| 1. |
- Abdul Azeem, Hafiz
(författare)
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Extraction and Chromatography of targeted emission markers in atmospheric aerosols
- 2018. - 1st
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Atmospheric aerosols are a highly complex and dynamic mixture of solid particles, liquid deplots and gases. They travel across the continents and affect global climate and human health in various ways, often negatively. One important aspect of research in atmospheric aerosols is the investigation of emissions to the atmosphere from various sources. Emission markers are compounds unique to their sources of emission, hence, they act as fingerprints and are extensively used in source apportionment studies. It is highly challenging to sample, extract and quantify the compounds of interest, e.g. emission markers, from a complex mixture of thousands of organic and inorganic compounds, minerals and metals. A common bottleneck is the stringent requirements on the analytical methods, demanding high selectivity and low limits of detection. The work presented here focuses on the development of various extraction and chromatography methodsfollowed by mass spectrometry detection for the extraction, islation andquantitative anlaysis of targeted emission markers from complex aerosol samples.Development and optimization of various extraction and microextraction methods, optimization of different chromatography methods and mass spectrometry detection was motivated by the goals of higher selectivity, sensitivity, precision, accuracy, low limits of detection and low limits of quantification. Selection of greener solvents, reduced solvent use, shorter run times and eventually cheaper solutions were emphasised. The developed methods were compared with already existing methods in terms of 1) lower limits of detection, 2) reduced bias in analytical measurements and 3) greener alternatives. An interesting discovery on the formation of iron(III) complexes of 3-methyl-1,2,3-butane tricarboxylic acid, one of the emission markers for secondary biogenic emissions from monoterpenes,was also presented for the first time. The potential of the methods wasdemonstrated by their applications to aerosol samples as well as to solve societalproblems like early detection of smouldering fire using a unique emission marker.Finally, detailed description of hollow-fibre liquid-phase microextraction methodstudied for the extraction of 3-methyl-1,2,3-butane tricarboxylic acid waspresented along with the drawbacks of the method observed for the compound. It is expected that the research presented here will be a positive contribution in the estimation of emission markers and similar compounds from complex samples.
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| 2. |
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| 3. |
- Azeem, Hafiz Abdul, et al.
(författare)
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Can you smell smoke?
- 2019
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Ingår i: Spectroscopy Europe. - 0966-0941. ; 31:1, s. 22-23
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Tidskriftsartikel (refereegranskat)
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| 4. |
- Azeem, Hafiz Abdul, et al.
(författare)
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Extending the scope of dispersive liquid–liquid microextraction for trace analysis of 3-methyl-1,2,3-butanetricarboxylic acid in atmospheric aerosols leading to the discovery of iron(III) complexes
- 2019
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Ingår i: Analytical and Bioanalytical Chemistry. - : Springer Science and Business Media LLC. - 1618-2642 .- 1618-2650. ; 411:13, s. 2937-2944
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Tidskriftsartikel (refereegranskat)abstract
- 3-Methyl-1,2,3-butanetricarboxylic acid (MBTCA) is a secondary organic aerosol and can be used as a unique emission marker of biogenic emissions of monoterpenes. Seasonal variations and differences in vegetation cover around the world may lead to low atmospheric MBTCA concentrations, in many cases too low to be measured. Hence, an important tool to quantify the contribution of terrestrial vegetation to the loading of secondary organic aerosol may be compromised. To meet this challenge, a dispersive liquid–liquid microextraction (DLLME) method, known for the extraction of hydrophobic compounds, was extended to the extraction of polar organic compounds like MBTCA without compromising the efficiency of the method. The extraction solvent was fine-tuned using tri-n-octyl phosphine oxide as additive. A multivariate experimental design was applied for deeper understanding of significant variables and interactions between them. The optimum extraction conditions included 1-octanol with 15% tri-n-octyl phosphine oxide (w/w) as extraction solvent, methanol as dispersive solvent, 25% NaCl dissolved in 5 mL sample (w/w) acidified to pH 2 using HNO 3 , and extraction time of 15 min. A limit of detection of 0.12 pg/m 3 in air was achieved. Furthermore, unique complexation behavior of MBTCA with iron(III) was found when analyzed with ultra-high-performance liquid chromatography coupled with electrospray ionization–quadrupole time-of-flight mass spectrometry (UHPLC–ESI–QToF). A comprehensive overview of this complexation behavior of MBTCA was examined with systematically designed experiments. This newly discovered behavior of MBTCA will be of interest for further research on organometallic photooxidation chemistry of atmospheric aerosols. [Figure not available: see fulltext.].
