@misc{KuhnJenschBryantetal., author = {Kuhn, Ramona and Jensch, Robert and Bryant, Isaac Mbir and Fischer, Thomas and Liebsch, Stephan and Martienssen, Marion}, title = {Rapid sample clean-up procedure for aminophosphonate determination by LC/MS analysis}, series = {Talanta}, volume = {208}, journal = {Talanta}, issn = {0039-9140}, doi = {10.1016/j.talanta.2019.120454}, pages = {6}, abstract = {Aminophosphonates are commonly utilised for complexing bivalent ions such as calcium and magnesium. With regard to environmental samples, the analysis of these highly polar compounds is still challenging due to matrix effects and lacking analytical standard methods. We have recently developed a LC/MS method for common aminophosphonates without derivatisation. This LC/MS method delivers precise and accurate measurement for standard samples with very low concentration of cations disturbing the analysis. However, due to matrix effects this LC/MS method requires a sample clean-up being also applicable to natural water or wastewater samples. We developed and optimised a sample clean-up procedure applying strong cation exchange resin Dowex 50WX8. This clean-up allows a single LC/MS analysis of hydroxyethelidene(diphosphonic acid) (HEDP), aminotris(methylenephosphonic acid) (ATMP), ethylenediaminetetra(methyloenephosphonic acid) (EDTMP), diethylenetriaminepenta(methylenephosphonic acid) (DTPMP) and its major intermediates amino(methylphosphonic acid) (AMPA) and iminodi(methylenephosphonic acid) (IDMP). We compared different test conditions with six aminophosphonates in either ultra pure water or tap water. The latter was used to simulate cation concentrations typical for natural waters. To elute all aminophosphonate including AMPA, ammonium acetate addition was necessary. The addition of ammonium acetate was combinable with all tested aminophosphonates and provides high sample quality for LC/MS analysis. For acceptable recovery, the smallest aminophosphonate AMPA required the highest addition of ammonium acetate (1000 mg L-1) during the sample clean-up. Finally, the optimised clean-up procedure was successfully applied to identify and quantify phosphonates from an industrial wastewater sample. The sample clean-up procedure is simple, cheap, rapid and precise and can be further combined with solid phase extraction and more sensitive LC/MS methods.}, language = {en} } @misc{PreussVornholtKuhnetal., author = {Preuß, Volker and Vornholt, Carsten and Kuhn, Ramona and Martienssen, Marion}, title = {Untersuchung zur Membrang{\"a}ngikeit von Antiscalants}, series = {Verfahren der Wasseraufbereitung und Abwasserbehandlung : 13. Aachener Tagung Wassertechnologie : Begleitbuch : 29.-30. Oktober 2019}, journal = {Verfahren der Wasseraufbereitung und Abwasserbehandlung : 13. Aachener Tagung Wassertechnologie : Begleitbuch : 29.-30. Oktober 2019}, editor = {Pinnekamp, Johannes and Wessling, Matthias}, publisher = {Aachener Verfahrenstechnik, RWTH Aachen ; Institut f{\"u}r Siedlungswasserwirtschaft, RWTH Aachen}, address = {Aachen}, isbn = {978-3-95886-305-7}, pages = {117 -- 123}, language = {de} } @misc{KuhnJenschBryantetal., author = {Kuhn, Ramona and Jensch, Robert and Bryant, Isaac Mbir and Fischer, Thomas and Liebsch, Stephan and Martienssen, Marion}, title = {Photodegradation of ethylenediaminetetra(methylenephosphonic acid) - The effect of the system configuration}, series = {Journal of Photochemistry \& Photobiology A: Chemistry}, volume = {388}, journal = {Journal of Photochemistry \& Photobiology A: Chemistry}, issn = {1010-6030}, doi = {10.1016/j.jphotochem.2019.112192}, pages = {9}, abstract = {Photodegradation of aminophosphonates such as ethylenediaminetetra(methylenephosphonic acid) (EDTMP) is recently assumed being the major degradation pathway in aquatic