An innovative classification system for ranking the biological effects of marine aromatic hydrocarbons based on fish embryotoxicity

Petroleum hydrocarbon pollution is a global concern,particularly in coastal environments.Polycyclic aromatic hydrocarbons(PAHs) are regarded as the most toxic components of petroleum hydrocarbons.In this study,the biomonitoring and ranking effects of petroleum hydrocarbons and PAHs on the marine fish model Oryzias melastigma embryos were determined in the Jiulong River Estuary(JRE) and its adjacent waters in China.The results showed that the levels of petroleum hydrocarbons from almost all sites met the primary standard for marine seawater quality,and the concentrations of the 16 priority PAHs in the surface seawater were lower compared with those in other coastal areas worldwide.A new fish expert system based on the embryotoxicity of O.melastigma(OME-FES) was developed and applied in the field to evaluate the biological effects of petroleum hydrocarbons and PAHs.The selected physiological index and molecular indicators in OME-FES were appropriate biomarkers for indicating the harmful effects of petroleum hydrocarbons and PAHs.The outcome of OME-FES revealed that the biological effect levels of the sampling sites ranged from level Ⅰ(no stress) to level Ⅲ(medium stress),which is further corroborated by the findings of nested analysis of variance(ANOVA) models.Our results suggest that the OME-FES is an effective tool for evaluating and ranking the biological effects of marine petroleum hydrocarbons and PAHs.This method may also be applied to evaluate other marine pollutants based on its framework.

Fabrication of pollution-free coal gangue-based catalytic material utilizing ferrous chloride as activator for efficient peroxymonosulfate activation

Novel coal gangue-based persulfate catalyst(CG-FeCl_(2))was successfully synthesized by the means of calcinating under nitrogen atmosphere with the addition of ferrous chloride tetrahydrate(FeCl_(2)·_(4)H_(2)O).The phase transformation of the prepared materials and gas products during the heating process are thoroughly investigated.It is suggested that ferrous chloride participated in the phase transformation and formed Si-O-Fe bonds.And the main gaseous products are H_(2)O,H_(2),and HCl during the heating process.Besides,the ability of CG-FeCl_(2) to activate peroxymonosulfate(PMS)for catalytic degradation of polycyclic aromatic hydrocarbons(PAHs)and phenol was deeply studied.More than 95%of naphthyl,phenanthrene and phenol were removed under optimizied conditions.In addition,1O_(2),·OH,and SO_(4)·−were involved in the CG-FeCl_(2)/PMS system from the free radical scavenging experiment,where 1O_(2) played a major role during the oxidation process.Furthermore,CG-FeCl_(2)/PMS system exhibited superior stability in a relatively wide pH range and the presence of common anion from related degradation experiments.Overall,the novel CG-FeCl_(2) is an efficient and environmentally friendly catalyst,displaying potential application prospect in the field of PAHs and phenol-contaminated wastewater treatment.

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.

Mitigation of polycyclic aromatic hydrocarbons(PAHs)in roasted beef patties by cold plasma treatment and products quality evaluation

The cold plasma(CP)technique was applied to alleviate the contamination of polycyclic aromatic hydrocarbon(PAH)in this investigation.Two different CP treatments methods were implemented in the production of beef patties,to investigate their inhibition and degradation capacity on PAHs.With 5 different cooking oils and fats addition,the inhibition mechanism of in-package cold plasma(ICP)pretreatment was explored from the aspect of raw patties fatty acids composition variation.The results of principal component analysis showed that the first two principal components accounted for more than 80%of the total variation in the original data,indicating that the content of saturated fatty acids was significantly positively correlated with the formation of PAHs.ICP pretreatment inhibited the formation of PAHs by changing the composition of fatty acids,which showed that the total amount of polyunsaturated fatty acids decreased and the total amount of monounsaturated fatty acids increased.Sensory discrimination tests demonstrated there were discernable differences between 2 CP treated samples and the controls,utilization of the ICP pretreatment in meat products processing was expected to achieve satisfying eating quality.In conclusion,CP treatment degraded PAHs through stepwise ring-opening oxidation in 2 reported pathways,the toxicity of PAHs contaminated products was alleviated after CP treatment.

