Monitoring Pharmaceuticals and Personal Care Products in Healthcare Effluent Wastewater Samples and the Effectiveness of Drug Removal in Wastewater Treatment Plants Using the UHPLC-MS/MS Method.

A multi-residue UHPLC-MS/MS analytical method, previously developed for monitoring 52 pharmaceuticals in drinking water, was used to analyse these pharmaceuticals in wastewater originating from healthcare facilities in the Czech Republic. Furthermore, the methodology was expanded to include the evaluation of the effectiveness of drug removal in Czech wastewater treatment plants (WWTPs). Of the 18 wastewater samples analysed by the validated UHPLC-MS/MS, each sample contained at least one quantifiable analyte. This study reveals the prevalence of several different drugs; mean concentrations of 702 µg L-1 of iomeprol, 48.8 µg L-1 of iopromide, 29.9 µg L-1 of gabapentin, 42.0 µg L-1 of caffeine and 82.5 µg L-1 of paracetamol were present. An analysis of 20 samples from ten WWTPs revealed different removal efficiencies for different analytes. Paracetamol was present in the inflow samples of all ten WWTPs and its removal efficiency was 100%. Analytes such as caffeine, ketoprofen, naproxen or atenolol showed high removal efficiencies exceeding 80%. On the other hand, pharmaceuticals like furosemide, metoprolol, iomeprol, zolpidem and tramadol showed lower removal efficiencies. Four pharmaceuticals exhibited higher concentrations in WWTP effluents than in the influents, resulting in negative removal efficiencies: warfarin at -9.5%, indomethacin at -53%, trimethoprim at -54% and metronidazole at -110%. These comprehensive findings contribute valuable insights to the pharmaceutical landscape of wastewater from healthcare facilities and the varied removal efficiencies of Czech WWTPs, which together with the already published literature, gives a more complete picture of the burden on the aquatic environment.

Is the reliability of wastewater-based epidemiology affected by season? Comparative analysis with pharmaceuticals prescriptions.

Wastewater-based epidemiology (WBE) has been already proposed by several authors for estimating the consumption of drugs, mainly the illicit ones. However, not much information is available about the actual reliability of this tool given the absence of comparison with the actual consumption. This work aims to evaluate the reliability of the WBE as a tool for estimating the consumption of pharmaceuticals in urban area. Measured consumption back-calculated with a WBE approach was compared with prescription of pharmaceutical products as "control." Moreover, seasonal influence on (i) pharmaceutical consumption, (ii) load of pharmaceutical products in the sewer system, and (iii) reliability of WBE was evaluated. Ciprofloxacin, sulfamethoxazole, metoprolol, carbamazepine, and citalopram were estimated by WBE with a difference respect to the "control" value lower than 0.2 order of magnitude while only trimethoprim and sotalol exceeded the 0.5 order of magnitude of difference but below the 1 order of magnitude. Sedatives were the best represented by WBE (on average 0.15 order of magnitude of difference compared to prescription data). However, further studies are suggested to fully estimate the influence of the type of APs on the reliability of the WBE. Seasonal patterns were found for the load of ciprofloxacin in the sewer and for the consumption of sulfamethoxazole and trimethoprim by population but seasonal changes did not have a significant impact (p > 0.05) on the reliability of WBE. Despite some gaps remained to optimize the reliability of the tool, WBE can be considered a valid method to estimate the consumption of prescribed drugs from the analysis of the sewer system.

Monitoring Pharmaceuticals and Personal Care Products in Drinking Water Samples by the LC-MS/MS Method to Estimate Their Potential Health Risk.