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| 5. |
- Azeem, Hafiz Abdul, et al.
(författare)
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Towards the isolation and estimation of elemental carbon in atmospheric aerosols using supercritical fluid extraction and thermo-optical analysis
- 2017
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Ingår i: Analytical and Bioanalytical Chemistry. - : Springer Science and Business Media LLC. - 1618-2642 .- 1618-2650. ; 409:17, s. 4293-4300
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Tidskriftsartikel (refereegranskat)abstract
- Air-starved combustion of biomass and fossil fuels releases aerosols, including airborne carbonaceous particles, causing negative climatic and health effects. Radiocarbon analysis of the elemental carbon (EC) fraction can help apportion sources of its emission, which is greatly constrained by the challenges in isolation of EC from organic compounds in atmospheric aerosols. The isolation of EC using thermo-optical analysis is however biased by the presence of interfering compounds that undergo pyrolysis during the analysis. EC is considered insoluble in all acidic, basic, and organic solvents. Based on the property of insolubility, a sample preparation method using supercritical CO2 and methanol as co-solvent was developed to remove interfering organic compounds. The efficiency of the method was studied by varying the density of supercritical carbon dioxide by means of temperature and pressure and by varying the methanol content. Supercritical CO2 with 10% methanol by volume at a temperature of 60 °C, a pressure of 350 bar and 20 min static mode extraction were found to be the most suitable conditions for the removal of 59 ± 3% organic carbon, including compounds responsible for pyrolysis with 78 ± 16% EC recovery. The results indicate that the method has potential for the estimation and isolation of EC from OC for subsequent analysis methods and source apportionment studies.
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| 6. |
- Azeem, Muhammad, et al.
(författare)
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Combined Economic Emission Dispatch in Presence of Renewable Energy Resources Using CISSA in a Smart Grid Environment
- 2023
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Ingår i: Electronics. - : MDPI. - 2079-9292. ; 12:3
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Tidskriftsartikel (refereegranskat)abstract
- The geographically spatial and controlled distribution of fossil fuel resources, catastrophic global warming, and depletion of fossil fuel resources have forced us to integrate zero- or low-emissions energy resources, such as wind and solar, in the generation mix. These renewable energy resources are unexhausted, available around the globe, and free of cost. The advancement in wind and solar technologies has caused an appreciable decrease in installed the and global levelized costs of electricity via these sources. Therefore, the penetration of renewable energy resources in the generation mix can provide a promising solution to the above-mentioned problems. The aim of simultaneously reducing fuel consumption in terms of “Fuel Cost” and “Emission” in thermal power plants is called a combined economic emission dispatch problem. It is a combinatorial and multi-objective optimization problem. The solution of this problem is to allocate the load demand and losses on the committed units in such way that the overall costs of the generation and emission of thermal units are reduced, while the legal bounds (constraints) are met. It is a highly non-linear and complex optimization problem. The valve-point loading effect makes this problem non-convex. The addition of renewable energy resources (RERs) adds more complexities to this problem because they are intermittent. In this work, chaotic salp swarm algorithms (CISSA) are used to solve the combined economic emission dispatch problem. Chaos is used as an alternative to randomization for the tuning of the control variable to improve the trait of obtaining global extrema. Different test cases having different combinations of thermal, solar, and wind units are solved using the proposed algorithm. The results show the superiority of this study in comparison to the existent research results in terms of the cost of generation and emissions.
