Tomasz Kowalkowski

Determination of volatile organic compounds as biomarkers of lung cancer by SPME–GC–TOF/MS and chemometrics

A method for qualitative and quantitative the determination of concentrations volatile organic compounds (VOCs) in human breath samples using solid phase microextraction (SPME) and gas chromatography-time of flight-mass spectrometry (GC-TOF/MS) has been carried out. They are employed for the preconcentration, separation and analysis of biological samples. The technique to rapid determination compounds present in human air, at the level of parts per billion (ppb) is applied. This method was optimized and evaluated. It showed linear correlations ranging from 0.83 to 234.05 ppb, limit of detection in the range of 0.31 to 0.75 ppb and precision, expressed as the RSD, was less then 10.00%. The unique combination of statistical methods allowed reduce the number of compounds to significant ones only and indicate the potential way to find the biomarkers of the lung cancer. Presented an analytical and statistical methods for detection composition of exhaled air could be applied as a potential non-intrusive tool for screening of lung cancer.

The application of statistical methods using VOCs to identify patients with lung cancer

In this work, an attempt was made to determine a group of lung cancer biomarkers. For this study, breath samples collected from 137 patients with confirmed lung cancer were analyzed by the SPME-GC/MS method. As a reference group, exhaled air from 143 healthy volunteers with different smoking habits (active smokers, passive smokers and nonsmokers) was applied. Statistical methods such as discriminant analysis (DA) and the CHAID model tree were used for data processing and evaluation. In the breath of patients with lung cancer, increased concentration of ethanol, acetone, butane, dimethyl sulfide, isoprene, propanal, 1-propanol, 2-pentanone, furan, o-xylene and ethylbenzene was observed in comparison to healthy nonsmokers. Furthermore, pentanal, hexanal and nonane were identified only in the breath of people who suffered from cancer. DA confirmed the importance of these compounds and allowed us to identify patients with lung cancer from healthy volunteers. In the exhaled air of healthy smokers (passive and active), a higher concentration of acetonitrile, benzene and furan derivatives was observed than in nonsmokers. DA revealed that in order to recognize healthy volunteers with different smoking habits by breath analysis, butyrolactone, carbon disulfide and dimethyl sulfide have to be considered.

Determination of volatile organic compounds in human breath for Helicobacter pylori detection by SPME‐GC/MS

Helicobacter pylori living in the human stomach release volatile organic compounds (VOCs) that can be detected in expired air. The aim of the study was the application of breath analysis for bacteria detection. It was accomplished by determination of VOCs characteristic for patients with H. pylori and the analysis of gases released by bacteria in suspension. Solid-phase microextraction was applied as a selective technique for preconcentration and isolation of analytes. Gas chromatography coupled with mass spectrometry was used for the separation and identification of volatile analytes in breath samples and bacterial headspace. For data calculation and processing, discriminant and factor analyses were used. Endogenous substances such as isobutane, 2-butanone and ethyl acetate were detected in the breath of persons with H. pylori in the stomach and in the gaseous mixture released by the bacteria strain but they were not identified in the breath of healthy volunteers. The canonical analysis of discrimination functions showed a strong difference between the three examined groups. Knowledge of substances emitted by H. pylori with the application of an optimized breath analysis method might become a very useful tool for noninvasive detection of this bacterium.

Investigation of lung cancer biomarkers by hyphenated separation techniques and chemometrics

Abstract Background: Volatile organic compounds (VOCs) present in breath of lung cancer patients and released by lung cancer cells were determined. As a reference sample breath collected from healthy volunteers and lung segments of cells with proper morphology were used. Methods: Solid phase microextraction and gas chromatography mass spectrometry (SPME-GC/MS) method was applied for VOC analysis. Statistical methods have been developed to find similarities between patterns of investigated compounds within three populations of samples: exhaled air samples from patients with lung cancer, headspace of lung tissues with healthy and cancer cells. Results: Quantitative analysis of VOCs in the headspace of lung tissues revealed that cancer cells released higher concentrations of ethanol, acetone, carbon disulfide, dimethyl sulfide, 1-propanol, 2-propanol, 2-butanone and 2-pentanone than healthy tissues. The increase of concentration of the same compounds was observed in the breath of patients with lung cancer in comparison to breath from healthy non-smoking volunteers. Conclusions: Detection of lung cancer is possible by volatile biomarkers analysis in breath.

