Changes in the Non-targeted Metabolomic Profile of Three-year-old Toddlers with Elevated Exposure to Polycyclic Aromatic Hydrocarbons

Objective To investigate changes in the urinary metabolite profiles of children exposed to polycyclic aromatic hydrocarbons(PAHs)during critical brain development and explore their potential link with the intestinal microbiota.Methods Liquid chromatography-tandem mass spectrometry was used to determine ten hydroxyl metabolites of PAHs(OH-PAHs)in 36-month-old children.Subsequently,37 children were categorized into low-and high-exposure groups based on the sum of the ten OH-PAHs.Ultra-high-performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry was used to identify non-targeted metabolites in the urine samples.Furthermore,fecal flora abundance was assessed by 16S rRNA gene sequencing using Illumina MiSeq.Results The concentrations of 21 metabolites were significantly higher in the high exposure group than in the low exposure group(variable importance for projection>1,P<0.05).Most of these metabolites were positively correlated with the hydroxyl metabolites of naphthalene,fluorine,and phenanthrene(r=0.336–0.531).The identified differential metabolites primarily belonged to pathways associated with inflammation or proinflammatory states,including amino acid,lipid,and nucleotide metabolism.Additionally,these distinct metabolites were significantly associated with specific intestinal flora abundances(r=0.34–0.55),which were mainly involved in neurodevelopment.Conclusion Higher PAH exposure in young children affected metabolic homeostasis,particularly that of certain gut microbiota-derived metabolites.Further investigation is needed to explore the potential influence of PAHs on the gut microbiota and their possible association with neurodevelopmental outcomes.

Study on Adsorption Removal of Polycyclic Aromatic Hydrocarbons by Modified Mussel Shells

Polycyclic aromatic hydrocarbons(PAHs)are typical persistent organic pollutants(POPs)that are commonly found in the environment.They are carcinogenic,teratogenic,mutagenic and biodegradable obviously.In this paper,the modified mussel shells were used to adsorb and remove anthracene.The results show that the adsorption removal rate of the mussel shells was higher after calcination at 600℃.5%H_(3)PO_(4) solution was more suitable for shell treatment than 3 mol/L ZnCl_(2) solution.As the dosage of the modified shells was 0.5 g/L,the adsorption reached a stable state,and the removal rate of PAHs was about 69.44%;the adsorption efficiency rose with the increase of time.It can be seen that as a new and cheap biological adsorbent,the modified shells can be used to remove PAHs from wastewater.

Coking and decoking chemistry for resource utilization of polycyclic aromatic hydrocarbons(PAHs)and low-carbon process

Low-carbon process for resource utilization of polycyclic aromatic hydrocarbons(PAHs)in zeolitecatalyzed processes,geared to carbon neutrality-a prominent trend throughout human activities,has been bottlenecked by the lack of a complete mechanistic understanding of coking and decoking chemistry,involving the speciation and molecular evolution of PAHs,the plethora of which causes catalyst deactivation and forces regeneration,rendering significant CO_(2) emission.Herein,by exploiting the high-resolution matrix-assisted laser desorption/ionization Fourier-transform ion cyclotron resonance mass spectrometry(MALDI FT-ICR MS),we unveil the missing fingerprints of the mechanistic pathways for both formation and decomposition of cross-linked cage-passing PAHs for SAPO-34-catalyzed,industrially relevant methanol-to-olefins(MTO)as a model reaction.Notable is the molecule-resolved symmetrical signature:their speciation originates exclusively from the direct coupling of in-cage hydrocarbon pool(HCP)species,whereas water-promoted decomposition of cage-passing PAHs initiates with selective cracking of inter-cage local structures at 8-rings followed by deep aromatic steam reforming.Molecular deciphering the reversibly dynamic evolution trajectory(fate)of full-spectrum aromatic hydrocarbons and fulfilling the real-time quantitative carbon resource footprints advance the fundamental knowledge of deactivation and regeneration phenomena(decay and recovery motifs of autocatalysis)and disclose the underlying mechanisms of especially the chemistry of coking and decoking in zeolite catalysis.The positive yet divergent roles of water in these two processes are disentangled.These unprecedented insights ultimately lead us to a steam regeneration strategy with valuable CO and H_(2) as main products,negligible CO_(2) emission in steam reforming and full catalyst activity recovery,which further proves feasible in other important chemical processes,promising to be a sustainable and potent approach that contributes to carbon-neutral chemical industry.