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| 7. |
- Drabińska, Natalia, et al.
(författare)
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A targeted metabolomic protocol for quantitative analysis of volatile organic compounds in urine of children with celiac disease
- 2018
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Ingår i: RSC Advances. - : Royal Society of Chemistry (RSC). - 2046-2069. ; 8:64, s. 36534-36541
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Tidskriftsartikel (refereegranskat)abstract
- Volatile organic compounds (VOCs) in biological samples have gained popularity for disease monitoring and diagnosis. Celiac disease (CD) is one of the many prevalent health conditions which are challenging to diagnose. The aim of this study was to optimize a solid phase microextraction followed by gas chromatography-mass spectrometry, for quantitative analysis of a wide range of VOCs in the urine of patients with CD. Multivariate design of experiment was used to optimize the extraction conditions for the analysis of 15 urinary VOCs. Based on the performed experiments, extraction using 2.98 g of sodium chloride and 21 μL of 6 M hydrochloric acid for 15 min at 30 °C, using a CAR/PDMS fiber in headspace mode was found to be the most effective procedure for the analysis of the selected biomarkers. It was also demonstrated that the proposed method could distinguish between children with CD and healthy children based on the profile of VOCs. It is believed that quantitative analysis of these biomarkers will extend our understanding of CD and could be used for monitoring in patients under treatment.
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| 8. |
- Madsen, Dan, et al.
(författare)
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Levoglucosan as a Tracer for Smouldering Fire
- 2018
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Ingår i: Fire Technology. - : Springer Science and Business Media LLC. - 0015-2684 .- 1572-8099. ; 54:6, s. 1871-1885
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Tidskriftsartikel (refereegranskat)abstract
- Detecting fires at an early stage is crucial for mitigating and extinguishing fires. The increased use of biofuels in Northern Europe has led to an increased number of fires in storage facilities. These fires are often caused by self-heating in the interior of the stored materials and slowly develop to smouldering fires. Consequently, these smouldering fires are usually detected several days or weeks after the initial smouldering fire had started. At this point, measures to extinguish the smouldering fire inside the material are difficult as the fire has grown for a long time and is located inside the material. This makes it difficult to gain a successful effect of any extinguishing agents. This paper presents a pilot study in lab scale suggesting levoglucosan as an early tracer for smouldering fires using 600 g cotton as the biomass source. The advantage of detecting levoglucosan as a fire signature is that it serves as a tracer compound for biomass burning and is produced at temperatures of 200–400°C reducing the risk of false alarms from emissions produced at lower temperatures. In this paper, levoglucosan was detected in aerosols emitted in an early stage from smouldering fires and was analyzed by ultrasonic assisted extraction followed by gas chromatographic separation and mass spectrometric detection. First detection of levoglucosan was made in the first sample, collected after 30 min when the smouldering fire was only a few cubic centimeters of the cotton package. In addition, levoglucosan was found in the solid residues of carbonized cotton after the initial smouldering process had moved through the material. The findings should be regarded as screening results to be used for the development of sensors and technology for smouldering fire detection.
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| 9. |
- Martinsson, Johan, et al.
