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Catalytic hydrogenolysis of plastic to liquid hydrocarbons over a nickel-based catalyst
2022
Zhao, Zhigang | Li, Zheng | Zhang, Xiangkun | Li, Tan | Li, Yuqing | Chen, Xingkun | Wang, Kaige
The catalytic hydrogenolysis of a typical model compound of mulching film waste, polyethylene, was investigated as a potential way to improve economic efficiency of mulching film recycling. Nickel-based heterogeneous catalysts are proposed for polyethylene hydrogenolysis to produce liquid hydrocarbons. Among catalysts supported on various carriers, Ni/SiO₂ catalyst shows the highest activity which may due to the interactions between nickel and silica with the formation of nickel phyllosilicate. As high as 81.18% total gasoline and diesel range hydrocarbon was obtained from the polyethylene hydrogenolysis at relatively mild condition of 280 °C, and 3 MPa cold hydrogen pressure. The result is comparable to what have been reported in previous studies using noble metal catalysts. The gasoline and diesel range hydrocarbon are n-alkanes with a distribution at a range of C₄–C₂₂. The gas products are primarily CH₄ along with a small amount of C₂H₆ and C₃H₈. High yield of CH₄ as much as 9.68% was observed for the cleavage of molecule occurs along the alkane chain.
Afficher plus [+] Moins [-]Latitudinal difference in the molecular distributions of lipid compounds in the forest atmosphere in China
2022
Zhang, Donghuan | Ren, Hong | Hu, Wei | Wu, Libin | Ren, Lujie | Deng, Junjun | Zhang, Qiang | Sun, Yele | Wang, Zifa | Kawamura, Kimitaka | Fu, Pingqing
Lipids are important biogenic markers to indicate the sources and chemical process of aerosol particles in the atmosphere. To better understand the influences of biogenic and anthropogenic sources on forest aerosols, total suspended particles (TSP) were collected at Mt. Changbai, Shennongjia, and Xishuangbanna that are located at different climatic zones in northeastern, central and southwestern China. n-Alkanes, fatty acids and n-alcohols were detected in the forest aerosols based on gas chromatography-mass spectrometry. The total concentrations of aliphatic compounds ranged from 15.3 ng m⁻³ to 566 ng m⁻³, and fatty acids were the most abundant (44–95%) followed by n-alkanes and n-alcohols. Low molecular weight- (LFAs) and unsaturated fatty acids (UnFAs) showed diurnal variation with higher concentrations during the nighttime in summer, indicating the potential impact from microbial activities on forest aerosols. The differences of oleic acid (C₁₈:₁) and linoleic acid (C₁₈:₂) concentrations between daytime and nighttime increased at lower latitude, indicating more intense photochemical degradation occurred at lower latitude regions. High levels of n-alkanes during daytime in summer with higher values of carbon preference indexes, combining the strong odd carbon number predominance with a maximum at C₂₇ or C₂₉, implied the high contributions of biogenic sources, e.g., higher plant waxes. In contrast, higher concentrations of low molecular weight n-alkanes were detected in winter forest aerosols. Levoglucosan showed a positive correlation (R² > 0.57) with high- and low molecular weight aliphatic compounds in Mt. Changbai, but such a correlation was not observed in Shennongjia and Xishuangbanna. These results suggest the significant influence of biomass burning in Mt. Changbai, and fossil fuel combustion might be another important anthropogenic source of forest aerosols. This study adds useful information to the current understanding of forest organic aerosols at different geographical locations in China.
Afficher plus [+] Moins [-]Full-scale bioremediation of diesel-polluted soil in an Arctic landfarm
2021
Johnsen, Anders R. | Boe, Uffe S. | Henriksen, Peter | Malmquist, Linus M.V. | Christensen, Jan H.
A full-scale, experimental landfarm was tested for the capacity to biodegrade oil-polluted soil under high-Arctic tundra conditions in northeast Greenland at the military outpost 9117 Station Mestersvig. Soil contaminated with Arctic diesel was transferred to the landfarm in August 2012 followed by yearly addition of fertilizer and plowing and irrigation to optimize microbial diesel biodegradation. Biodegradation was determined from changes in total petroleum hydrocarbons (TPH), enumeration of specific subpopulations of oil-degrading microorganisms (MPN), and changes in selected classes of alkylated isomers and isomer ratios. Sixty-four percent of the diesel was removed in the landfarm within the first year, but a recalcitrant fraction (18%) remained after five years. n-alkanes and naphthalenes were biodegraded as demonstrated by changing isomer ratios. Dibenzothiophenes and phenanthrenes showed almost constant isomer ratios indicating that their removal was mostly abiotic. Oil-degrading microorganisms were present for the major components of diesel (n-alkanes, alkylbenzenes and alkylnaphthalenes). The degraders showed very large population increases in the landfarm with a peak population of 1.2 × 10⁹ cells g⁻¹ of total diesel degraders. Some diesel compounds such as cycloalkanes, hydroxy-PAHs and sulfur-heterocycles had very few or no specific degraders, these compounds may consequently be degraded only by slow co-metabolic processes or not at all.
