Four Years of Active Sampling and Measurement of Atmospheric Polycyclic Aromatic Hydrocarbons and Oxygenated Polycyclic Aromatic Hydrocarbons in Dronning Maud Land, East Antarctica.

Antarctica, protected by its strong polar vortex and sheer distance from anthropogenic activity, was always thought of as pristine. However, as more data on the occurrence of persistent organic pollutants on Antarctica emerge, the question arises of how fast the long-range atmospheric transport takes place. Therefore, polycyclic aromatic hydrocarbons (PAHs) and oxygenated (oxy-)PAHs were sampled from the atmosphere and measured during 4 austral summers from 2017 to 2021 at the Princess Elisabeth station in East Antarctica. The location is suited for this research as it is isolated from other stations and activities, and the local pollution of the station itself is limited. A high-volume sampler was used to collect the gas and particle phase (PM10) separately. Fifteen PAHs and 12 oxy-PAHs were quantified, and concentrations ranging between 6.34 and 131 pg m3 (Σ15PAHs-excluding naphthalene) and between 18.8 and 114 pg m3 (Σ13oxy-PAHs) were found. Phenanthrene, pyrene, and fluoranthene were the most abundant PAHs. The gas-particle partitioning coefficient log(Kp) was determined for 6 compounds and was found to lie between 0.5 and -2.5. Positive matrix factorization modeling was applied to the data set to determine the contribution of different sources to the observed concentrations. A 6-factor model proved a good fit to the data set and showed strong variations in the contribution of different air masses. During the sampling campaign, a number of volcanic eruptions occurred in the southern hemisphere from which the emission plume was detected. The FLEXPART dispersion model was used to confirm that the recorded signal is indeed influenced by volcanic eruptions. The data was used to derive a transport time of between 11 and 33 days from release to arrival at the measurement site on Antarctica.

Development of an analytical method to determine oxy-PAHs and PAHs in Taxus baccata leaves.

An analytical method was developed and optimized for the quantification of 16 polycyclic aromatic hydrocarbons (PAHs) and 12 oxygenated PAHs in Taxus baccata leaves. Emphasis was given to the development of an in-cell cleanup step using pressurized solvent extraction, a cleanup step using solid-phase extraction, and the instrumental analysis by GC-HRMS. Different extraction temperatures (between 50 and 200 °C) and Florisil quantities were evaluated for the extraction process. Based on the evaluation of both recoveries and matrix effect factors, a temperature of 200 °C and 1 g Florisil was selected as the optimum. However, the in-cell cleanup was not sufficient in the long term due to increasing chromatographic peak broadening, and further cleanup was necessary. Solid-phase extraction (using Florisil) was evaluated, and breakthrough curves were acquired for all target compounds to determine the optimal elution volume and avoiding matrix interference. Recoveries of the target compounds ranged from 58 to 87 % for the PAHs and from 5 to 105 % for the oxy-PAHs. Matrix effects were determined for all individual target compounds. The optimized method was applied to T. baccata samples obtained from ten sampling locations in Ghent, Belgium. This is the first biomonitoring study in Ghent for PAHs and oxy-PAHs. The presence of significant amounts of toxicologically relevant oxygenated PAHs (Oxy-PAHs) (can enhance ROS formation in human lung cells) in T. baccata was confirmed (max ∑Oxy-PAHs: 230 ng/g; max ∑PAHs: 389 ng/g). This means that these oxygenated PAHs are important pollutants and should be included in future monitoring studies.

Quality control in quantification of volatile organic compounds analysed by thermal desorption-gas chromatography-mass spectrometry.

This paper presents a detailed study on the calibration of a thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS)-based methodology for quantification of volatile organic compounds (VOCs) in gaseous and liquid samples. For the first time, it is documented to what extent three widely encountered problems affect precise and accurate quantification, and solutions to improve calibration are proposed. The first issue deals with the limited precision in MS quantification, as exemplified by high relative standard deviations (up to 40%, n=5) on response factors of a set of 69 selected VOCs in a volatility range from 16 Pa to 85 kPa at 298 K. The addition of [(2)H(8)]toluene as an internal standard, in gaseous or liquid phase, improves this imprecision by a factor of 5. Second, the matrix in which the standard is dissolved is shown to be highly important towards calibration. Quantification of gaseous VOCs loaded on a sorbent tube using response factors obtained with liquid standards results in systematic deviations of 40-80%. Relative response factors determined by the analysis of sorbent tubes loaded with both analytes and [(2)H(8)]toluene from liquid phase are shown to offer a reliable alternative for quantification of airborne VOCs, without need for expensive and often hardly available gaseous standards. Third, a strategy is proposed involving the determination of a relative response factor being representative for a group of analytes with similar functionalities and electron impact fragmentation patterns. This group method approach indicates to be useful (RSD approximately 10%) for quantifying analytes belonging to that class but having no standards available.

Statistical procedures for the determination of linearity, detection limits and measurement uncertainty: A deeper look into SPE-LC-Orbitrap mass spectrometry of pharmaceuticals in wastewater.

This research addresses some critical challenges regarding the validation of a quantitative multi-residue method for pharmaceuticals in wastewater making use of modern SPE-LC-Orbitrap high-resolution mass spectrometry. Particular attention is given to study in detail response linearity, to realistically estimate detection limits, and to express the measurement precision of the analyte concentration, obtained by external calibration. First, linearity of the Orbitrap response showed to be matrix dependent in a counter intuitive way: stronger deviations from linearity were observed for pure solvent standards than for complex matrices like wastewater. Second, detection limits risk to be overestimated for ubiquitously present compounds for which true blank matrix samples are hard to find, leading to false negative findings. A novel and easy applicable methodology is presented to allow a better estimation of detection limits using the response of the natural isotopes. Third, a statistical methodology to estimate the measurement precision of the analyte concentration using basic validation parameters is developed specifically for the context of multi-residue quantification.