Transport and behavior of marine oil spill containing polycyclic aromatic hydrocarbons in mesocosm experiments

Polycyclic aromatic hydrocarbons(PAHs)are one of the most important groups in oil,and re sponsible for major toxic and/or carcinogenic impact on humans and wildlife.It is important to understand the behavior of PAHs in marine environment after an oil-spill incident.However,interaction between petroleum PAHs and microbial communities in a marine environment remains unclear.Therefore,a series of mesocosm experiments were conducted.in which water-accommodated fraction(WAF)of oil was generated to simulate an oil-spill scenario and to analyze the transport and behavior of marine oil spill containing PAHs with and without dispersants.Results indicate that the application of dispersant could increase the concentration of total PAHs in water column due mainly to significant increase in the concentration of highmolecular weight(HMW)PAHs at a lower removal rate.At the end of the 7-day experiment,significant amount of HMW PAHs were accumulated in sediment.In general,the application of dispersant did not increase the sediment uptake of PAHs but increased the PAHs concentration in water column.

Inhibitory effect of coriander(Coriandrum sativum L.)extract marinades on the formation of polycyclic aromatic hydrocarbons in roasted duck wings

Coriander(Coriandrum sativum L.)is recognized for its antioxidant property,as a kind of natural phenolic-rich ingredient.Polycyclic aromatic hydrocarbons(PAHs)present a class of heat-driven hazards in foods,especially the processed meat.In this study,the effect of coriander root and leaf extract on the formation and inhibition of PAH8 in roasted duck wings was firstly investigated.Coriander root extract(CRE)and coriander leaf extract(CLE)with five concentration groups(200,400,600,800,1000 mg/L)were prepared respectively to marinate the duck wings.CRE marinade exhibited greater inhibitory effect on PAH8 formation in roasted duck wings that ranged from 65.0%-87.4%.The electron spin resonance study indicated a significantly positive correlation between PAH8 and free radical level,suggesting the participation of radicals in PAHs formation.Also,it was speculated that the inhibitory effect on PAH8 was related to the phenolic compounds identified in coriander marinades.CRE made greater inhibitory effect on the formation of PAH8 and could be considered as a kind of natural source to mitigate PAHs in heat-processed meat products.

Fate of Parent and Substituted Polycyclic Aromatic Hydrocarbons in SBR/MBBR Treatment Process:Experimental Value Against Model Prediction

The knowledge of the existence,distribution and fate of polycyclic aromatic hydrocarbons(PAHs)and substituted polycyclic aromatic hydrocarbons(SPAHs)in wastewater treatment plants(WWTPs)was vital for reducing their concentrations entering the aquatic environment.The concentrations of 13 SPAHs and 16 PAHs were all determined in a WWTP with styrene butadiene rubber(SBR)in partnership with the moving bed biofilm reactor(MBBR)process.SPAHs presented a higher concentration lever than PAHs in nearly all samples.The total removal efficiencies of PAHs and SPAHs ranged from 64.0%to 71.36%and 78.4%to 79.7%,respectively.The total yearly loads of PAHs(43.0 kg)and SPAHs(73.0 kg)were mainly reduced by the primary and SBR/MBBR biological treatment stages.The tertiary treatment stage had a minor contribution to target compounds removal.According to a synthesis and improvement fate model,we found that the dominant processes changed as the chemical octanol water partition coefficient(K_(ow))increased.But the seasonal variations of experimental removal efficiencies were more obvious than that of predicted data.In the primary sedimentation tank,dissolution in the aqueous phase and sorption to sludge/particulate matter were controlling processes for the removal of PAHs and SPAHs.The sorption to sludge and biodegradation were the principal removal mechanisms during the SBR/MBBR biological treatment process.The contribution of volatilization to removal was always insignificant.Furthermore,the basic physicochemical properties and operating parameters influenced the fate of PAHs and SPAHs in the WWTP.

