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.

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

在现在的工作，不同样品收集，为多不的芳香的烃的预告的处理 andanalytical 方法(哼) 在里面 issystematacially 考察的在空中的微粒，和预告的处理和在 detail.Some 比较的分析方法 forPAHsare 在未来期望上评价的这些的应用也被介绍。

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.

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.

Polycyclic aromatic hydrocarbons in soils of Beijing and Tianjin region: Vertical distribution, correlation with TOC and transport mechanism

The contents and distribution of 20 polycyclic aromatic hydrocarbons (PAHs) and heterocyclic aromatic hydrocarbons (HAHs) were investigated in 16 soil profiles of Beijing and Tianjin region. Transport of high molecular weight PAHs (HMWPAHs) and the correlation between total organic carbon (TOC) and their concentrations were also discussed. The results indicated that highly contaminated sites were located at urban or wastewater irrigation areas and pollutants mainly accumulated in topsoil (< 40 cm), with a sharp content decrease at the vertical boundary of 30-40 cm. Total PAHs/HAHs concentrations in soils from Tianjin were markedly greater than those from Beijing. Even the contents at bottoms of soil profiles in Tianjin were higher than those in topsoils of Beijing soil profile. HMWPAHs dominated the PAH profiles, exhibiting a uniform distribution of pyrogenic origin between topsoils and deep layers. Furthermore, the percentages of HMWPAHs remained relative constant with the depth of soil profiles, which were consistent with the distribution of particulate matter-associated PAHs in the local atmospheric environments. Therefore, HMWPAHs transport with particulates might be the predominant source found in soil profiles.

Emission characteristics of dioxins,furans and polycyclic aromatic hydrocarbons during fluidized-bed combustion of sewage sludge

Pre-dried sewage sludge with high sulfur content was combusted in an electrically heated lab-scale fluidized-bed incinerator. The emission characteristics of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polycyclic aromatic hydrocarbons (PAHs) were studied. Coal and calcium oxide (CaO) were added during the sewage sludge combustion tests to optimize combustion conditions and control SO2 emission. The results indicated that the flue gases emitted during mono-combustion of sewage sludge were characterized by relatively high concentrations of SO2, NOx and organic pollutants, due to the high sulfur, nitrogen, and volatile matter content of sewage sludge. The total 16 USEPA priority PAHs and 2,3,7,8-substituted PCDD/Fs produced from sewage sludge combustion were found to be 106.14 μg/m3 and 8955.93 pg/m3 in the flue gas, respectively. In the case of co- combustion with coal (msludge/mcoal = 1:1), the 16 PAHs and 2,3,7,8-substituted PCDD/Fs concentrations were markedly lower than those found during mono-combustion of sewage sludge. During co-combustion, a suppressant effect of CaO on PCDD/Fs formation was observed.

Influence of rice straw burning on the levels of polycyclic aromatic hydrocarbons in agricultural county of Taiwan

Atmospheric particulate and polycyclic aromatic hydrocarbons(PAHs)size distribution were measured at Jhu-Shan(a rural site) and Sin-Gang(a town site)in central Taiwan during the rice straw burning and non-burning periods.The concentrations of total PAHs accounting for a roughly 58%(34%)increment in the concentrations of total PAHs due to rice-straw burning.Combustion-related PAHs during burning periods were 1.54-2.57 times higher than those during non-burning periods.The mass median diameter(MMD) of 0.88-1.21μm in the particulate phase suggested that rice-straw burning generated the increase in coarse particle number.Chemical mass balance(CMB)receptor model analyses showed that the primary pollution sources at the two sites were similar.However,ricestraw burning emission was specifically identified as a significant source of PAH during burning periods at the two sites.Open burning of rice straws was estimated to contribute approximately 6.3%-24.6%to total atmospheric PAHs at the two sites.