Afficher plus [+] Moins [-]Variations and characteristics of carbonaceous substances emitted from a heavy fuel oil ship engine under different operating loads
2021
Zhang, Fan | Chen, Yingjun | Su, Penghao | Cui, Min | Han, Yong | Matthias, Volker | Wang, Gehui
Heavy fuel oil (HFO) accounts for approximately 80% of the fuel consumption of ocean-going ships in the world. Multiple toxic species are found in HFO exhaust, however, carbonaceous substances emitted from low-speed marine engine exhaust at different operating loads have not been thoroughly addressed. Therefore, a bench test for a low-speed marine engine with HFO fuel under different operating modes was carried out in this study. Emission factors and characteristics of CO₂, CO, organic carbon (OC), elemental carbon (EC), as well as OC and EC fragments, organic matters of n-alkanes and polycyclic aromatic hydrocarbons (PAHs) are given and discussed. Combined with the correlation analysis results among the measured species and engine technical parameters, the formation processes and influence factors of carbonaceous components are also inferred in this study. Besides, together with OC to EC ratio, n-alkanes to PAHs ratio, etc., EC1 to soot-EC ratio in PM can be considered as tracer characteristic of high-sulfur-content HFO ship distinguished from diesel fuel ships. Profiles of n-alkanes and PAHs in PM can be used to distinguish shipping emission source from other combustion sources. Moreover, characteristics of carbonaceous components in size-segregated particles are also discussed, including OC, EC, OC and EC fragments, as well as organic matters. Results show that most of the particle mass, OC, EC, and organic matters are concentrated in fine particles with size of less than 1.1 μm, indicating the significance of ultrafine particles. Formation processes of OC and EC fragments, EC1 and soot-EC are also deduced and proved combined with the characteristics of OC and EC fragments, organic matters, and especially PAHs. Besides, the large variations of OC to EC ratios and speciated profiles of n-alkanes and PAHs in different particle size bins indicate that particle size should be considered when they are used as characteristic tracer in source apportionment studies.
Afficher plus [+] Moins [-]Column tests for evaluation of the enzymatic biodegradation capacity of hydrocarbons (C10–C50) contaminated soil
2021
Kadri, Tayssir | Robert, Thomas | Rouissi, Tarek | Sebastian, Joseph | Magdouli, Sara | Brar, Satinder Kaur | Martel, Richard | Lauzon, Jean-Marc
Though many studies pertaining to soil bioremediation have been performed to study the microbial kinetics in shake flasks, the process efficiency in column tests is seldom. In the present study, soil columns tests were carried out to study the biodegradation of soil contaminated with a high concentration of diesel (≈19.5 g/kg) petroleum hydrocarbons expressed as C₁₀–C₅₀. Experiments were done with crude enzymatic cocktail produced by the hydrocarbonoclastic bacterium, Alcanivorax borkumensis. A. borkumensis was grown on a media with 3% (v/v) motor oil as the sole carbon and energy source. The effects of the enzyme concentration, treatment time and oxidant on the bioremediation efficiency of C₁₀–C₅₀ were investigated. A batch test was also carried out in parallel to investigate the stability of the enzymes and the effect of the biosurfactants on the desorption and the bioconversion of C₁₀–C₅₀. Batch tests indicated that the biosurfactants significantly affected the desorption and alkane hydroxylase and lipase enzymes, maintained their catalytic activity during the 20-day test, with a half-life of 7.44 days and 8.84 days, respectively. The crude enzyme cocktail, with 40 U/mL of lipase and 10 U/mL of alkane hydroxylase, showed the highest conversion of 57.36% after 12 weeks of treatment with a degradation rate of 0.0218 day⁻¹. The results show that the soil column tests can be used to optimize operating conditions for hydrocarbon degradation and to assess the performance of the overall bioremediation process.
Afficher plus [+] Moins [-]Tracking petrogenic hydrocarbons in lakes of the Peace-Athabasca Delta in Alberta, Canada using petroleum biomarkers
2021
Thienpont, Joshua R. | Yang, Zeyu | Hall, Roland I. | Wolfe, Brent B. | Hollebone, Bruce P. | Blais, Jules M.