Abundance and Source Identification of Polycyclic Aromatic Hydrocarbons in Sediments of the Ivory Coastal Zone (Toukouzou Hozalem-Assinie)

Polycyclic aromatic hydrocarbons (PAHs) are strongly associated with agricultural, residential, transportation, industrial and petroleum activities. In this study, the presence of PAHs (polycyclic aromatic hydrocarbons) was investigated in sediments of the ivory coastal zone (Toukouzou Hozalem-Assinie). The main objectives of this study were to determine the abundance and to predict the source of PAHs in the sediments. Gas chromatography-mass spectrometry (GC-MS) was used to analyze sixteen priority PAHs. Total PAHs concentrations were from 1.31 to 3992.68 mg/kg in sediment with an average concentration of (307.54 ± 16.10) mg/kg. Among all PAHs, Naphthalene (Nap = 332.72 mg/kg) and Phenanthrene (Phe = 41.75 mg/kg) were found in the highest concentration, whereas Benzo (k) Fluoranthene was found in the least concentration in the range of 0 - 0.85 mg/kg (mean 0.24 mg/kg). Bassam-Modeste Lagune (BML) sampling site was the site with the highest concentration of total PAHs (all 16 PAHs) compared to the others due to their location in a highly populated estuary area that receives commercial, tourism, port, petroleum and heavy industrial activities. Diagnostic ratios were used to determine the sources of PAHs and suggested that the PAH profile in the sediments was dominated by 2 and 3 ring PAHs. The patterns of PAH compounds in sediment indicated that contamination is from mixed sources, with a strong indication of petrogenic contamination potentially from spills of fuel, oil and industrial activities.

Development of analytical methods for polycyclic aromatic hydrocarbons (PAHs) in airborne particulates: A review

In the present work, the different sample collection, pretreatment and analytical methods for polycyclic aromatic hydrocarbons （PAHs） in airborne particulates is systematacially reviewed, and the applications of these pretreatment and analytical methods for PAHs are compared in detail. Some comments on the future expectation are also presented.

Characterization of Hapten-Protein Conjugates for Immunoassay of Polycyclic Aromatic Hydrocarbons(PAHs)

Preparation and characterization of the hapten-protein conjugates are fundamental to developing environmental immunoassays. As a hapten, 1-pyrenebutyric acid（PBA） was conjugated to the carrier protein of bovine serum albumin（BSA） or ovalbumin（OVA） by active ester method. Infrared spectra（IR） showed that PBA-BSA and PBA-OVA conjugates were successfully prepared. The number of the haptens conjugated to the carrier protein was determined by ultraviolet spectra（UV） and matrix-assisted laser desorption ionization time-of-flight mass spectrometry（MALDI-TOF-MS）. The calculated average binding ratios of PBA/BSA and PBA/OVA were 18：1 and 10：1 by UV, and 31：1 and 22：1 by MALDI-TOF-MS, respectively. Although there was a discrepancy between the results determined by the two methods, both of them were useful for the characterization of the hapten-protein conjugates. The antibody was produced against the antigen of PBA-BSA, and the affinity was tested by the double agar diffusion method The conjugates and the antibody could be used for developing a sensitive and selective immunoassay of polycyclic aromatic hydrocarbons（PAHs）.

Survey of polycyclic aromatic hydrocarbons(PAHs)in arterial street air of Hangzhou

The presence of particulate and vapor PAHs, SO2 and NOx and other interrelated conditions (temperature, traffic intensity and wind velocity) were investigated in the arterial street air of Hangzhou. The concentration of the nine PAHs in the air was mean to 11.7 μg/m3, and the content of benzo(a) pyrene was up to 0.108 μg/m3. The contents of PAHs in the sampling sites were in good relation to the traffic intensity, and would be also affected by the terrain and meteorological conditions. The occurrences of PAHs in ambient air were mainly affected by their physical, chemical characters and temperature. The three- and four-ring PAHs (MW&le228) mainly existed in the vapor phase and the five-ring PAHs (MW > 228) existed predominately in the particulate phase. The fraction of vapor PAHs in the total nine PAHs was 84.2% in the air of the sampling sites. In the morning and evening, the concentrations of PAHs in the arterial street air were higher than that on the noon and the diurnal variation of PAHs was similar to that of the traffic gas NOx. A conclusion would be drawn that the major source of PAHs in the arterial street air was the traffic. And the results indicated that 75% of BaP would come from traffic source and remaining 25% of BaP would come from non-traffic source.