environments. Several photolysis studies were reported about EDTMP and possible breakdown products occurring in natural ecosystems. Reliable prediction of environmental photolysis of parent compounds and possible release of breakdown products requires different set-up conditions and varying the parameters influencing the photodegradation. We studied the influence of three different system configurations during UV degradation of EDTMP. These three configurations differed either in geometry and/or treated sample volumes. System 1 was equipped with a direct cooling jacket at the UV lamp. System 2 had the geometry of system 1 but there was no usage of a direct cooling jacket. System 3 was a gas-tight system with a larger sample volume. Using the chemical actinometer potassium ferrioxalate, we determined the highest photon flux for system 3 followed by system 2 and 1. In addition, we performed scavenger experiments with methanol and ascorbic acid in order to prove the dominating radical species. In system 1, the addition of methanol showed almost no effect while the ascorbic acid resulted in a reduction of 57.1\% orthophosphate released. Therefore we conclude that in system 1 the radical-drive degradation of EDTMP is mainly based on superoxide radicals. In system 2 and 3 both radical species, i.e., hydroxyl radicals and superoxide radicals, contribute to the photodegradation of EDTMP. We determined different half-lives for EDTMP for the three different systems configurations. For system 1, the estimated half-life achieved was 14.09 ± 0.15 min. For system 2 and 3, the half-lives were almost similar and averaged 4.75 ± 0.05 min and 5.02 ± 0.20 min, respectively. Contrary to our assumption to also find the highest degradation rate for system 3, we found the highest degradation rate for system configuration 2 as a result of the differences in the construction and geometry of the three systems. Our findings lead us to recommend the three system configuration for different research purposes. Thus, we recommend system 1 for detailed studies on the degradation pathway of the parent compound and their breakdown products. System 2 is recommended as a suitable configuration for kinetic studies of the parent compound. And finally, we recommend the system configuration 3 for complete mass balances. The gas-tight system allows determining all soluble and gaseous compounds.}, language = {en} } @misc{PreussVornholtKuhnetal., author = {Preuß, Volker and Vornholt, Carsten and Kuhn, Ramona and Martienssen, Marion}, title = {Untersuchung zur Membrang{\"a}ngigkeit von Antiscalants}, series = {13. Aachener Tagung Wassertechnologie : Verfahren der Wasseraufbereitung und Abwasserbehandlung}, volume = {2019}, journal = {13. Aachener Tagung Wassertechnologie : Verfahren der Wasseraufbereitung und Abwasserbehandlung}, editor = {Wessling, Matthias and Pinnekamp, Johannes}, edition = {1. Auflage}, publisher = {Verlagshaus Mainz GmbH Aachen}, address = {Aachen}, isbn = {978-3-95886-305-7}, doi = {10/35549368458}, pages = {117 -- 123}, abstract = {Aminophosphonate sind synthetisch hergestellte Komplexbildner, die kovalente C-P Bindungen aufweisen. Durch zus{\"a}tzlich eingef{\"u}gte Aminogruppen (NH2) komplexieren Amino-phosphonate besonders gut Metallionen, weshalb sie in einem sehr breiten Anwendungsspektum zum Einsatz kommen. So werden Phosphonate vielseitig als Haushalts- und Industriereiniger, aber auch als Komponenten von Kosmetika und in der Medizin verwendet. Des weiteren werden sie zur K{\"u}hlwasserkonditionierung, Stabilisierung von Peroxiden oder Bleichb{\"a}dern und als Korrosionsinhibiter eingesetzt. Entsprechend der vielseitigen Anwendungsgebiete lag bereits in den fr{\"u}her 90igern des vergangenen Jahrhunderts die Gesamtproduktion an Phosphonaten in Europa bei {\"u}ber 11.000 Tonnen pro Jahr (Jaworska et al., 2002). Weltweit zeigen die Nutzung und der damit verbundene Bedarf an Phosphonaten einen immer weiter steigenden Trend. Dem entgegen steht der noch immer wenig untersuchte Verbleib und das chemische Verhalten von Phosphonaten in der Umwelt. Die gegenw{\"a}rtig technisch eingesetzten Phosphonate {\"a}hneln in ihrer Struktur den bekannteren Aminocarboxylaten wie dem EDTA und NTA. Chemisch synthetisierte Phosphonate sind nur schwer biologisch abbaubar, weshalb zu einer kontinuierlichen Anreicherung in der aquatischen Umwelt kommen kann (Jaworska et al., 2002). Dies liegt unter anderem auch daran, dass Phosphonate als Phosphatersatz in großen Mengen in Waschmitteln enthalten sind und {\"u}ber das Abwasser in die Kl{\"a}ranlagen gelangen, wo sie nicht weiter biologisch abgebaut werden. Sie werden haupts{\"a}chlich durch Absorption an die Oberfl{\"a}che vom Belebtschlamm aus den Abwasser entfernt. Nowack (2004) beschrieb die Toxizit{\"a}t von Phosphonaten in Kl{\"a}ranlagen als gering, verwies aber gleichzeitig darauf, dass aufgrund ihrer hohen Stabilit{\"a}t Phosphonate hemmend auf Proteasen und Syntheasen (Enzyme) von Mikroorganismen wirken. Der photochemische und biologische Abbau von dem Phosphonat EDTMP wurde eingehend untersucht, um dessen Umweltverhalten besser absch{\"a}tzen zu k{\"o}nnen. Ziel der Untersuchungen war es den Abbauprozess zu entschl{\"u}sseln als Grundlage f{\"u}r die langfristige Entwicklung umweltvertr{\"a}glicher Aminophosphonatstrukturen. Der photochemische Abbau von EDTMP und die Bildung von Metaboliten konnte mittels LC-MS und 31P-NMR bereits aufgekl{\"a}rt werden. So zeigt sich das EDTMP bereits nach wenigen Minuten im UV-Licht zerf{\"a}llt und nicht mehr nachgewiesen werden kann. Als Hauptprodukt konnte das Phosphonat IDMP identifiziert werden. Als weitere Abbauprodukte konnten die Phosphonate EABMP und AMPA identifiziert werden. In allen Versuchen konnte nach 300 min UV-Behandlung mindestens 75\% des Endprodukts CO2 nachgewiesen werden. Weitere drei maßgebliche Abbauprodukte wurden mit Hilfe der LC-MS gefunden. Deren chemische Struktur konnte bisher jedoch noch nicht eindeutig beschrieben werden. Im Anschluss an die UV-Experimente wurde ein Versuch mit Sonnenlicht simuliert. Insgesamt verlief der EDTMP-Abbau im Sonnenlicht wesentlich langsamer. Auch hier konnten wieder dieselben Abbauprodukte IDMP, EABMP und AMPA identifiziert werden. Zus{\"a}tzlich traten auch die drei noch nicht eindeutig identifizierten Metaboliten von EDTMP auf. Aus den gewonnen Daten kann somit geschlussfolgert werden, dass EDTMP unter Einwirkung von UV-Licht abbaubar ist. Die Annahme, dass EDTMP und dessen Abbauprodukte langfristig zur Sch{\"a}digung des aquatischen {\"O}kosystems f{\"u}hrt, kann somit nicht best{\"a}tigt werden. In weiteren Untersuchungen wurde der biologische Abbau von EDTMP und seiner photochemischen Abbauprodukten eingehend studiert. F{\"u}r die Abbauversuche wurden die beiden St{\"a}mme Pseudomonas aeruginosa und Ochrobactrum sp. aus Boden isoliert. Es konnte gezeigt werden, dass sie 1mM EDTMP innerhalb von 35 Tagen zu mindestens 94\% abbauen. Zus{\"a}tzlich zum biologischen Abbau von EDTMP wurden auch die Verdopplungszeitung der beiden St{\"a}mme f{\"u}r EDTMP, IDMP, EABMP und AMAP ermittelt. Es zeigte sich, dass der Stamm P. aeruginosa f{\"u}r alle vier Phosphonate ein besseres wachstum zeigte als Ochrobactrum sp. Der Stamm P. aeruginosa erreichte f{\"u}r die Verstoffwechselung von EDTMP eine Verdopplungszeit von 10,1 Tagen, f{\"u}r IDMP 7,4 Tage, f{\"u}r EABMP 7,4 Tage und f{\"u}r AMPA 13,7 Tage. Der Stamm Ochrobactrum sp. erreichte f{\"u}r das Substrat EDTMP eine Verdopplungszeit von 11,8 Tagen, f{\"u}r IDMP 18,9 Tage, f{\"u}r EABMP 7,7 Tage und f{\"u}r AMPA 22,0 