Organochlorine pesticides and polycyclic aromatic hydrocarbons in water and sediment of the Bosten Lake,Northwest China

We evaluated organic pollution in Bosten Lake, Xinjiang, China, by measuring the concentrations and distributions of organochlorine pesticides(OCPs) and polycyclic aromatic hydrocarbons(PAHs). Water and sediment samples were collected from 19 sites(B1–B19) in the lake for analysis. Our analytical results show that the concentrations of total OCPs in water ranges from 30.3 to 91.6 ng/L and the concentrations of PAHs ranges from undetectable(ND) to 368.7 ng/L. The concentrations of total OCPs in surface(i.e., lake bottom) sediment ranges from 6.9 to 16.7 ng/g and the concentrations of PAHs ranges from 25.2 to 491.0 ng/g. Hexachlorocyclohexanes(HCHs) and dichlorodiphenyltrichloroethanes(DDTs) account for large proportions of the OCPs. Low α- to γ-HCH ratios in both water and sediment samples indicate possible contributions from both industrial products and lindane. DDTs in water are probably from historical input, whereas DDTs in sediments are from both historical and recent inputs. Moreover, DDT products in both water and sediments were from multiple sources in the northwestern part of the lake(B11, B12, B13, and B14). Fugacity ratios for DDT isomers(p,p′-DDE and p,p′-DDT) at these sites were generally higher than equilibrium values. These results suggest that the input from the Kaidu River and diffusion of DDTs from the sediment to the water are responsible for DDT pollution in the water. Lower-molecular-weight PAHs, which originate primarily from wood and coal combustion and petroleum sources, represent the major fraction of the PAHs in both water and sediment samples. Our findings indicate that OCPs and PAHs in Bosten Lake can be attributed primarily to human activities. A risk assessment of OCPs and PAHs in water and sediment from Bosten Lake, however, suggests that concentrations are not yet high enough to cause adverse biological effects on the aquatic ecosystem.

Distribution and Source Apportionment of Polycyclic Aromatic Hydrocarbons from Atmospheric Particulate Matter PM2.5 in Beijing

A total of 11 PM2.5 samples were collected from October 2003 to October 2004 at 8 sampling sites in Beijing city. The PM2.5 concentrations are all above the PM2.5 pollution standard (65μg m-3) established by Environmental Protection Agency, USA (USEPA) in 1997 except for the Ming Tombs site. PM2.5 concentrations in winter are much higher than in summer. The 16 Polycyclic aromatic hydrocarbons (PAHs) listed as priority pollutants by USEPA in PM2.5 were completely identified and quantified by high performance liquid chromatography (HPLC) with variable wavelength detector (VWD) and fluorescence detector (FLD) employed. The PM2.5 concentrations indicate that the pollution situation is still serious in Beijing. The sum of 16 PAHs concentrations ranged from 22.17 to 5366 ng m-3. The concentrations of the heavier molecular weight PAHs have a different pollution trend from the lower PAHs. Seasonal variations were mainly attributed to the difference in coal combustion emission and meteorological conditions. The source apportionment analysis suggests that PAHs from PM2.5 in Beijing city mainly come from coal combustion and vehicle exhaust emission. New measures about restricting coal combustion and vehicle exhaust must be established as soon as possible to improve the air pollution situation in Beijing city.

Treatment of tunnel wash waters-experiments with organic sorbent materials.PartⅠ:Removal of polycyclic aromatic hydrocarbons and nonpolar oil

Tunnel wash waters characterize all waters that run off after washing procedures of tunnels are performed.These waters represent a wide spectrum of organic and inorganic pollutants,such as polycyclic aromatic hydrocarbons(PAHs)and toxic metals.Removal of such contaminants from water runoff was investigated using laboratory tests after washing procedure was performed on two road tunnels in eastern Norway(Hanekleiv and Bragernes).Due to diverse character of both,treatment media and treated wash waters, the...