Ultrasensitive Detection of Polycyclic Aromatic Hydrocarbons(PAHs) in Water Using Three-Dimensional SERS Substrate Based on Porous Material and pH 13 Gold Nanoparticles

Sensitivity is crucially important for surface-enhanced Raman spectroscopy(SERS)application to detect trace-level polycyclic aromatic hydrocarbons(PAHs)in the seawater.In this study,a high sensitivity three-dimensional(3-D)SERS substrate composed with syringe filter,glycidyl methacrylate-ethylene dimethacrylate(GMA-EDMA)porous material and optimal parameters(57 nm,pH 13)gold nanoparticles(Au NPs)was developed for the detection of PAHs in water.The enhancement effect and repeatability of this 3-D substrate were also explored.The Raman intensity of pyrene using 3-D SERS substrate is about 8 times higher than that of substrate only using p H 13 gold colloid solution and about 12 times higher than that of substrate using natural Au NPs and GMA-EDMA porous material,which means both the pH 13 AuN Ps and the GMA-EDMA porous material are important factors for the sensitivity of this 3-D SERS substrate.Good repeatability of this optimal 3-D substrate was obtained.The relative standard deviation(RSD)is less than 8.66% on the same substrate and less than 3.69% on other different substrates.Four kinds of PAHs,i.e.,phenanthrene,pyrene,benzo(a)pyrene,benzo(k)fluoranthene and their mixture,were detected at the different concentrations.Their limits of detection(LODs)are 8.3×10^-10(phenanthrene),2.1×10^-10(pyrene),3.8×10^-10(benzo(a)pyrene)and 1.7×10^-10 mol L^-1(benzo(k)fluoranthene),respectively.In addition,these four PAHs were also detected by fluorescence spectroscopy to evaluate the sensitivity of SERS technology using this optimal 3-D SERS substrate.The results showed that the sensitivity of SERS based on the 3-D SERS substrate even using the portable Raman system was closed to that of fluorescence spectroscopy.Therefore,the SERS technology using this optimal 3-D substrate is expected to be an in-situ method for the detection of environmental PAHs.

Ultrasonic wave extraction and simultaneous analysis of polycyclic aromatic hydrocarbons (PAHs) and phthalic esters in soil

A method is developed for detection of polycyclic aromatic hydrocarbons(PAHs) and Phthalic Acid Esters(PAEs) in soil samples. Ultrasonic Wave Extraction under airtight circumstances is adopted to extract the analytes in soil samples with n-hexane–acetone(V:V=1:1) as extraction solvent. This method has several advantages, including high extraction efficiency, short time, convenience and simplicity. It can be used to detect polycyclic aromatic hydrocarbons(PAHs) and Phthalic Acid Esters(PAEs) in soil.

Study on polycyclic aromatic hydrocarbons (PAHs) contents and sources in the surface soil of Huizhou City, South China, based on multivariate statistics analysis

Studies of polycyclic aromatic hydrocarbons (PAHs) in the surface soil were conducted in Huizhou City, which is located in the Pearl River Delta, South China. Sixteen PAHs in 42 soil samples were detected. The results showed that 4 components of PAHs were detectable in all soil samples, and other 12 components were also detect- able to some extent. The total PAHs contents range from 35.40 to 534.5 μg/kg with the mean value of 123.09 μg/kg. Soil in Huizhou was slightly polluted by PAHs according to Maliszewska-Kordybach’s study. It can be confirmed that the increase of PAHs contents in the surface soil of Huizhou City is closely connected to human activities. Mul- tivariate analysis was also made in this study. Principal component analysis was used to constrain their origins, and 3 principal components (PCs) were extracted. The results showed that coal combustion and oil spilling made the major contributions to PAHs. Cluster analysis was made and 16 priority PAHs were classified as 4 sorts, and the result revealed the differences in environmental behavior, chemical properties and sources of PAHs.