Tage. Offensichtlich war f{\"u}r beide St{\"a}mme der Abbau von AMPA der limitierende, aber nicht hemmende Schritt im biologischen Abbau. Somit kann geschlussfolgert werden, dass die Abbauprodukte der Photolyse auch biologisch abgebaut werden k{\"o}nnen. In weiteren Untersuchungen soll der biologische Abbau auf enzymatischer Ebene entschl{\"u}sselt werden. Die Identifizierung der Sch{\"u}sselenzyme spielt hierbei eine wesentliche Rolle, um neuartige Phosphonatstrukturen herzuleiten, die auf der einen Seite ihre Funktionalit{\"a}t und Eigenschaften behalten, aber auf der anderen Seite eine erheblich verbesserte Bioverf{\"u}gbarkeit aufweisen, so dass eine dauerhafte Akkumulation in der Umwelt und Folgebeeintr{\"a}chtigungen minimiert ggf. ausgeschlossen werden k{\"o}nnen.}, language = {de} } @misc{KuhnBryantJenschetal., author = {Kuhn, Ramona and Bryant, Isaac Mbir and Jensch, Robert and Liebsch, Stephan and Martienssen, Marion}, title = {Photolysis of hexamethylenediaminetetra(methylenephosphonic acid) (HDTMP) using manganese and hydrogen peroxide}, series = {Emerging Contaminants}, volume = {2020}, journal = {Emerging Contaminants}, number = {6}, doi = {10.1016/j.emcon.2019.11.003}, pages = {10 -- 19}, abstract = {Aminophosphonates such as hexamethylenediaminetreta(methylene phosphonic acid) (HDTMP) are categorised as persistent substances. They are commonly used as scale inhibitors in cooling water systems and desalination processes. After utilisation, they are often discharged into aquatic environment without pre-treatment. Advanced oxidation processes (AOP) are promising pre-treatments for industrial wastewater treatments. We investigated the photodegradation of HDTMP with or without addition of manganese (Mn2þ) and/or H2O2. Similar to results of our former photodegradation studies, we found that HDTMP also undergoes conversion with or without additives during the ultra violet (UV) irradiation. The reaction rate was most affected by the addition of H2O2, i.e. the HDTMP degradation was accelerated by a factor 3.85 compared with UV treatment without additives. The addition of Mn2þ accelerated the degradation of HDTMP only by a factor 1.53 compared with the UV treatment without additives. The combined addition of Mn2þ and H2O2 accelerated the HDTMP degradation by a factor 2.81. Interestingly, the initial cleavage is not initiated as expected at the CeN bond but at the CeP bond of the methyl carbon and the phosphorus of the methylenephosphonic acid group of HDTMP. This initial cleavage was independent whether the UV treatment was performed with or without additives. Therefore, we conclude that the degradation mechanism is similar independent of the four tested treatment conditions. We identified amino(methylenephosphonic acid) AMPA, dimethylamino(methylenephosphonic acid) DAMP and iminodi(methylenephosphonic acid) IDMP as the major breakdown products by performing LC/MS analyses. The major mineralisation products were ortho-phosphate, ammonium and carbon dioxide. The mass balances of unknown breakdown products}, language = {en} } @misc{KuhnBryantMartienssen, author = {Kuhn, Ramona and Bryant, Isaac Mbir and Martienssen, Marion}, title = {Supplementary data on rapid sample clean-up procedure for aminophosphonate determination by LC/MS analysis}, series = {MethodsX}, volume = {07}, journal = {MethodsX}, issn = {2215-0161}, doi = {10.1016/j.mex.2020.100933}, pages = {1 -- 11}, abstract = {Minimising matrix effects through high sample purity is of major importance for LC/MS analysis. Here we provide supplementary data and protocols related to the article "Rapid sample clean-up procedure of aminophosphonates for LC/MS analysis"(revised article submitted to Talanta) [1] . It is demonstrated that the tested phosphonates iminodi(methylenephosphonic