The Peace-Athabasca Delta (PAD) receives a mixture of hydrocarbons from biogenic, pyrogenic, and petrogenic processes. Source apportionment in the PAD has focussed on polycyclic aromatic compounds (PACs), which are ubiquitous in the environment and susceptible to weathering. In contrast, petroleum biomarkers of terpanes, hopanes, and steranes are degradation-resistant organic compounds found uniquely in petroleum products that can identify the input and origin of petrogenic hydrocarbons (PHCs). We provide an analysis of environmentally-relevant PHCs (including n-alkanes, PACs, and petroleum biomarkers) in surficial sediments of strategically selected lakes in the Athabasca and Peace deltas and adjacent boreal uplands. Alkanes were found to be predominately biogenic in all lakes. PAC sources were identified as wood combustion in the upland boreal lakes, a mixture of petrogenic and pyrogenic combustion in two closed-drainage lakes in the Peace Delta, and predominately petrogenic in two flood-prone Athabasca Delta lakes. Using multivariate analyses, raw Alberta oil sands were identified as a potential source of PHCs to the two flood-prone lakes in the Athabasca Delta. Biomarkers of terpanes and hopanes were identified in the Peace Delta and boreal uplands, likely from bitumen and transported atmospherically. These findings validate the use of petroleum biomarkers as tracers for bituminous sands in surficial lake sediments and their potential use in paleolimnological investigations at the PAD to improve understanding of relative roles of natural and industrial processes on far-field deposition of PHCs.
Afficher plus [+] Moins [-]Size−resolved source apportionment of particulate matter from a megacity in northern China based on one-year measurement of inorganic and organic components
2021
Tian, Yingze | Harrison, Roy M. | Feng, Yinchang | Shi, Zongbo | Liang, Yongli | Li, Yixuan | Xue, Qianqian | Xu, Jingsha
This research apportioned size-resolved particulate matter (PM) contributions in a megacity in northern China based on a full year of measurements of both inorganic and organic markers. Ions, elements, carbon fractions, n-alkanes, polycyclic aromatic hydrocarbons (PAHs), hopanes and steranes in 9 p.m. size fractions were analyzed. High molecular weight PAHs concentrated in fine PM, while most other organic compounds showed two peaks. Both two-way and three-way receptor models were used for source apportionment of PM in different size ranges. The three-way receptor model gave a clearer separation of factors than the two-way model, because it uses a combination of chemical composition and size distributions, so that factors with similar composition but distinct size distributions (like more mature and less mature coal combustion) can be resolved. The three-way model resolved six primary and three secondary factors. Gasoline vehicles and coal and biomass combustion, nitrate and high relative humidity related secondary aerosol, and resuspended dust and diesel vehicles (exhaust and non-exhaust) are the top two contributors to pseudo-ultrafine (<0.43 μm), fine (0.43–2.1 μm) and coarse mode (>2.1 μm) PM, respectively. Mass concentration of PM from coal and biomass combustion, industrial emissions, and diesel vehicle sources showed a bimodal size distribution, but gasoline vehicles and resuspended dust exhibited a peak in the fine and coarse mode, separately. Mass concentration of sulphate, nitrate and secondary organic aerosol exhibited a bimodal distribution and were correlated with temperature, indicating strong photochemical processing and repartitioning. High relative humidity related secondary aerosol was strongly associated with size shifts of PM, NO₃⁻ and SO₄²⁻ from the usual 0.43–0.65 μm to 1.1–2.1 μm. Our results demonstrated the dominance of primary combustion sources in the <0.43 μm particle mass, in contrast to that of secondary aerosol in fine particle mass, and dust in coarse particle mass in the Northern China megacity.
Afficher plus [+] Moins [-]Occurrence and weathering of petroleum hydrocarbons deposited on the shoreline of the North Saskatchewan River from the 2016 Husky oil spill
2020
Yang, Zeyu | Shah, Keval | Laforest, Sonia | Hollebone, Bruce P. | Situ, Jane | Crevier, Charlotte | Lambert, Patrick | Brown, Carl E. | Yang, Chun
Following the 16TAN Husky oil spill along the North Saskatchewan River (NSR), the occurrence and natural attenuation of the petroleum hydrocarbons were assessed by analyzing the littoral zone sediments/oil debris collected from July 2016 to October 2017. Husky oil-free, mixed sediment-Husky oil, and Husky oil debris samples were identified for all the collected samples. Shoreline sediments were contaminated by mixed biogenic, pyrogenic and petrogenic inputs prior to the spill. Oil stranded on the shoreline of NSR was moved or buried due to the very dynamic conditions of the shoreline, or cleaned through a series of cleanup activities after the spill. Most normal alkanes were naturally weathered, whereas most of the branched alkanes and all of the saturated petroleum biomarkers remained. Some lighter molecular weight (e.g., 2 to 3-ring) polycyclic aromatic hydrocarbons (PAHs) were lost rapidly after the spill, whereas sulfur containing components, e.g., dibenzothiophenes and benzonaphthothiiophenes, and those having a heavier molecular weight did not change markedly even 15 months post-spill. Similarly, some light hydrocarbons (e.g., <C₁₀) were lost over the first kilometers from the point of entry (POE), while heavier hydrocarbons did not show any major differences away from the POE. Very large inter-site and inter-survey discrepancies were found for samples. Evaporation into the air and dissolution into water, combined with biodegradation, were together or independently the main contributors to the loss of the light molecular hydrocarbons.