The Pollution Characteristic of Polycyclic Aromatic Hydrocarbons (PAHs) in Typical Sewage Irrigation Area in North of China

This research aims to investigate the pollution characteristic of PAHs in Xiaodian sewage irrigation area. The result shows that the concentrations ofPAHs range from 47.94 to 46432.85ng/g while that of the total components of the 16 kinds of PAHs are 5969.81ng/g. PAHs with for rings and more than 4 rings are the main and important pollutants in topsoils of Xiaodian District. The main input of PAHs is combustion source, and the main pollution source in this area is fired coal. The topsoils in Xiaodian District are polluted by human activity in varying degrees. 23 of all 31 topsoil samples have been heavily polluted, especially those located nearby developed industrial townships and irrigation channels.

CARBONIZED FIBROUS RESIN AS A NEW SORBENT FOR SAMPLING POLYCYCLIC AROMATIC HYDROCARBONS (PAHS) IN AMBIENT AIR

A new sampling method of ambient air analysis using carbonized fibrous resin as asorbent for polycyclic aromatic hydrocarbons (PAHs) was reported.The physical and chemical properties of the carbonized fibrous resins were measured. Thesample pretreatment with ultrasonic extraction and subsequent clean-up ehition through a silica gelcolumn was optimized. The suitable ultrasonic extraction conditions were selected as follows: resinweight was 1.5 g, ultrasonic extraction time 20 min, volume of extraction solvent 100 mi andextraction operation times 2～3. The concentrated extractable organic matter was submitted to nextstep of clean-up procedure of adsorption chromatography on silica gel column/n-hexane and amixture of dichloromethene:n-hexane solution 2:3 (v/v). The PAHs fractions in the real samplesfrom Changzhou, China were particularly analyzed using GC-MS data system and the data of massspectra, retention times and scan numbers of the real samples were compared with that of thestandards of 16 PAHs listed by the US EPA as 'priority pollutants' of the environment. Theanalysis of the real samples indicates that the carbonized fibrous resin is a good sorbent. Thepretreatment of samples of ambient air with carbonized fibrous resin as a sorbent for P,AHs isproved to be reliable and might be used for the procedure of the determination of PAHs inatmospheric environment.

2021年济南市大气PM_(2.5)中PAHs污染特征及其来源解析

目的分析济南市2021年细颗粒物(fine particulate matter,PM_(2.5))中PAHs污染特征及来源分析,为济南市大气环境综合治理提供相关数据支持。方法根据济南市区域分布特点选取2个有代表性监测点,每月的10—16日进行连续监测,使用超高效液相色谱仪对16种PAHs进行检测,分析济南市PM_(2.5)中PAHs变化趋势及特征,使用特征比值和PMF模型对PM_(2.5)中PAHs进行源解析。结果PAHs以4环和6环为主,具有显著的季节性变化趋势,即冬季>秋季>春季>夏季,1月份污染情况尤为突出;秋季和冬季中7种高致癌风险PAHs所占比例高于其他季节,历城区各季节PAHs质量浓度均高于市中区;结合特征比值和PMF对PAHs来源分析,冬季主要污染源是工业和石油产品挥发源、交通源;秋季主要为燃煤燃烧源、工业和石油产品挥发源和交通源。结论济南市PM_(2.5)中PAHs存在一定的污染,需加大清洁能源的使用,同时进一步加强秋、冬季,尤其是采暖季燃煤燃烧、工业和石油产品挥发和交通等污染源的控制。

