 0 µmol/m²/day for DO concentrations of 3.0 to 6.0 mg/L. This methane model was verified using a simple one-dimensional numerical model that showed good agreement with field observations. Our results thus suggest that the proposed methane model reduces uncertainty in estimating methane production in a eutrophic lake.     

Simultaneous oxidation of Mn(II) and As(III) on cupric oxide (CuO) promotes As(III) removal at circumneutral pH

Oxidation of Mn(II) or As(III) by molecular oxygen is slow at pH < 9, while they can be catalytically oxidized in the presence of oxide minerals and then removed from contaminated water. However, the reaction mechanisms on simultaneous oxidation of Mn(II) and As(III) on oxide mineral surface and their accompanied removal efficiency remain unclear. This study compared Mn(II) oxidation on four common metal oxides (γ-Al₂O₃, CuO, α-Fe₂O₃ and ZnO) and investigated the simultaneous oxidation and removal of Mn(II) and As(III) through batch experiments and spectroscopic analyses. Among the tested oxides, CuO and α-Fe₂O₃ possess greater catalytic activity toward Mn(II) oxidation. Oxidation and removal kinetics of Mn(II) and As(III) on CuO indicate that O₂ is the terminal electron acceptor for Mn(II) and As(III) oxidation on CuO, and Mn(II) acts as an electron shuttle to promote As(III) oxidation and removal. The main oxidized product of Mn(II) on CuO is high-valent MnO_x species. This newly formed Mn(III) or Mn(IV) phases promote As(III) oxidation on CuO at circumneutral pH 8 and is reduced to Mn(II), which may be then released into solution. This study provides new insights into metal oxide-catalyzed oxidation of pollutants Mn(II) and As(III) and suggests that CuO should be considered as an efficient material to remediate Mn(II) and As(III) contamination.     

Micropollutant removal and disinfection byproduct control by sequential peroxymonosulfate-UV treatment in water: A case study with sulfamethoxazole

UV/peroxymonosulfate (UV/PMS) advanced oxidation process has attracted significant attention for removal of micropollutants in water. However, during practical water treatment applications, the PMS treatment must be performed before the UV treatment to achieve full contact. In this study, sulfamethoxazole (SMX) was selected as the target micropollutant. Four different operational approaches, including UV alone, PMS alone, simultaneous UV/PMS and sequential PMS-UV, were compared for their differences in SMX removal and disinfection by-product (DBP) formation potentials during chlorine-driven disinfection. Among the four approaches, UV/PMS and PMS-UV achieved over 90% removal efficiencies for SMX without substantial differences. For raw water, the trichloronitromethane (TCNM) formation potential after treatment with PMS-UV was lower than that after UV/PMS treatment. The time interval over which the PMS-UV process was conducted had little effect on the final removal efficiency for SMX. However, a brief (5 min) pre-PMS treatment significantly reduced the TCNM formation potential and the genotoxicity from DBPs. The formation risk for TCNM during chlorination increased markedly with increasing PMS dosages, and the appropriate dosage under these experimental conditions was suggested to be 0.5–1.0 mmol/L. Under alkaline conditions, PMS-UV treatment can enhance SMX degradation as well as dramatically reduced the formation potentials for haloketones, haloacetonitriles and halonitromethanes. This study suggests that proper optimization of UV/PMS processes can remove SMX and reduce its DBP formation.     

An intercomparison of ozone taken from the Copernicus atmosphere monitoring service and the second Modern-Era retrospective analysis for research and applications over China during 2018 and 2019

Spatiotemporal variations of ozone (O₃) taken from the Copernicus Atmosphere Monitoring Service (CAMS) and the second Modern-Era Retrospective Analysis for Research and Applications (MERRA-2) were intercompared and evaluated with ground and ozone-sonde observations over China in 2018 and 2019. Intercomparison of the surface ozone from CAMS and MERRA-2 reanalysis showed significant negative bias (CAMS minus MERRA-2, same below) at Tibetan Plateau of up to 80 µg/m³, and the average R² was about 0.6 across China. Evaluated with the ground observations from China National Environmental Monitoring Center (CNEMC), we found that CAMS and MERRA-2 reanalysis were capable of capturing the key patterns of monthly and diurnal variations of surface ozone over China except for the western region, and MERRA-2 overestimated the observations compared to CAMS. Vertically, the CAMS profiles overestimated the ozone-sonde from the World Ozone and Ultraviolet Radiation Data Center (WOUDC) above 200 hPa with the magnitude reaching up to 150 µg/m³, while little bias was found between the reanalysis and observations below 200 hPa. Intercomparison drawn from the vertical distribution between CAMS and MERRA-2 reanalysis showed that the negative bias appeared throughout the troposphere over China, while the positive bias emerged in the upper troposphere and lower stratosphere (UTLS) with high order of magnitude exceeding 100 µg/m³, indicating large uncertainties at higher altitudes. In summary, we concluded that CAMS reanalysis showed better agreement with the observations in contrast to MERRA-2, and the large discrepancy especially at higher altitudes between these two reanalysis datasets could not be ignored.