(1) The occurrence and accumulation of pharmaceuticals and personal care products in the environment are recognized scientific concerns. Many of these compounds are disposed of in an unchanged or metabolized form through sewage systems and wastewater treatment plants (WWTP). WWTP processes do not completely eliminate all active substances or their metabolites. Therefore, they systematically leach into the water system and are increasingly contaminating ground, surface, and drinking water, representing a health risk largely ignored by legislative bodies. Especially during the COVID-19 pandemic, a significantly larger amount of medicines and protective products were consumed. It is therefore likely that contamination of water sources has increased, and in the case of groundwater with a delayed effect. As a result, it is necessary to develop an accurate, rapid, and easily available method applicable to routine screening analyses of potable water to monitor and estimate their potential health risk. (2) A multi-residue UHPLC-MS/MS analytical method designed for the identification of 52 pharmaceutical products was developed and used to monitor their presence in drinking water. (3) The optimized method achieved good validation parameters, with recovery of 70-120% of most analytes and repeatability achieving results within 20%. In real samples of drinking water, at least one analyte above the limit of determination was detected in each of the 15 tap water and groundwater samples analyzed. (4) These findings highlight the need for legislation to address pharmaceutical contamination in the environment.

Pharmaceutical and narcotics monitoring in Brno wastewater system and estimation of seasonal effect on the abuse of illicit drugs by a wastewater-based epidemiology approach.

The presence of pharmaceuticals (PHA) and narcotics (NAR) in wastewater (WW) has attracting growing interest due to concern for aquatic environment and the possibility to exploit their presence to estimate drug consumption by population. This work aims to (i) quantify PHA and NAR in the WW of the Brno metropolitan area, (ii) determine the effectiveness of the current conventional wastewater treatment plant (WWTP), and (iii) estimate the illicit drug (ID) consumption. 23 PHA and 9 NAR were frequently detected in the untreated WW and studied for their removal. One year monitoring was carried out to highlight a possible seasonal pattern with PHA and NAR load in WW, WWTP effectiveness, and illicit consumption. Results highlighted that the most abundant PHA and NAR were caffeine (73.9 ± 6.9 µg L-1) and methamphetamine (2.3 ± 0.1 µg L-1) while oxazepam (0.13 ± 0.05 µg L-1) and EDDP (0.02 ± 0.01 µg L-1) were the lowest ones, respectively. Only paracetamol, caffeine, atenolol, ciprofloxacin, amphetamine, cocaine, morphine, and benzoylecgonine exhibited a high biodegradability being removed almost completely (> 90 %). A predominant illicit use of methamphetamine was estimated (17 ± 0.6 doses 1000.inh-1 d-1) that might suggest a higher number of consumers than previous official estimation. A lower abuse of cocaine (2.7 ± 0.5 doses 1000.inh-1 d-1), amphetamine (2.2 ± 0.3 doses 1000.inh-1 d-1), methadone (1.1 ± 0.2 doses 1000.inh-1 d-1), heroin (0.9 ± 0.2 doses 1000.inh-1 d-1), and MDMA (0.7 ± 0.1 doses 1000.inh-1 d-1) was found. A seasonality pattern was highlighted for some PHA and NAR influent load and removal, and, about ID consumption, only for heroin and methadone. These results will be useful for water utilities, to enhance the knowledge about the presence and removal of PHA and NAR, and local and national authorities to evaluate and counteract the problem of ID abuse.

The investigation of honey bee pesticide poisoning incidents in Czechia.

Honey bees are major pollinators of crops with high economic value. Thus, bees are considered to be the most important nontarget organisms exposed to adverse effects of plant protection product use. The side effects of pesticides are one of the major factors often linked to colony losses. Fewer studies have researched acute poisoning incidents in comparison to the study of the sublethal effects of pesticides. Here, we compared pesticides in dead/dying bees from suspected poisoning incidents and the suspected crop source according to government protocols. Additionally, we analyzed live bees and bee bread collected from the brood comb to determine recent in-hive contamination. We used sites with no reports of poisoning for reference. Our analysis confirmed that not all of the suspected poisonings correlated with the suspected crop. The most important pesticides related to the poisoning incidents were highly toxic chlorpyrifos, deltamethrin, cypermethrin and imidacloprid and slightly toxic prochloraz and thiacloprid. Importantly, poisoning was associated with pesticide cocktail application. Almost all poisoning incidents were investigated in relation to rapeseed. Some sites were found to be heavily contaminated with several pesticides, including a reference site. However, other sites were moderately contaminated despite agricultural use, including rapeseed cultivation sites, which can influence the extent of pesticide use, including tank mixes and other factors. We suggest that the analysis of pesticides in bee bread and in bees from the brood comb is a useful addition to dead bee and suspected crop analysis in poisoning incidents to inform the extent of recent in-hive contamination.