重金属-PAHs污染土壤植物微生物修复效果及机理

针对焦化厂等土壤中铬(Cr)、砷(As)重(类)金属和菲(Phe)、苯并[a]芘(BaP)等多环芳烃(PAHs)风险高、绿色低碳修复技术缺乏等突出问题,以黑麦草-玉米-食醚红球菌(Rhodococcus aetherivorans,BW2)开展植物微生物联合。结果表明,63 d后植物微生物联合修复组土壤中Cr、As、Phe和BaP浓度分别下降9.63%、5.28%、45.14%和26.87%,其中重金属的去除主要依赖于植物作用,而PAHs去除则在很大程度上取决于微生物与植物的共同作用;植物主要吸收可提取态重金属,63 d后不同修复组土壤中可交换态Cr平均下降2.19%,而As则由于降解作用使修复过程中可交换态增加;可交换态Cr和碳酸盐结合态Cr与土壤中放线菌门呈强正相关,2种形态As则与拟杆菌门、装甲菌门、FBP菌门和浮霉菌门呈正相关。污染物去除效率间存在明显的相互作用,同时受酶活性和不同功能微生物丰度的动态影响,反之土壤微生物群落结构和功能也在土壤污染物种类、浓度及理化性质等综合作用下发生改变。

含过氧键化合物在土壤及地下水PAHs污染修复中的应用进展

土壤及地下水中多环芳烃(PAHs)污染的修复治理是当前亟需解决的问题,其中基于含过氧键化合物的高级氧化技术由于对土壤及地下水中PAHs具有高效的降解能力,在近年来受到越来越多的关注。本文重点总结了过氧化氢、过硫酸盐以及过氧乙酸在土壤及地下水中PAHs污染修复方面的研究,从过氧键断裂产生自由基的角度讨论了其活化机制与降解机理,探究了过氧乙酸在土壤及地下水中PAHs污染修复中的应用前景,分析了影响修复效率的主要外部因素。总体来看,不同活化方式所产生的自由基种类有所不同,对PAHs污染的修复效果也有所差异,与此同时,土壤及地下水复杂环境因素对修复效果有着重要的影响。因此在未来的研究中应开发新型活化材料,提高修复效果并降低二次污染,同时需针对不同的土壤及地下水环境选择合适的活化方式,采用表面活性剂增强氧化剂的修复范围,在过氧乙酸修复PAHs污染方面开展更深入的研究。含过氧键化合物修复PAHs污染土壤及地下水是一个值得深入研究的领域,未来具有广阔的应用前景,本综述为此提供了理论基础。

Selective Hydrogenation of Polycyclic Aromatics to Monocyclic Aromatics over NiMoC/HβCatalysts in a Methane and Hydrogen Environment

To obtain high yields of monocyclic aromatic hydrocarbons with methyl side chains,such as toluene and xylene,methane(CH_(4))can be introduced into the hydrocracking of polycyclic aromatic hydrocarbons.CH_(4)can participate in the reaction,supply methyl side chains to the product,and improve product distribution.In this study,the hydrogenation reaction of polycyclic aromatic hydrocarbons over a carbonized NiMo/Hβcatalyst in a CH_(4)and hydrogen(H_(2))environment was investigated to study the promotional effect of CH_(4)on the hydrocracking of polycyclic aromatics.Under conditions of 3.5 MPa,380℃,volume air velocity of 4 h^(-1),gas-oil volume ratio of 800,and H_(2):CH_(4)molar ratio of 1:1,the conversion rate of naphthalene was 99.97%,the liquid phase yield was 93.62%,and the selectivity of BTX were 17.76%,25.17%,and 20.47%,respectively.In comparison to the use of a H_(2)atmosphere,the selectivity of benzene was significantly decreased,whereas the selectivity of toluene and xylene were increased.It was shown that CH_(4)can participate in the hydrocracking of naphthalene and improve the selectivity of toluene and xylene in the liquid product.The carbonized NiMo/Hβcatalyst was characterized by a range of analytical methods(such as X-ray diffraction(XRD),ammonia-temperature-programmed desorption(NH3-TPD),hydrogen-temperature-programmed reduction(H_(2)-TPR),and X-ray photoelectron spectroscopy(XPS)).The results indicated that Ni and Mo carbides were the major species in the carbonized NiMo/Hβcatalyst and were considered to be active sites for the activation of CH_(4)and H_(2).After loading the metal components,the catalyst displayed prominent weak acidic sites,which may be suitable locations for cracking,alkylation,and other related reactions.Therefore,the carbonized NiMo/Hβcatalyst displayed multiple functions during the hydrocracking of polycyclic aromatic hydrocarbons in a CH_(4)and H_(2)environment.These results could be used to develop a new way to efficiently utilize polycyclic aromatic hydrocarbons and natural gas resources.