Study of ionic liquid cations transport in soil

Ionic liquids are a form of organic or inorganic molten salts consisting positive and negative ions. There have been several attempts of their utilization in industry. These substances can be released from industrial sites into water and soils thus causing contamination. The most significant chemical processes affecting the behavior of ionic liquid cations in soils are related to their transport. The major aim of this work was to investigate the transport process of imidazolium ionic liquids in soils by column leaching experiments. Five types of soil with varying total organic carbon (TOC) content (<0.1%, 0.5%, 4%, 9.9%, 44.8%), were utilized in the study of transportation of three ionic liquid chlorides namely: 1-ethyl-3-methylimidazolium (EMIM), 1-n-butyl-3-methylimidazolium (BMIM), 1-n-hexyl-3-methylimidazolium (HMIM). The results obtained indicated significant ability to immobilize ionic liquid cations by soils with higher organic carbon content. The higher TOC value in soil results in lower amounts of solutes migrating through the soil. Factorial regression has been applied to modeling of the results. It relates soil and the ionic liquid cation properties to the retardation of this cation in soil profile.

The Adsorption Properties of Agricultural and Forest Soils Towards Heavy Metal Ions (Ni, Cu, Zn, and Cd)

Adsorption of Cu, Cd, Ni, and Zn in single and multi-metal solutions by agricultural and forest soils was investigated in batch sorption experiments. The results showed significant differences in sorption capacities of the studied soils. The selectivity order was as follows: agricultural soil≫ top forest soil > bottom forest soil. The adsorption sequence Cu > Zn > Ni > Cd was established for the agricultural and bottom forest soil, while the order for the top forest soil was Cu > Ni > Zn > Cd. The experimental isotherms for the metal sorption were described satisfactorily by the Freundlich and Langmuir models. The competitive adsorption experiment indicated a reduction in the amount of metals adsorbed by the soils from the multi-metal solution compared to the single metal solution. Properties of the soils, such as pH, content of clay and organic matter, exchangeable bases and hydrolytic acidity, showed a significant influence on adsorption capacities of the studied soils.

Separation of flavonoids on different phenyl-bonded stationary phases-the influence of polar groups in stationary phase structure

Four phenyl-bonded stationary phases, differing in polar embedded group between spacer and phenyl ring, were used for the separation of flavonoids in reversed-phase conditions. In addition, the work was focused on the comparison of these stationary phases in terms of retention and nature of interactions between flavonoid solutes and both, mobile and stationary phases. The differences and similarities between the columns and between individual flavonoids were evaluated by a statistical analysis. The retention over the wider range of mobile phase composition was described using well known model suggested for partition chromatographic systems. Due to differences in polarity of flavonoids, gradient elution had to be applied to achieve appropriate conditions for the successful separation. A chromatographic optimization software was employed for establish the appropriate profiles of gradient separations using UV detection at 275 nm. The most appropriate conditions for the separation of flavonoids were apparent on the phenyl and phenoxy columns.

Organic and inorganic pollution of the Vistula River basin

The main aim of this work is focused therefore on water quality assessment of the Vistula river and its primary tributaries. The study presents the analytical results of the contamination level of different organic and inorganic pollutants as well as the chemometric evaluation of the entire data set. A broad spectrum of compounds have been determined, including pesticides, polichlorinated biphenyls (PCBs), phenols, polycyclic aromatic hydrocarbons (PAHs), heavy metals, inorganic ions and some aggregate parameters like BOD. Majority of the organic xenobiotics have been analyzed for first time in the Vistula region on a large, long-term scale. Chemometric evaluation allowed the determination of natural clusters and groups of monitoring locations with similar pollution character. Chemometric analysis confirmed the classification of water purity of the Vistula River basin is related to the land utilization character in this region.

Investigation of the solubilization of car-emitted Pt, Pd and Rh in street dust and spiked soil samples

A sequential extraction procedure (three-step), proposed by the Standards, Measurements and Testing Programme (formerly BCR) of the European Union, was applied to street dust and spiked soil samples for the determination of PGEs. Analyses were carried out using inductively coupled plasma-mass spectrometry (ICP-MS). The results indicate that up to 5% from Pt, 70% from Pd and 14% from Rh are in mobile forms in street dust. The results for the soil samples spiked with crushed catalytic converter are significantly lower indicating that PGEs are oxidised more efficiently in natural conditions. Additionally Pt and Pd bound to humic acids were investigated.

The comparison study of compost and natural organic matter samples

Sewage sludge is a serious problem facing modern wastewater treatment plants. One of the methods to safely utilize the sludge is through composting and the agricultural use of the final product.In this study the compost samples from municipal sewage sludge are compared to the natural, rich in organic matter samples. Based on physicochemical properties of the material, the maturity indices are obtained to evaluate the quality of organic matter and estimate the similarities between the samples.The study shows that one-dimensional analysis like that based on maturity indices does not provide satisfactory answers concerning the nature of such complex materials. The data set of the analysis naturally possesses a multidimensional character so that the employment of advanced chemometric techniques like cluster analysis show a number of features which were hidden within the ‘data flood’.The major conclusion of this work is that the compost from sewage sludge is similar to peat in the significance of the properties of the organic matter. Moreover, the organic matter of agricultural soil, which is most stable and has been naturally matured over a long period of time, differs substantially from the other samples.