acid) (IDMP), hydroxyethelidene(diphosphonic acid) (HEDP), aminotris(methylenephosphonic acid) (ATMP), ethylenediaminetetra(methyloenephosphonic acid) (EDTMP) and diethylenetriaminepenta(methylenephosphonic acid) (DTPMP) dissolved in tap water are not detectable by LC/MS without sample clean-up. Only the smallest aminophosphonate amino(methylenephosphonic acid) (AMPA) was detectable but the recovery is decreased drastically. The optimised sample clean-up with cation exchange resin (CER) Dowex 50WX8 is described in detail and illustrated. The protocol is provided. The influence of the incubation time, addition of different ammonium acetate concentrations, different samples pHs and different water qualities is demonstrated and preferred clean- up conditions are recommended. Calibration results of all tested aminophosphonates are validated regarding limit of detection, limit of quantification, lower limit of quantification, absolute and relative process standard deviation. A final recommendation for the best clean-up condition for all six tested aminophosphonates is provided.}, language = {en} } @misc{KuhnVornholtPreussetal., author = {Kuhn, Ramona and Vornholt, Carsten and Preuß, Volker and Bryant, Isaac Mbir and Martienssen, Marion}, title = {Aminophosphonates in Nanofiltration and Reverse Osmosis Permeates}, series = {Membranes}, volume = {11}, journal = {Membranes}, number = {6}, issn = {2077-0375}, doi = {10.3390/membranes11060446}, pages = {1 -- 16}, abstract = {Aminophosphonates such as aminotris(methylenephosphonic acid) (ATMP) are common constituents of antiscalants. In nanofiltration (NF) and reverse osmosis (RO) processes, ATMP prevents inorganic scaling leading to more stable membrane performance. So far, little attention has been paid to the possible permeation of aminophosphonates through NF and RO membranes. We have investigated the permeability of these membrane types for ATMP and its potential metabolites iminodi(methylenephosphonic acid) (IDMP) and amino(methylenephosphonic acid) (AMPA) with two different NF membranes (TS40 and TS80) and one RO membrane (ACM2) and three different water compositions (ultra-pure water, synthetic tap water and local tap water). We found traces of phosphonates in all investigated permeates. The highest phosphonate rejection occurred with local tap water for all three membranes investigated. Filtration experiments with a technical antiscalant formulation containing ATMP indicated similar trends of phosphonate permeability through all three membranes. We assume that the separation mechanisms of the membranes are the results of a very complex relationship between physico-chemical properties such as Donnan exclusion, feed pH, feed ionic strength and feed concentration, as well as solute-solute interactions.}, language = {en} } @misc{HertelGibhardtMartienssenetal., author = {Hertel, Robert and Gibhardt, Johannes and Martienssen, Marion and Kuhn, Ramona and Commichau, Fabian M.}, title = {Molecular mechanisms underlying glyphosate resistance in bacteria}, series = {Environmental Microbiology}, volume = {23}, journal = {Environmental Microbiology}, number = {6}, issn = {1462-2920}, doi = {10.1111/1462-2920.15534}, pages = {2891 -- 2905}, abstract = {Glyphosate is a nonselective herbicide that kills weeds and other plants competing with crops. Glyphosate specifically inhibits the 5-enolpyruvyl-shikimate-3-phosphate (EPSP) synthase, thereby depleting the cell of EPSP serving as a precursor for biosynthesis of aromatic amino acids. Glyphosate is considered to be toxicologically safe for animals and humans. Therefore, it became the most-important herbicide in agriculture. However, its intensive application in agriculture is a serious environmental issue because it may negatively affect the biodiversity. A few years