Multi-residue analysis of pharmaceuticals in wastewater by liquid chromatography-magnetic sector mass spectrometry: method quality assessment and application in a Belgian case study.

Through systematic research a novel analytical method using solid-phase extraction (SPE) and liquid chromatography magnetic sector mass spectrometry was developed for the measurement of 43 pharmaceuticals in wastewater. A thorough method validation quantified the contribution of both the extraction recovery and matrix effects in the overall method process efficiency, and a detailed uncertainty analysis was performed to elaborate a quality labelling strategy to be used in data interpretation. Compounds for which a precise (relative standard deviation<20%) process efficiency between 60% and 140% was determined, were labelled as 'quantitative' whereas the results for other compounds should be interpreted as 'indicative'. Method application on influent and effluent samples of (i) a conventional active sludge system and (ii) a parallel membrane bioreactor/conventional active sludge wastewater treatment plant in Belgium revealed the occurrence of 22 pharmaceuticals. The anti-inflammatory drug diclofenac and the antidepressant venlafaxine were measured in the effluents at concentrations ranging from 0.5 to 1.8 µg L(-1) and 0.2 to 0.5 µg L(-1), respectively, which indicated to be of high potential environmental risk for the receiving river Dender, Belgium.

From multi-residue screening to target analysis of pharmaceuticals in water: development of a new approach based on magnetic sector mass spectrometry and application in the Nairobi River basin, Kenya.

This paper presents the development and application of a new multi-residue analytical method providing the first data on the environmental occurrence of human pharmaceuticals in Africa, particularly the Nairobi River basin (Kenya). Based on pharmaceutical consumption data available for the Nairobi region, 43 'priority' pharmaceutically active ingredients (PAIs) were selected for this study. On the basis of magnetic sector high-resolution mass spectrometry, a new methodology involving both full-scan screening and selective target analysis has been developed to investigate the presence of the defined priority PAIs. Subsequent analysis of the corresponding standard compounds provided the full confirmation and indicative concentrations (low ng/L-high µg/L) of 10 human PAIs in the Nairobi River. The detected compounds belong to different classes, i.e. antibiotics, analgesic/anti-inflammatory and anti-epileptic drugs, antimalarials and antiretrovirals. Ibuprofen, paracetamol, sulfamethoxazole and zidovudine showed to be the most concentrated PAIs (about 10-30 µg/L). The concentration of the antiretrovirals (lamivudine, zidovudine and nevirapine) is clearly higher than those reported in the literature, although environmental data on this class of PAIs are still very limited. To the best of our knowledge, this is the first study that provides evidence of detection of lamivudine in surface water. The presented unique data on the occurrence of selected PAIs in the aquatic environment of Africa clearly show that the high prevalence of specific diseases like HIV/AIDS infection in developing countries might result in a different pattern of PAIs in environmental waters compared to the more developed regions.

Ciprofloxacin ozonation in hospital wastewater treatment plant effluent: effect of pH and H2O2.

The ozonation of ciprofloxacin was studied in hospital wastewater treatment plant effluent with focus on parent compound degradation, degradation product identification and residual antibacterial activity. Before ozonation, ciprofloxacin sorption on suspended solids was tested as a function of temperature (10.0-27.5 degrees C) and pH (3, 7 and 10). Temperature did not significantly affect ciprofloxacin sorption while sorption was highest at pH 7 (logK(d)=4.7) compared to pH 3 (logK(d)=4.3) and 10 (logK(d)=3.9) (n=3). Ozonation was slowest at pH 7 with ciprofloxacin half life times of 29 min, compared to 19 and 27 min at pH 10 and 3, respectively. Addition of 10-1000 microM H(2)O(2) increased ciprofloxacin half life times up to 38 min, probably influenced by competition with H(2)O(2) for ozone as well as radical species. Ciprofloxacin ozonation products were identical as previously detected during ciprofloxacin ozonation in deionized water and revealed strong pH dependence. Residual antibacterial activity was measured by agar diffusion tests. For Pseudomonas fluorescens and Escherichia coli, reduction of antibacterial activity was related to the parent compound degradation, while degradation products indicated to be the main compounds with respect to the antibacterial activity against Bacillus coagulans.

Ozonation of ciprofloxacin in water: HRMS identification of reaction products and pathways.

Degradation products formed during ozonation of an aqueous solution of the antibiotic ciprofloxacin in a bubble column are analyzed by HPLC-UV high-resolution mass spectrometry. Based on the identification of the reaction products, reaction pathways are proposed starting with (1) degradation at the piperazinyl substituent, (2) degradation at the quinolone moiety with formation of isatin analogues, and (3) degradation at the quinolone moiety with formation of anthranilic acid analogues. Unlike H2O2 addition (10 microM), pH (3,7, and 10) strongly affects degradation product formation during ozonation. Degradation at the quinolone core is favored at pH 7. Addition of t-butanol, a hydroxyl radical scavenger, ruled out formation of isatin and anthranilic acid analogues. Because the carboxylic group and the keto group at the quinolone moiety are essential for antibacterial activity, degradation at pH 7 seems to be promising for reduction of bacterial resistance against quinolones in contaminated water.