Microbial biofilm metabolization of benzalkonium compounds (benzyl dimethyl dodecyl ammonium & benzyl dimethyl tetradecyl ammonium chloride).

Benzalkonium chlorides (BACs) are quaternary ammonium compounds (QUATs) that are used as biocides. The degradation of these compounds in wastewater treatment plants is essential to reduce their spread into the environment and thus prevent the development of QUAT-resistant genes. The biodegradation of two BACs (BAC-12 and BAC-14) was investigated in moving bed biofilm reactors (MBBRs). Degradation half-lives of 12 and 20 h for BAC-12 and - 14, respectively, were detected as well as the formation of 42 metabolites. Two new degradation pathways for the BACs were identified in this study: 1) one involving an ω-oxidation, followed by ß-oxidation and 2) one via an ω-oxidation followed by an α-oxidation that was succeeded by ß-oxidation. Similar metabolites were detected for both BAC-12 and BAC-14. Additional metabolites were detected in the study, that could not be assigned to the above-mentioned pathways, revealing even more metabolic pathways in the MBBR which is probably due to the complexity of the microbial community in the biofilm. Interestingly, both TP194 (Benzyl-(carboxymethyl)-dimethylazanium) and TP208B (Benzyl-(2-carboxyethyl)-dimethylazanium) were identified as end products of the ω/ß-pathway and the α/ß-pathway. TP208B, TP152 and TP250 that were identified in this study, as well as the known BDMA were discovered in the effluent of a wastewater treatment plant.

Potential of nature-based solutions to reduce antibiotics, antimicrobial resistance, and pathogens in aquatic ecosystems. a critical review.

This comprehensive scientific review evaluates the effectiveness of nature-based solutions (NBS) in reducing antibiotics (ABs), combating antimicrobial resistance (AMR), and controlling pathogens in various aquatic environments at different river catchment levels. It covers conventional and innovative treatment wetland configurations for wastewater treatment to reduce pollutant discharge into the aquatic ecosystems as well as exploring how river restoration and saltmarshes can enhance pollutant removal. Through the analysis of experimental studies and case examples, the review shows NBS's potential for providing sustainable and cost-effective solutions to improve the health of aquatic ecosystems. It also evaluates the use of diagnostic indicators to predict NBS effectiveness in removing specific pollutants such as ABs and AMR. The review concludes that NBS are feasible for addressing the new challenges stemming from human activities such as the presence of ABs, AMR and pathogens, contributing to a better understanding of NBS, highlighting success stories, addressing knowledge gaps, and providing recommendations for future research and implementation.

Sartan blood pressure regulators in classical and biofilm wastewater treatment - Concentrations and metabolism.

Sartans are a group of pharmaceuticals widely used to regulate blood pressure. Their concentration levels were monitored in 80 wastewater treatment plants (WWTP) in the Baltic Sea Region, reached from limit of detection up to 6 µg/L. The concentrations were significantly different in different countries, but consistent within the respective country. The degradation of sartans (losartan, valsartan, irbesartan) in moving bed biofilm reactors (MBBRs) that utilize biofilms grown on mobile carriers to treat wastewater was investigated for the first time, and compared with the degradation in a conventional activated sludge (CAS) treatment plant. The results showed the formation of six microbial transformation products (TPs) of losartan, four of valsartan, and four of irbesartan in biological wastewater treatment. Four of these metabolites have not been described in the literature before. Chemical structures were suggested and selected TPs were verified and quantified depending on availability of true standards. Valsartan acid was a common TP of losartan, valsartan, and irbesartan. Losartan and irbesartan also shared one TP: losartan/irbesartan TP335. Based on the mass balance analysis, losartan carboxylic acid is the main TP of losartan, and valsartan acid is the main TP of valsartan during the biotransformation process. For irbesartan, TP447 is likely to be the main TP, as its peak areas were two orders of magnitude higher than those of all the other detected TPs of this compound. The effects of adapting biofilms to different biological oxygen demand (BOD) loading on the degradation of sartans as well as the formation of their TPs were investigated. Compared to feeding a poor substrate (pure effluent wastewater from a CAS), feeding with richer substrate (1/3 raw and 2/3 effluent wastewater) promoted the metabolism of most compounds (co-metabolization). However, the addition of raw wastewater inhibited some metabolic pathways of other compounds, such as from losartan/irbesartan to TP335 (competitive inhibition). The formation of irbesartan TP447 did not change with or without raw wastewater. Finally, the sartans and their TPs were investigated in a full-scale CAS wastewater treatment plant (WWTP). The removal of losartan, valsartan, and irbesartan ranged from 3.0 % to 72% and some of the transformation products (TPs) from human metabolism were also removed in the WWTP. However, some of the sartan TPs, i.e., valsartan acid, losartan carboxylic acid, irbesartan TP443 and losartan TP453, were formed in the WWTP. Relative high amounts of especially losartan carboxylic acid, which was detected with concentrations up to 2.27 µg/L were found in the effluent.