Afficher plus [+] Moins [-]Sorption of dispersed petroleum hydrocarbons by activated charcoals: Effects of oil dispersants
2020
Ji, Haodong | Xie, Wenbo | Liu, Wen | Liu, Xiaona | Zhao, Dongye
Marine oil spill often causes contamination of drinking water sources in coastal areas. As the use of oil dispersants has become one of the main practices in remediation of oil spill, the effect of oil dispersants on the treatment effectiveness remains unexplored. Specifically, little is known on the removal of dispersed oil from contaminated water using conventional adsorbents. This study investigated sorption behavior of three prototype activated charcoals (ACs) of different particle sizes (4–12, 12–20 and 100 mesh) for removal of dispersed oil hydrocarbons, and effects of two model oil dispersants (Corexit EC9500A and Corexit EC9527A). The oil content was measured as n-alkanes, polycyclic aromatic hydrocarbons (PAHs), and total petroleum hydrocarbons (TPHs). Characterization results showed that the smallest AC (PAC100) offered the highest BET surface area of 889 m2/g and pore volume of 0.95 cm3/g (pHPZC = 6.1). Sorption kinetic data revealed that all three ACs can efficiently adsorb Corexit EC9500A and oil dispersed by the two dispersants (DWAO-I and DWAO-II), and the adsorption capacity followed the trend: PAC100 > GAC12 × 20 > GAC4 × 12. Sorption isotherms confirmed PAC100 showed the highest adsorption capacity for dispersed oil in DWAO-I with a Freundlich KF value of 10.90 mg/g∙(L/mg)1/n (n = 1.38). Furthermore, the presence of Corexit EC9500A showed two contrasting effects on the oil sorption, i.e., adsolubilization and solubilization depending on the dispersant concentration. Increasing solution pH from 6.0 to 9.0 and salinity from 2 to 8 wt% showed only modest effect on the sorption. The results are useful for effective treatment of dispersed oil in contaminated water and for understanding roles of oil dispersants.
Afficher plus [+] Moins [-]Assessment of pops contaminated sites and the need for stringent soil standards for food safety for the protection of human health
2019
Weber, R. | Bell, L. | Watson, A. | Petrlik, J. | Paun, M.C. | Vijgen, J.
Persistent organic pollutants (POPs) including PCDD/Fs, PCBs and organochlorine pesticides (OCPs) are among the most important and hazardous pollutants of soil. Food producing animals such as chicken, beef, sheep and goats can take up soil while grazing or living outdoors (free-range) and this can result in contamination.In recent decades, large quantities of brominated flame retardants such as polybrominated diphenyl ethers (PBDEs), short-chain chlorinated paraffins (SCCPs) and per- and polyfluorinated alkylated substances (PFAS) have been produced and released into the environment and this has resulted in widespread contamination of soils and other environmental matrices. These POPs also bioaccumulate and can contaminate food of animal origin resulting in indirect exposure of humans.Recent assessments of chicken and beef have shown that surprisingly low concentrations of PCBs and PCDD/Fs in soil can result in exceedances of regulatory limits in food. Soil contamination limits have been established in a number of countries for PCDD/Fs but it has been shown that the contamination levels which result in regulatory limits in food (the maximum levels in the European Union) being exceeded, are below all the existing soil regulatory limits. ‘Safe’ soil levels are exceeded in many areas around emission sources of PCDD/Fs and PCBs. On the other hand, PCDD/F and dioxin-like PCB levels in soil in rural areas, without a contamination source, are normally safe for food producing animals housed outdoors resulting in healthy food (e.g. meat, eggs, milk).For the majority of POPs (e.g. PBDEs, PFOS, PFOA, SCCP) no regulatory limits in soils exist.There is, therefore, an urgent need to develop appropriate and protective soil standards minimising human exposure from food producing animals housed outdoors. Furthermore, there is an urgent need to eliminate POPs pollution sources for soils and to control, secure and remediate contaminated sites and reservoirs, in order to reduce exposure and guarantee food safety.
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