Determination of Trace Amount of Polycyclic Aromatic Hydrocarbons in Urban Sewage by Solid-phase Extraction Coupled with High Performance Liquid Chromatograph

[Method] This study aimed to determine trace amount of polycyclic aromatic hydrocarbons(PAHs) in urban sewage by using solid-phase extraction(SPE) coupled with high performance liquid chromatograph(HPLC).[Method] From the aspects of solid-phase extraction column,elution solvent,elution volume,elution speed and so forth,the test conditions of SPE-HPLC method were optimized,and trace amount of PAHs in urban sewage was determined.[Result] The optimized solid-phase extraction conditions were SUPELCLEAN LC-18 solid-phase extraction column,methylene dichloride as elution solvent,15 ml elution volume,2 ml/min elution speed,5 ml/min loading speed,1 000 ml water with 200 ml methanol loading volume.Under the optimized extraction conditions,the recovery was high,namely 76.3%-105.2%;relative standard deviation was 3.8%-6.0%,showing good precision;detection limit was low,only 0.000 8-0.048 0 μg/L.[Conclusion] This method is user-friendly,with high sensitivity and good precision,and suitable for continuous determination of a large volume of water samples.

Distribution and Sources of Polycyclic Aromatic Hydrocarbon (PAH) in Marine Environment of China

Polycyclic aromatic hydrocarbons (PAHs) are potentially carcinogenic and mutagenic compounds that have raised considerable environmental concern. The highest concentrations of PAHs in the coastal sediment samples in China was 5.8-11.0μg/g (dry weight) in the core from the Huangpu River, Shanghai. The second highest concentration of PAHs was 4.42μg/g (dry weight) in surface sediment of Victoria Harbour in Hong Kong, and 5.73μg/g (dry weight) in sediment of Jiaozhou Bay, Qingdao City. The low concentrations of PAHs were always in the sediments far away from industrial zones and cities, and ranged from 0.10 to 0.30μg/g (dry weight). Several environmental parameters are considered for the identification of sources of PAHs in marine environment. High proportion of naphthalene, low molecular weight PAHs and alkylated PAHs, plus high ratio of phenanthrene to anthracene (>15) and low ratio of fluoranthene to pyrene (<1) suggested a petrogenic source. According to these parameters, the Changjiang (Yangtze) River estuary of Shanghai, Jiaozhou Bay of Qingdao City, Zhujiang (Pearl) River mouth, Jiulong River mouth and most of Hong Kong coastal waters were heavily contaminated by PAHs from petrogenic sources. However, PAHs in rural coastal areas were dominated by pyrolytic origin PAHs. This review clearly showed that oil pollution and incomplete combustion of oil, coal and biomass are the main reason for PAHs anormalies in the study areas.

Polycyclic aromatic hydrocarbons in surface sediments of the Zhelin Bay in the South China Sea

This study examined the concentrations of polycyclic aromatic hydrocarbons (PAHs) in surface sediments collected in July 2004 from eight stations in the Zhelin Bay, one of the most important bays for large-scale mariculture in Guangdong Province. Thirteen individual parent PAH compounds were identified using high performance liquid chromatography with UV detection. The overall average concentration of total PAHs was 477.0 ng/g, ranging from 146.1 to 928.8 ng/g. Low molecular mass PAHs with two to three rings (e.g., acenaphthene) were dominant in each sample. The PAH concentration varied among sampling stations, with the highest concentration observed at bay outlets and the lowest found at stations outside the bay. Ratios of low to high molecular mass PAHs and fluoranthene to pyrene were used to determine the origin of PAHs, and results indicated mainly petroleum-derived contamination. Compared with other bays and harbors around the world, the total concentrations of PAHs in surface sediments at the Zhelin Bay are moderate, but this does not exclude the possibility of potential impact on human consumers because some strong carcinogenic PAHs with high molecular mass were found at the station with a nearby caged-fish and oyster farm. Long-term monitoring of PAH contamination in the Zhelin Bay is recommended to reduce the potential toxicological effects on aquatic organisms and humans.