Pesticide comparison of Phylloneta impressa (Araneae: Theridiidae) females, cocoons and webs with prey remnants collected from a rape field before the harvest.

BACKGROUND: Pesticides or plant protection products (PPPs) are risky for spiders in or near agricultural landscapes. However, the risks posed by pesticides to spiders are largely understudied compared with the risks to pollinators. Here, we investigated the distribution of PPPs in adult females, cocoons and webs with prey remnants of Phylloneta impressa. RESULTS: Three sample types were collected from the tops of rapeseed on 18 July (before the harvest). Three different ultraperformance liquid chromatograph coupled with triple-quadrupole tandem mass spectrometer (UHPLC-QqQ-MS/MS) analyses were performed: (i) pesticides and selected metabolites; (ii) quaternary ammonium pesticides (quats); and (iii) pyrethroids. Overall, 23 compounds, 22 pesticides and the metabolite imidacloprid-urea were detected. The array of pesticides was largest in webs with prey remnants, and according to evaluation via redundancy analysis (RDA), pesticides were similar in spiders and cocoons; however, data inspection revealed differences in pesticide distribution among these samples. Clothianidin was detected in only female spiders, whereas thiamethoxam prevailed in webs with remnants of prey, and acetamiprid, thiacloprid and imidacloprid were found in all three matrices. One of the most abundant compounds was chlormequat, indicating that quats should be considered a possible risk for these spiders. None of the pyrethroids were detected despite being applied in the sampling area, indicating rapid biodegradation. By contrast, some pesticides were detected despite not being applied in the field, indicating that the source of contamination is prey or particles carried by wind and attached to webs. CONCLUSION: Overall, the results indicate the different distribution or behavior of several pesticides in the spider matrices. © 2019 Society of Chemical Industry.

tau-Fluvalinate and other pesticide residues in honey bees before overwintering.

BACKGROUND: Pesticides have often been linked to honey bee colony losses, which occur mainly over winter. In this study, we investigated residues in nine colonies at a model agricultural research site during the period before wintering. Moreover, we applied the acaricide tau-fluvalinate to the colonies via a strip formulation. The pesticide content was determined by UHPLC-QqQ-MS/MS in bees from brood comb initially collected in mid-September immediately prior to the start of tau-fluvalinate treatment and 30 later at the time of tau-fluvalinate strip removal. RESULTS: In addition to commonly analyzed pesticides, we detected two plant growth regulators, chlormequat and metazachlor, in the bee colonies. Whereas thiacloprid, chlormequat and acetamiprid decreased after 30 days and contributed considerably to differences between sample time points, other pesticides appeared to be rather stable. Interestingly, we identified diazinon, which has been banned in the European Union since 2007. The residues of methiocarb sulfoxide and imidacloprid-urea in the absence of their parent compounds indicate historical environmental contamination that can be identified by the detection of residues in a bee colony. tau-Fluvalinate was detected only after the 30-day treatment at an average (± SD) concentration of 1.29 ± 1.93 ng/bee, ranging from 0.06 to 7.13 ng/bee. CONCLUSION: The multidimensional behavior of pesticides in a bee colony was indicated. Although the research area is used for agriculture, the measured pesticide level was relatively low. The recorded concentrations of tau-fluvalinate should not be dangerous to bees, as the values were ∼ 200-5000-fold lower than the reported median lethal dose (LD50 ) values. © 2019 Society of Chemical Industry.

Chronic exposure of bumblebees to neonicotinoid imidacloprid suppresses the entire mevalonate pathway and fatty acid synthesis.