Eco-toxicity and health risk assessment of polycyclic aromatic hydrocarbons in surface sediments of Burullus Lake in Egypt

Polycyclic aromatic hydrocarbons(PAHs)are ubiquitous environmental contaminants of growing concern due to their potential ecological and human health risks.This study presents a comprehensive assessment of PAHs contamination in the surface sediments of Burullus Lake,a vital and second largest delta lake in Egypt.The aim was to evaluate the eco-toxicity and potential health risks associated with the presence of these compounds.Surface seven sediment samples were collected from various drains in the southern part of Burullus Lake.Soxhlet extraction method was employed to extract PAHs(16PAHs)from the sediment sample.Analytically,target compounds were located using HPLC.The results showed that samples contained PAHs levels ranging from 0.038×10^(-6)to 0.459×10^(-6),which is considered heavily polluted by the European standard for PAHs pollution.Additionally,there was no apparent source of PAHs in the ElKhashah drain or the Brinbal Canal,as HPLC found none of the compounds.The most prevalent compound in sediment samples along the study area was fluoranthene.The diagnostic indices in the present study indicated that the hydrocarbons in the region originated from pyrolytic and man-made sources along the drains of Burullus Lake.The principal component analysis(PCA)and diagnostic ratios revealed that coal combustion and pyrolytic sources were responsible for the PAHs contamination in the surface sediments.The non-carcinogenic risk(HI),which is the product of the HQs for the adult and child populations,respectively,was calculated.HI values under 1,therefore,demonstrated that they had no carcinogenic effects on human health.TEQs and MEQs in the sediments of Burullus Lake do not have a cancer-causing impact on people.For the safety of nearby wildlife,aquatic life,and people,all activities that raise petroleum hydrocarbon levels in Burullus Lake must be adequately regulated and controlled.According to the ecological risk assessment,there is little chance that PAHs will be found in the sediments of Burullus Lake.This study underscores the urgent need for effective pollution control measures and regular monitoring of PAHs levels in Burullus Lake sediments to protect the aquatic ecosystem and public health.It also highlights the importance of considering eco-toxicity and human health risks in integrated risk assessments of PAHs-contaminated environments.

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.

Organic-Inorganic Interaction Recorded by Polycyclic Aromatic Steranes in Continental Epithermal Ore Deposits

Continental epithermal ore deposits are commonly associated with sedimentary organic matter,oils or solid bitumen.These organics embedded in mineral deposits can convey valuable information of the ore genesis.However,the extent to which the formation of ore minerals was recorded by organic compounds remains largely unknown,as also is how metal-rich ores interfere with the molecular proxies in the temperature regime envisaged for hydrothermal activity.The molecular compositional changes of various polycyclic aromatic steranes and polycyclic aromatic hydrocarbons and compounds derived from the Jinding Pb/Zn deposit,SW China provide new data.Aliphatic regular steranes are present as traces.The transformation from polycyclic aromatic steranes to unsubstituted polycyclic aromatic hydrocarbons is observed to show an increased trend with increasing hydrothermal alteration levels;this is consistent with the transformation from unsubstituted polycyclic aromatic hydrocarbons to heterocyclic compounds.Dehydrocyclization(aromatization)of polycyclic biological compounds and hydrodecyclization(dearomatization)of polycyclic aromatic compounds are two important reaction pathways in hydrothermal systems with moderate temperature.This detailed investigation of organicinorganic interactions of two groups of polycyclic compounds with metal-rich ores provides insights into the questions on how and to what extent the formation of Pb/Zn deposits can be recorded by organics.This work will improve our understanding of carbon reduction,oxidation or condensation in the deep Earth and the carbon exchange between the Earth's crust and mantle,and may shed light on the processes for ultra-deep hydrocarbon exploration.

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.

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.

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.

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.

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.

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.

厦门西海域表层水中PAHs污染与PAHs降解菌分布的关系

在厦门西海域设置6个站位,于2001年7月和10月两个航次对各站位表层水中多环芳烃(polycyclicaromatichydrocarbons,PAHs)的含量及几种常见PAHs的降解菌的数量进行调查,结果表明:表层水中PAHs的含量很不稳定,存在明显的时间变化。在7月的调查中,表层水中能检测到的PAHs以2—3环的为主,而在10月以4—6环的为主。低分子量的PAHs—芴和菲的含量与其降解菌的数量之间具有明显的正相关,而高分子量的PAHs—荧蒽和芘的含量与其降解菌的数量之间没有表现出相关性。

水泥窑PM_(2.5)排放特性及其PAHs风险分析

采用荷电低压颗粒物撞击器(ELPI)、便携式PM2.5采样器和稀释系统,对国内3家新型干法水泥生产厂(5条生产线)的水泥窑(包括窑头和窑尾)进行现场采样,分析水泥窑排放PM2.5的质量浓度、粒数浓度及其中的多环芳烃(PAHs)浓度,对呼吸致癌风险进行评价.结果表明:从粒数浓度分析,PM2.5中70%以上为PM0.33,这部分颗粒物主要是由气化凝结形成的.各采样点排放的PAHs主要以二环和三环的低环PAHs为主.第3个水泥厂窑头排放的PAHs含量最高,而且苯并[a]芘(BaP)超过国家所规定的8ng/m3标准限值,同时其呼吸致癌风险水平为4.46×10-4,高于可接受致癌风险水平的上限,需要有效处理.