Triacontyl modified silica gel as a sorbent for the preconcentration of polycyclic aromatic hydrocarbons in aqueous samples prior to gas chromatographic-mass spectrometry determination

Triacontyl modified silica gel as a sorbent coupled with gas chromatography-mass spectrometry (GC-MS) was developed to determine EPA prior 16 polycyclic aromatic hydrocarbons (PAHs) in water samples. Various parameters of solid-phase extraction such as organic modifier solvent, eluent, sample flow rate and volume were optimized. The developed method was found to yield a linear calibration curve in the concentration range of 0.05-8 μg/L with respect to naphthalene, acenaphthylene, acenaphthene and 0.01-8μg/L for dibenz[a,h]anthracene and 0.05-14 μg/L for fluorene, phenanthrene, anthracene and 0.01-14 μg/L for the rest of analytes. Furthermore, the good accuracy and repeatability of the method made sure the requirements for achieving reliable analysis of PAHs in the environmental water samples, and the recoveries of optimal method were in the range of 80-120% except to higher volatility PAHs. C30-bonded silica was proved to be an efficient sorbent for extraction of high molecular weight PAHs.

Fast Quantification of the Mixture of Polycyclic Aromatic Hydrocarbons Using Surface-Enhanced Raman Spectroscopy Combined with PLS-GA-BP Network

To realize the fast and accurate quantitative analysis of the mixture of polycyclic aromatic hydrocarbons(PAHs),surface-enhanced Raman spectroscopy(SERS)coupled with multivariate calibrations were employed.In this study,three kinds of calibration algorithms were used to quantitative analysis of the mixture of naphthalene(Nap),phenanthrene(Phe),and pyrene(Pyr).Firstly,partial least squares(PLS)algorithm was used to select characteristic variables,then the global search capability of genetic algorithm(GA)was used for the determining of the initial weights and thresholds of back propagation(BP)neural network so that local minima was avoided.The PLS-GA-BP model exhibited superiority to quantify PAHs mixture,which achieved R2=0.9975,0.9710,0.9643,ARE=10.07%,19.28%,16.72%and RMSE=13.10,5.40,5.10 nmol L−1 for Nap,Phe,Pyr(in the PAHs mixture)concentration prediction respectively.The forecast error,ARE and RMSE have been reduced more than 50%and 60%respectively compared with the whole spectral BP model.The study indicates that accurate quantitative spectroscopic analysis of the mixture of PAHs samples can be achieved through the combination of SERS technique and PLS-GA-BP algorithm.

Spatial Distribution and Sources Identification of Polycyclic Aromatic Hydrocarbons in Wolong Lake, Northeast China

The aquatic ecosystem maybe significantly affected by polycyclic aromatic hydrocarbons(PAHs) released from fresh water sediments. In order to protect biodiversity, the spatial distribution and sources of PAHs in the sediment of Wolong Lake in Northeast China were studied. A total of 17 surface sediment samples were collected and 12 PAHs were analyzed. The results were as follows. The concentration of total PAHs(TPAHs) ranged between 1412.9 μg/kg and 3948.3 μg/kg(dry weight). Indeno [1, 2, 3-c, d] pyrene was the dominant contaminant which accounted for 87%–98% of TPAHs. Diagnostic ratios of PAHs and principal component analysis showed that biomass combustion and vehicle emissions were likely to be the dominant sources of PAHs in the sediment. PAHs can be considered safe in the context of environmental and human health protection, based on the overall toxicity. Individual PAHs were positively correlated with total organic carbons. These results will be helpful to control PAHs and protect the aquatic ecosystem in the lake.

On-line enrichment and determination of polycyclic aromatic hydrocarbons in atmospheric particulates using high performance liquid chromatography with fluorescence as detector

七多不的芳族烃(哼) 与用方向注射和联机丰富陷井列的荧光察觉者在大气的微粒是由高效液体层析(HPLC ) 的 determinated。方法简化了样品预告的处理，节省了时间并且增加了效率。与联机陷井列，哼被分开有效地平的地下的注射有七的相对高的 columnefficiency.The 恢复的 1.0 ml 样品哼从 85% ～ 120% 因为察觉的刺的大气的 particulatesample.The 限制是 15.3-39.6 ng/L (S/N=3.3 ) 。在山峰区域和在有超过 0.9970 的相关系数的 1-50 ng/ml 的范围的七种 PAHs 的集中之间有好线性相关。而且，它也显示方法是可得到的决定在大气的微粒哼很好。