Determining the side effects of pesticides on pollinators is an important topic due to the increasing loss of pollinators. We aimed to determine the effects of chronic sublethal exposure of the neonicotinoid pesticide imidacloprid on the bumblebee Bombus terrestris under laboratory conditions. The analytical standard of imidacloprid in sugar solution was used for the treatment. Verification of pesticides using UHPLC-QqQ-MS/MS in the experimental bumblebees showed the presence of only two compounds, imidacloprid and imidacloprid-olefin, which were found in quantities of 0.57 ±â€¯0.22 and 1.95 ±â€¯0.43 ng/g, respectively. Thus, the level of the dangerous metabolite imidacloprid-olefin was 3.4-fold higher than that of imidacloprid. Label-free nanoLC-MS/MS quantitative proteomics of bumblebee heads enabled quantitative comparison of 2883 proteins, and 206 proteins were significantly influenced by the imidacloprid treatment. The next analysis revealed that the highly downregulated markers are members of the terpenoid backbone biosynthesis pathway (KEGG: bter00900) and that imidacloprid treatment suppressed the entire mevalonate pathway, fatty acid synthesis and associated markers. The proteomics results indicate that the consequences of imidacloprid treatment are complex, and the marker changes are associated with metabolic and neurological diseases and olfaction disruption. This study provides important markers and can help to explain the widely held assumptions from biological observations. SIGNIFICANCE: The major finding is that all markers of the mevalonate pathway were substantially downregulated due to the chronic imidacloprid exposure. The disbalance of mevalonate pathway has many important consequences. We suggest the mechanism associated with the novel toxicogenic effect of imidacloprid. The results are helpful to explain that imidacloprid impairs the cognitive functions and possesses the delayed and time cumulative effect.

The different behaviors of glyphosate and AMPA in compost-amended soil.

The broad-spectrum herbicide glyphosate is one of the most widely used pesticides. Both glyphosate and its major metabolite, aminomethylphosphonic acid (AMPA), persist in waters; thus, their environmental fates are of interest. We investigated the influence of compost dose, sampling depth, moisture and saturated hydraulic conductivity (Ks) on the persistence of these substances. The amounts of AMPA quantified by triple quadrupole liquid chromatography-mass spectrometry (LC-QqQ-MS/MS) using isotopically labeled extraction standards were higher than those of glyphosate and differed among the samples. Both glyphosate and AMPA showed gradually decreasing concentrations with soil depth, and bootstrapped ANOVA showed significant differences between the contents of glyphosate and AMPA and their behavior related to different compost dosages and sampling depths. However, the compost dose alone did not cause significant differences among samples. Bayesian statistics revealed that the amounts of glyphosate and AMPA were both dependent on the sampling depth and compost dose, but differences were found when considering the physical factors of Ks and moisture. Glyphosate was influenced by moisture but not Ks, whereas AMPA was influenced by Ks but not moisture. Importantly, we found behavioral differences between glyphosate and its major metabolite, AMPA, related to the physical properties of Ks and moisture.

Distributions of imidacloprid, imidacloprid-olefin and imidacloprid-urea in green plant tissues and roots of rapeseed (Brassica napus) from artificially contaminated potting soil.

BACKGROUND: Imidacloprid-urea is the primary imidacloprid soil metabolite, whereas imidacloprid-olefin is the main plant-relevant metabolite and is more toxic to insects than imidacloprid. We artificially contaminated potting soil and used quantitative UHPLC-QqQ-MS/MS to determine the imidacloprid, imidacloprid-olefin and imidacloprid-urea distributions in rapeseed green plant tissues and roots after 4 weeks of exposure. RESULTS: In soil, the imidacloprid/imidacloprid-urea molar ratios decreased similarly after the 250 and 2500 µg kg-1 imidacloprid treatments. The imidacloprid/imidacloprid-urea molar ratios in the root and soil were similar, whereas in the green plant tissue, imidacloprid-urea increased more than twofold compared with the root. Although imidacloprid-olefin was prevalent in the green plant tissues, with imidacloprid/imidacloprid-olefin molar ratios of 2.24 and 1.47 for the 250 and 2500 µg kg-1 treatments respectively, it was not detected in the root. However, imidacloprid-olefin was detected in the soil after the 2500 µg kg-1 imidacloprid treatment. CONCLUSION: Significant proportions of imidacloprid-olefin and imidacloprid-urea in green plant tissues were demonstrated. The greater imidacloprid supply increased the imidacloprid-olefin/imidacloprid molar ratio in the green plant tissues. The absence of imidacloprid-olefin in the root excluded its retransport from leaves. The similar imidacloprid/imidacloprid-urea ratios in the soil and root indicated that the root serves primarily for transporting these substances. © 2016 Society of Chemical Industry.