土壤样品中多环芳烃的GC-MS快速分析方法

In this study,a GC-MS/SIM method was used to analyze 16 PAHs in soil by ASE on-line clean-up.The average recoveries were ranged from 67% to 129%.The relative standard deviations were between 2.7% and 21.1%.The calculated limits of detection were no more than 0.95 ng/g.This method was fast,simple,and cost-saving,and can be used in the large quantities of samples analysis.

加速溶剂萃取-GPC纯化-气相色谱-质谱法测定油区土壤中的16种多环芳烃

为了排除背景干扰,使测定数据更加准确,先通过加速溶剂萃取和GPC纯化方法富集油区土壤中约16种多环芳烃,再借助于气相色谱-质谱建立了高效、准确的分析方法.该方法对16种多环芳烃的相关系数在0.997以上,检出限为0.8 ～7.3 ng/mL,回收率为82.8％～94.2％,相对标准偏差为1.38％ ～ 8.86％.对实际样品的分析检测结果表明,本方法在油区土壤中的多环芳烃分析方面值得推广.

Extraction of the Residual Polycyclic Aromatic Hydrocarbons in the Long-term Contaminated Soil in the Field

[Objective] The aim of this study was to find a better method to exactly quantify the residual polycyclic aromatic hydrocarbons（PAHs）in the long-term contaminated soil in the field so as to provide basis for the remediation for PAHs contaminated soil.[Method]The comparisons of soxhlet extraction,ultrasonic extraction and shaking extraction were studied in the agricultural soil irrigated with oil sewage over a long period of time.[Result]The total PAHs extracted by soxhlet extraction were the highest（6 873.7 μg/kg）,followed by shaking extraction（6 698.8 μg/kg）and ultrasonic extraction（5 737.6 μg/kg）.Among these methods,the highest extracted 4 and 6 rings PAHs were in the soxhlet extraction,the highest extracted 2 and 5 rings PAHs were in the shaking extraction,and the highest extracted 3 rings PAHs were in the ultrasonic extraction.[Conclusion]This study had provided basis for the selection of the assessment method of residual PAHs in the field soil.

Distribution and Risk Assessment of Polycyclic Aromatic Hydrocarbons in Mussels from the Middle and Lower Main Stream of Huaihe River

[ Object] The aim was to discuss the pollution status of polycyclic aromatic hydrocarbons （PAHs） in mussels from the middle and lower main stream of Huaihe River, which will provide a scientific basis for dietary safety of mussels. [ Method] Suspended matter, sediment, and mussel samples were collected from Wuxiaojie and Fushanji in middle and lower reaches of Huaihe River. All samples were extracted with Soxhlet, separated through Silica GeI-Al2O3 column, and determined by GC-MS, and then 16 typical PAHs contents in the prior table listed by American EPA were obtained. [ Result] The results indicated that total PAHs concentrations in suspended matters and sediments of Wuxiaojie were significantly higher than those in Fushanji respectively. However, PAHs concentrations in mussels of the two samplings showed little difference; as for single PAH component, low-ring PAHs were more advantaged in suspended matters of two sampling sites, while high-ring PAHs were more advantaged in mussels. PAHs in sediments of Wuxiaojie assumed low-ring aspect, though PAHs in sediments of Fushanji assumed high-ring aspect. [ Conclusion] In spite of that sediments and mussels were not yet contaminated according to the ecological risk assessment of PAHs, its potential hazards couldn＇t be ignored any more.

基于Polycycle信号的干扰抑制UWB自适应脉冲设计

针对认知超宽带与现存窄带系统干扰问题,采用Polycycle信号作为超宽带原始脉冲,使用Hermite矩阵特征向量方法设计了认知超宽带自适应脉冲,实现了干扰抑制.仿真结果表明,提出的自适应脉冲功率谱密度分布符合FCC室内和室外频谱规范,实现了自适应频段陷波.基于PAM-TH UWB系统性能分析表明自适应脉冲具有较强的多用户干扰和窄带干扰抑制能力.