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Formation of Nonextractable Residues of Sulfonamides with Soil Organic Matter- Mechanisms and Detection by High Resolution Tandem Mass Spectrometry

Applicant Hollender Juliane
Number 132746
Funding scheme Project funding
Research institution Swiss Federal Institute of Aquatic Science and Technology (EAWAG)
Institution of higher education Swiss Federal Institute of Aquatic Science and Technology - EAWAG
Main discipline Other disciplines of Environmental Sciences
Start/End 01.10.2010 - 31.07.2011
Approved amount 46'131.00
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Keywords (7)

Sulfonamides; Nonextractable Residues; High Resolution Mass Spectrometry; Soil Organic Matter; Sorption; soil; antibiotics

Lay Summary (English)

Lead
Lay summary
The input of veterinary antibiotics such as sulfonamides into the environment is of concern because of their potential to invoke bacterial resistance or to exert adverse effects on microbial communities. After input into soils, a major part cannot be recovered by conventional extraction methods. The added sulfonamides thus form "nonextractable residues" (NER). The mechanisms postulated for NER formation are either physical entrapment in organic matter or covalent bond formation. Our own and other studies suggest that the rapid initial NER formation of sulfonamides is probably caused by covalent bonding. Based on long- and short-term batch studies with humic acids, quinone and other carbonyl-containing monomers, we could show that the main pathway of covalent bond formation of sulfonamides occurs by nucleophilic addition rather than by radical reactions, and the formation of reactive quinones by oxidative enzymes or Mn oxides is the rate-limiting step. Currently, we are developing a method to detect NERs of sulfonamides based on high pressure size-exclusion chromatography coupled to soft ionization high resolution mass spectrometry (HPSEC-MS/MS) to detect sulfonamide NERs in organic matter isolates. The objectives of the project are (i) combining this HPSEC-MS/MS method with a sequential extraction procedure to detect sulfonamide NER in soils, and (iv) to study the relevant mechanisms of sulfonamide covalent bond formation in soil by selective sample manipulation. For these studies, 14C-labeled sulfamethazine will be used. The sequential extraction procedure starts with a pressurized liquid extraction (PLE) of sulfonamides. To release organic matter and sulfonamide NER from the PLE-extracted soil, we will evaluate two different extraction procedures and develop appropriate purification steps to make these extracts SEC-MS amendable. The relevant mechanisms in soils will be assessed by applying this method to soil samples, in which either Mn oxides are selectively removed, oxidative enzymes are inhibited or Mn oxides and free enzymes are added prior to incubation. Furthermore, the nucleophilic addition reaction itself will be targeted by addition of a competing nucleophile and addition of selected model hydroquinones to increase the pools of compounds available to form quinones. From a direct comparison of the different treatments we will get insights in the limiting factors and mechanisms driving the NER formation of sulfonamides in soils from both, macroscopic distribution among different fractions and application of the HPSEC-MS/MS method.
Direct link to Lay Summary Last update: 21.02.2013

Responsible applicant and co-applicants

Employees

Name Institute

Publications

Publication
Nonextractable residue formation of sulfonamide antimicrobials: new insights from soil incubation experiments,
Gulkowska A. B. Thalmann J. Hollender M. Krauss (2014), Nonextractable residue formation of sulfonamide antimicrobials: new insights from soil incubation experiments,, in Chemosphere, 10, 366-372.
Covalent binding of sulfamethazine to natural and synthetic humic acids: Assessing laccase catalysis and covalent bond stability
Gulkowska Anna, Sander Michael, Hollender Juliane, Krauss Martin (2013), Covalent binding of sulfamethazine to natural and synthetic humic acids: Assessing laccase catalysis and covalent bond stability, in Environmental Science and Technology, 47(13), 6916-6924.
Reactions of a sulfonamide antimicrobial with model humic constituents: Assessing pathways and stability of covalent bonding
Gulkowska Anna, Krauss Martin, Rentsch Daniel, Hollender Juliane (2012), Reactions of a sulfonamide antimicrobial with model humic constituents: Assessing pathways and stability of covalent bonding, in Environmental Science and Technology, 46(4), 2102-2111.
NONEXTRACTABLE RESIDUES OF SULFONAMIDE ANTIMICROBIALS IN SOIL - FORMATION MECHANISMS WITH ORGANIC MATTER AND STABILITY
Anna Gulkowska (2011), NONEXTRACTABLE RESIDUES OF SULFONAMIDE ANTIMICROBIALS IN SOIL - FORMATION MECHANISMS WITH ORGANIC MATTER AND STABILITY, e-collection library ethz, Zürich.

Collaboration

Group / person Country
Types of collaboration
EMPA Switzerland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure

Scientific events

Active participation

Title Type of contribution Title of article or contribution Date Place Persons involved
ACS (American Chemical Society) conference Talk given at a conference Nonextractable residue formation of sulfonamides 28.08.2011 Denver, United States of America Gulkowska Anna; Krauss Martin; Hollender Juliane;
21th Annual Meeting of SETAC Europe (Society of Environmental Toxicology and Chemistry) Talk given at a conference Nonextractable residue formation of sulfonamides 15.05.2011 Milano, Italy Gulkowska Anna; Hollender Juliane; Krauss Martin;


Associated projects

Number Title Start Funding scheme
116557 Formation of Nonextractable Residues of Sulfonamides with Soil Organic Matter- Mechanisms and Detection by High Resolution Tandem Mass Spectrometry 01.08.2007 Project funding

Abstract

The input of veterinary antibiotics such as sulfonamides into the environment is of concern because of their potential to invoke bacterial resistance or to exert adverse effects on microbial communities. After input into soils, a major part cannot be recovered by conventional extraction methods. The added sulfonamides thus form “nonextractable residues” (NER). The mechanisms postulated for NER formation are either physical entrapment in organic matter or covalent bond formation. Our own and other studies suggest that the rapid initial NER formation of sulfonamides is probably caused by covalent bonding. Based on long- and short-term batch studies with humic acids, quinone and other carbonyl-containing monomers, we could show that the main pathway of covalent bond formation of sulfonamides occurs by nucleophilic addition rather than by radical reactions, and the formation of reactive quinones by oxidative enzymes or Mn oxides is the rate-limiting step. Currently, we are developing a method to detect NERs of sulfonamides based on high pressure size-exclusion chromatography coupled to soft ionization high resolution mass spectrometry (HPSEC-MS/MS) to detect sulfonamide NERs in organic matter isolates. The objectives of the fourth year of this project are (i) combining this HPSEC-MS/MS method with a sequential extraction procedure to detect sulfonamide NER in soils, and (iv) to study the relevant mechanisms of sulfonamide covalent bond formation in soil by selective sample manipulation. For these studies, 14C-labeled sulfamethazine will be used. The sequential extraction procedure starts with a pressurized liquid extraction (PLE) of sulfonamides. To release organic matter and sulfonamide NER from the PLE-extracted soil, we will evaluate two different extraction procedures and develop appropriate purification steps to make these extracts SEC-MS amendable. The relevant mechanisms in soils will be assessed by applying this method to soil samples, in which either Mn oxides are selectively removed, oxidative enzymes are inhibited or Mn oxides and free enzymes are added prior to incubation. Furthermore, the nucleophilic addition reaction itself will be targeted by addition of a competing nucleophile and addition of selected model hydroquinones to increase the pools of compounds available to form quinones. From a direct comparison of the different treatments we will get insights in the limiting factors and mechanisms driving the NER formation of sulfonamides in soils from both, macroscopic distribution among different fractions and application of the HPSEC-MS/MS method.
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