Produced water is the largest by-product of oil and gas production. At off-shore installations, the produced water is typically reinjected or discharged into the sea. The water contains a complex mixture of dispersed and dissolved oil, solids and inorganic ions. A better understanding of its composition is fundamental to (1) improve environmental impact assessment tools and (2) develop more efficient water treatment technologies. The objective of the study was to screen produced water sampled from a producing field in the Danish region of the North Sea to identify any containing organic compounds. The samples were taken at a test separator and represent an unfiltered picture of the composition before cleaning procedures. The analytes were isolated by liquid-liquid extraction and derivatized using a silylation reagent to increase the volatility of oxygenated compounds. The final extracts were analyzed by comprehensive multi-dimensional gas chromatography coupled to a high-resolution mass spectrometer. A non-target processing workflow was implemented to extract features and quantify the confidence of library matches by correlation to retention indices and the presence of molecular ions. Approximately 120 unique compounds were identified across nine samples. Of those, 15 were present in all samples. The main types of compounds are aliphatic and aromatic carboxylic acids with a small fraction of hydrocarbons. The findings have implications for developing improved environmental impact assessment tools and water remediation technologies.
Produced water is the largest by-product of oil and gas production. At off-shore installations, the produced water is typically reinjected or discharged into the sea. The water contains a complex mixture of dispersed and dissolved oil, solids and inorganic ions. A better understanding of its composition is fundamental to 1) improve environmental impact assessment tools and 2) develop more efficient water treatment technologies. The objective of the study was to screen produced water sampled from a producing field in the Danish region of the North Sea to identify any containing organic compounds. The samples were taken at a test separator and represent an unfiltered picture of the composition before cleaning procedures. The analytes were isolated by liquid-liquid extraction and derivatized using a silylation reagent to increase the volatility of oxygenated compounds. The final extracts were analyzed by comprehensive multi-dimensional gas chromatography coupled to a high-resolution mass spectrometer. A non-target processing workflow was implemented to extract features and quantify the confidence of library matches by correlation to retention indices and the presence of molecular ions. Approximately 120 unique compounds were identified across nine samples. Of those, 15 were present in all samples. The main types of compounds are aliphatic and aromatic carboxylic acids with a small fraction of hydrocarbons. The findings have implications for developing improved environmental impact assessment tools and water remediation technologies.
Characterization of crude oil remains a challenge for analytical chemists. With the development of multi-dimensional chromatography and high-resolution mass spectrometry, an impressive number of compounds can be identified in a single sample. However, the large diversity in structure and abundance makes it difficult to obtain full compound coverage. Sample preparation methods such as solid-phase extraction and SARA-type separations are used to fractionate oil into compound classes. However, the molecular diversity within each fraction is still highly complex. Thus, in the routine analysis, only a small part of the chemical space is typically characterized. Obtaining a more detailed composition of crude oil is important for production, processing and environmental aspects. We have developed a high-resolution fractionation method for isolation and preconcentration of trace aromatics, including oxygenated and nitrogen-containing species. The method is based on semi-preparative liquid chromatography. This yields high selectivity and efficiency with separation based on aromaticity, ring size and connectivity. By the separation of the more abundant aromatics, i.e., monoaromatics and naphthalenes, trace species were isolated and enriched. This enabled the identification of features not detectable by routine methods. We demonstrate the applicability by fractionation and subsequent GC-MS analysis of 14 crude oils sourced from the North Sea. The number of tentatively identified compounds increased by approximately 60 to 150% compared to solid-phase extraction and GC × GC-MS. Furthermore, the method was used to successfully identify an extended set of heteroatom-containing aromatics (e.g., amines, ketones). The method is not intended to replace traditional sample preparation techniques or multi-dimensional chromatography but acts as a complementary tool. An in-depth comparison to routine characterization techniques is presented concerning advantages and disadvantages.
Produced water is the largest by-product of oil and gas production. At off-shore installations, the produced water is typically reinjected or discharged into the sea. The water contains a complex mixture of dispersed and dissolved oil, solids and inorganic ions. A better understanding of its composition is fundamental to 1) improve environmental impact assessment tools and 2) develop more efficient water treatment technologies. The objective of the study was to screen produced water sampled from a producing field in the Danish region of the North Sea to identify any containing organic compounds. The samples were taken at a test separator and represent an unfiltered picture of the composition before cleaning procedures. The analytes were isolated by liquid-liquid extraction and derivatized using a silylation reagent to increase the volatility of oxygenated compounds. The final extracts were analyzed by comprehensive multi-dimensional gas chromatography coupled to a high-resolution mass spectrometer. A non-target processing workflow was implemented to extract features and quantify the confidence of library matches by correlation to retention indices and the presence of molecular ions. Approximately 120 unique compounds were identified across nine samples. Of those, 15 were present in all samples. The main types of compounds are aliphatic and aromatic carboxylic acids with a small fraction of hydrocarbons. The findings have implications for developing improved environmental impact assessment tools and water remediation technologies.
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