after the discovery of the mode of action of glyphosate, it has been observed that bacteria evolve glyphosate resistance by acquiring mutations in the EPSP synthase gene, rendering the encoded enzyme less sensitive to the herbicide. The identification of glyphosate-resistant EPSP synthase variants paved the way for engineering crops tolerating increased amounts of the herbicide. This review intends to summarize the molecular mechanisms underlying glyphosate resistance in bacteria. Bacteria can evolve glyphosate resistance by (i) reducing glyphosate sensitivity or elevating production of the EPSP synthase, by (ii) degrading or (iii) detoxifying glyphosate and by (iv) decreasing the uptake or increasing the export of the herbicide. The variety of glyphosate resistance mechanisms illustrates the adaptability of bacteria to anthropogenic substances due to genomic alterations.}, language = {en} } @misc{HertelSchoeneMittelstaedtetal., author = {Hertel, Robert and Sch{\"o}ne, Kerstin and Mittelst{\"a}dt, Carolin and Meißner, Janek and Zschoche, Nick and Collignon, Madeline and Kohler, Christian and Friedrich, Ines and Schneider, Dominik and Hoppert, Michael and Kuhn, Ramona and Schwedt, Inge and Scholz, Patricia and Poehlein, Anja and Martienssen, Marion and Ischebeck, Till and Daniel, Rolf and Commichau, Fabian M.}, title = {Characterization of glyphosate-resistant Burkholderia anthina and Burkholderia cenocepacia isolates from a commercial Roundup® solution}, series = {Environmental Microbiology Reports}, volume = {14}, journal = {Environmental Microbiology Reports}, number = {1}, issn = {1758-2229}, doi = {10.1111/1758-2229.13022}, pages = {70 -- 84}, abstract = {Roundup® is the brand name for herbicide solutions containing glyphosate, which specifically inhibits the 5-enolpyruvyl-shikimate-3-phosphate (EPSP) synthase of the shikimate pathway. The inhibition of the EPSP synthase causes plant death because EPSP is required for biosynthesis of aromatic amino acids. Glyphosate also inhibits the growth of archaea, bacteria, Apicomplexa, algae and fungi possessing an EPSP synthase. Here, we have characterized two glyphosate-resistant bacteria from a Roundup solution. Taxonomic classification revealed that the isolates 1CH1 and 2CH1 are Burkholderia anthina and Burkholderia cenocepacia strains respectively. Both isolates cannot utilize glyphosate as a source of phosphorus and synthesize glyphosate-sensitive EPSP synthase variants. Burkholderia. anthina 1CH1 and B. cenocepacia 2CH1 tolerate high levels of glyphosate because the herbicide is not taken up by the bacteria. Previously, it has been observed that the exposure of soil bacteria to herbicides like glyphosate promotes the development of antibiotic resistances. Antibiotic sensitivity testing revealed that the only the B. cenocepacia 2CH1 isolate showed increased resistance to a variety of antibiotics. Thus, the adaptation of B. anthina 1CH1 and B. cenocepacia 2CH1 to glyphosate did not generally increase the antibiotic resistance of both bacteria. However, our study confirms the genomic adaptability of bacteria belonging to the genus Burkholderia.}, language = {en} } @misc{KuhnBryantJenschetal., author = {Kuhn, Ramona and Bryant, Isaac Mbir and Jensch, Robert and B{\"o}llmann, J{\"o}rg}, title = {Applications of Environmental Nanotechnologies in Remediation, Wastewater Treatment, Drinking Water Treatment, and Agriculture}, series = {Applied Nano}, volume = {3}, journal = {Applied Nano}, number = {1}, issn = {2673-3501}, doi = {10.3390/applnano3010005}, pages = {54 -- 90}, abstract = {Today, nanotechnologies (NTs) are well established in both private households and commercial markets. NTs are fully accepted in several sectors, such as medicine and pharmacy, and in industries, such as chemistry, electricity, food