Occurrence and stability of ptesculentoside, caudatoside and ptaquiloside in surface waters.

The illudane glycosides ptesculentoside (PTE), caudatoside (CAU) and ptaquiloside (PTA) are found in bracken ferns (Pteridium sp.). PTA is known to contaminate water bodies adjacent to bracken ferns and hence contribute to water toxicity. This study for the first time reports the presence of PTE and CAU in surface waters with concentrations up to 5.3 µg L-1 and outlines their stability under semi-natural conditions using water of two diverse lakes at their natural pH or pH adjusted to 6.5, with temperature controlled at 5 or 15 °C, and in the presence or absence of microbial activity. Under the same set of tested conditions the three illudane glycosides degraded at similar rates: with half-lives of approximately two days at pH 7.4 and 15 °C, and approximately 12 days at pH 5.2-6.5 and 5 °C. The water origin had significant influence on the degradation rates, but only due to its difference in pH. In most cases, the degradation rates of all the three illudane glycosides could be predicted using the existing first-order model for PTA hydrolysis. As PTE and CAU exhibit the same leaching pattern and stability as PTA, previous predictions of bracken environmental impact are likely underestimated, as PTE and CAU have not been monitored and included in the risk assessment.

The invasive butterbur contaminates stream and seepage water in groundwater wells with toxic pyrrolizidine alkaloids.

Pyrrolizidine alkaloids (PAs) are persistent mutagenic and carcinogenic compounds produced by many common plant species. Health authorities recommend minimising human exposure via food and medicinal products to ensure consumer health and safety. However, there is little awareness that PAs can contaminate water resources. Therefore, no regulations exist to limit PAs in drinking water. This study measured a PA base concentration of ~ 70 ng/L in stream water adjacent to an invasive PA-producing plant Petasites hybridus (Asteraceae). After intense rain the PA concentration increased tenfold. In addition, PAs measured up to 230 ng/L in seepage water from groundwater wells. The dominant PAs in both water types corresponded to the most abundant PAs in the plants (senkirkine, senecionine, senecionine N-oxide). The study presents the first discovery of persistent plant toxins in well water and their associated risks. In addition, it for the first time reports monocrotaline and monocrotaline N-oxide in Petasites sp.

Fast LC-MS quantification of ptesculentoside, caudatoside, ptaquiloside and corresponding pterosins in bracken ferns.

Ptaquiloside (PTA) is an illudane glycoside partly responsible for the carcinogenicity of bracken ferns (Pteridium sp.). The PTA analogues ptesculentoside (PTE) and caudatoside (CAU) have similar biochemical reactivity. However, both compounds are highly under-investigated due to the lack of analytical standards and appropriate methods. This study presents a robust method for preparation of analytical standards of PTE, CAU, PTA, the corresponding hydrolysis products: pterosins G, A and B, and an LC-MS based method for simultaneous quantification of the six compounds in bracken. The chromatographic separation of analytes takes 5 min. The observed linear range of quantification was 20-500 µg/L for PTA and pterosin B, and 10-250 µg/L for the remaining compounds (r > 0.999). The limits of detection were 0.08-0.26 µg/L for PTE, CAU and PTA and 0.01-0.03 µg/L for the pterosins, equivalent to 2.0-6.5 µg/g and 0.25-0.75 µg/g in dry weight, respectively. The method was applied on 18 samples of dried fern leaves from 6 continents. Results demonstrated high variation in concentrations of PTE, CAU and PTA with levels prior to hydrolysis up to 3,900, 2,200 and 2,100 µg/g respectively. This is the first analytical method for simultaneous and direct measurement of all six compounds. Its application demonstrated that bracken ferns contain significant amounts of PTE and CAU relative to PTA.

Hemorrhagic diathesis in cattle due to consumption of Adiantopsis chlorophylla (Swartz) Fée (Pteridaceae).

An outbreak of acute febrile syndrome associated with coagulopathy and severe pancytopenia occurred in cattle grazing in paddocks with high infestation by Adiantopsis chlorophylla. The administration of the plant to a calf reproduced the same signs and lesions seen in spontaneous cases. Similar syndromes are caused by ptaquiloside from bracken fern. Traces of the ptaquiloside-like molecule caudatoside were detected together with 0.03-0.24 mg/g of it's degradation product pterosin A, in dry fronds of the plant. In conclusion, A. chlorophylla is a cause of hemorrhagic diathesis in cattle.