(författare)
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Carbonaceous aerosol source apportionment using the Aethalometer model - evaluation by radiocarbon and levoglucosan analysis at a rural background site in southern Sweden
- 2017
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Ingår i: Atmospheric Chemistry and Physics. - : Copernicus GmbH. - 1680-7316 .- 1680-7324. ; 17:6, s. 4265-4281
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Tidskriftsartikel (refereegranskat)abstract
- With the present demand on fast and inexpensive aerosol source apportionment methods, the Aethalometer model was evaluated for a full seasonal cycle (June 2014June 2015) at a rural atmospheric measurement station in southern Sweden by using radiocarbon and levoglucosan measurements. By utilizing differences in absorption of UV and IR, the Aethalometer model apportions carbon mass into wood burning (WB) and fossil fuel combustion (FF) aerosol. In this study, a small modification in the model in conjunction with carbon measurements from thermal-optical analysis allowed apportioned non-light-absorbing biogenic aerosol to vary in time. The absorption differences between WB and FF can be quantified by the absorption angstrom ngstrom exponent (AAE). In this study AAE(WB) was set to 1.81 and AAE(FF) to 1.0. Our observations show that the AAE was elevated during winter (1.36 +/- 0.07) compared to summer (1.12 +/- 0.07). Quantified WB aerosol showed good agreement with levoglucosan concentrations, both in terms of correlation (R-2 = 0 : 70) and in comparison to reference emission inventories. WB aerosol showed strong seasonal variation with high concentrations during winter (0.65 mu gm(-3), 56% of total carbon) and low concentrations during summer (0.07 mu gm(-3), 6% of total carbon). FF aerosol showed less seasonal dependence; however, black carbon (BC) FF showed clear diurnal patterns corresponding to traffic rush hour peaks. The presumed non-light-absorbing biogenic carbonaceous aerosol concentration was high during summer (1.04 mu gm(-3), 72% of total carbon) and low during winter (0.13 mu gm(-3), 8% of total carbon). Aethalometer model results were further compared to radiocarbon and levoglucosan source apportionment results. The comparison showed good agreement for apportioned mass of WB and biogenic carbonaceous aerosol, but discrepancies were found for FF aerosol mass. The Aethalometer model overestimated FF aerosol mass by a factor of 1.3 compared to radiocarbon and levoglucosan source apportionment. A performed sensitivity analysis suggests that this discrepancy can be explained by interference of non-light-absorbing biogenic carbon during winter. In summary, the Aethalometer model offers a costeffective yet robust high-time-resolution source apportionment at rural background stations compared to a radiocarbon and levoglucosan alternative.
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| 10. |
- Martinsson, Johan, et al.
(författare)
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On the Relationship of Biogenic Primary and Secondary Organic Aerosol Tracer Compounds on the Aethalometer Model Parameters
- 2020
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Ingår i: Aerosol and Air Quality Research. - : Taiwan Association for Aerosol Research. - 2071-1409 .- 1680-8584. ; 20:12, s. 2654-2668
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Tidskriftsartikel (refereegranskat)abstract
- The aethalometer model has shown to offer a fast, inexpensive and robust method for source apportionment. The method relies on aerosol light absorption attribution, mass balance of the total carbon and results in a fraction of unaccounted, residual carbon that has been associated to biogenic carbon due to its presumably non-light absorbing properties. This residual carbon and its relation to tracers of biogenic primary and secondary organic aerosol was investigated at a rural measurement station in Sweden. Special focus is devoted to 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA), a second-generation oxidation compound in biogenic secondary organic aerosols. The results show that the residual carbon and the biogenic tracers show a high degree of correlation and that the tracers were highly seasonally dependent with largest carbon contributions during summer. MBTCA showed positive correlation with the aethalometer model derived absorption coefficients from fossil fuel carbonaceous aerosol, stressing the suspicion that biogenic aerosol might be falsely apportioned to fossil fuel carbon in the aethalometer model. MBTCA showed an increasing degree of correlation with higher aethalometer absorption coefficient wavelengths. However, spectrophotometric analysis revealed that the ambient concentrations of MBTCA are most likely to low to give a significant response in the aethalometer. These results support the application of MBTCA as a molecular tracer for biogenic secondary organic aerosol and indicates that a large fraction of the aethalometer model residual carbon is of biogenic origin. Future studies should investigate the light absorbing properties of precursor monoterpenes such as α-pinene, their oxidation products and eventual influence on the aethalometer model.
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