production, military, and other commercial branches, due to their unique properties. With regard to the growing demands for environmental resources caused by the still-growing global population, the application of NTs is an extremely important new branch in the environmental sector, delivering several advantages. Our review provides a comprehensive overview of the current developments in environmental remediation, wastewater treatment, drinking water treatment, and agriculture. More specifically, in the section on environmental remediation, we review the application of NTs towards enhanced reductive dechlorination, removal of heavy metals and remediation of oil spills. In the section on wastewater treatment, we highlight developments in the adsorption of heavy metals and persistent substances, advanced photocatalytic degradation of common wastewater pollutants, and improvements in membrane filtration processes. In the section on drinking water treatment, we discuss applications for the enhanced disinfection of pathogens, removal of heavy metals, point-of-use treatments, and the removal of organic matter. In the final section, on agriculture, we provide an overview of precision farming and the current state of the art concerning nanofertilisers, nanopesticides, nanoherbicides, and nano(bio)sensors.}, language = {en} } @misc{KuhnJenschFischeretal., author = {Kuhn, Ramona and Jensch, Robert and Fischer, Thomas and Keuler, Klaus and Bryant, Isaac Mbir and Martienssen, Marion}, title = {Sunlight Degradation of the Aminophosphonate Diethylenetriamine Penta-(Methylenephosphonic Acid)}, series = {Solar}, volume = {2}, journal = {Solar}, number = {2}, issn = {2673-9941}, doi = {10.3390/solar2020009}, pages = {141 -- 157}, abstract = {Aminophosphonate diethylenetriamine penta(methylenephosphonic acid) (DTPMP) is a scale inhibitor commonly used in several industries. DTPMP is suspected to cause anthropogenic pollution through discharge into the aquatic environment. DTPMP is assumed to be degraded by sunlight radiation. We recently predicted a preliminary degradation pathway of DTPMP applyingUV treatment. Currently, we have not yet evidenced that DTPMP shows the same degradation pattern with natural sunlight. One major reason leads to the fact that the light spectrum emitted by UV lamps does not completely represent the natural sunlight spectrum, and the emitted UVB and UVA irradiation flux is much higher than for solar light. For that reason, the degradation pattern and kinetics might be different between artificial UV treatment and natural sunlight treatment. Here, we investigated whether DTPMP is degradable under natural sunlight radiation, and whether the degradation mechanisms determined through UV treatment are transferable to sunlight. We investigated five different treatment conditions, i.e., DTPMP degradation in direct or diffuse sunlight, in diffuse sunlight with addition of Ca2+ or Mg2+, and in diffuse sunlight with local TW. Our experiment was carried out from March 2021 to October 2021. We performed LC/MS analyses and measured the release of o-PO4 3 . DTPMP was degraded with all five treatment conditions. The fastest DTPMP degradation occurred in direct and diffuse sunlight without addition of bivalent cations. The addition of Ca2+ and Mg2+ resulted in inhibited degradation. Similar effects occurred for sunlight treatment with local TW. We evidenced different degradation mechanisms for DTPMP depending on the presence of alkaline earth metals as we previously proposed for UV-treated DTPMP. However, both degradation mechanisms of DTPMP belong to the same degradation pathway determined with UV treatment. Therefore, we conclude that DTPMP undergoes a similar degradation pathway in sunlight as compared to UV light.}, language = {en} }