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In regulatory environmental monitoring programs, only a very small fraction of the vast number of per- and polyfluoroalkyl substances (PFAS) are investigated by target analysis. Therefore, non-target analysis (NTA) studies are increasingly conducted to detect unknown or unnoticed PFAS. These studies are often based on a few grab samples. Thus, discontinuously emitted PFAS from industrial batch processes might be easily overlooked. To address this deficiency and obtain in-depth information on the occurrence and temporal trend of PFAS in surface water impacted by treated industrial waste water, a comprehensive target and NTA study was implemented for 29 months. Elevated PFAS concentrations with up to 10.8 μg L−1 were detected in the river water by target analysis. In addition to PFAS target analysis, the water samples were analyzed by liquid chromatography-high-resolution tandem mass spectrometry (LC-HRMS/MS). Data processing strategies and various filtering steps were applied to prioritize PFAS. Substances were identified by comparing data to available internal and external PFAS suspect lists, a fragment ion and neutral loss list, and spectral libraries. Several compounds were unequivocally identified based on reference standards. Fifty-five PFAS were (tentatively) identified using NTA. Of those, 43 could be assigned to 13 different homologous series. Partly fluorinated short-chain carboxylic acids (H-PFCA) and sulfonic acids (H-PFSA) were predominantly found in addition to perfluoroalkyl carboxylic acids (PFCA) and the alkyl ether carboxylic acid DONA. To the best of our knowledge, 12 PFAS were reported in surface water for the first time. Signal intensities of individual PFAS and signal ratios varied widely over time, which may indicate batch operations leading to discontinuous emission. Results and insights from this screening approach on PFAS can be used to optimize forthcoming surface water monitoring programs by including newly identified PFAS and selecting appropriate sampling intervals. [Display omitted] • Development of a monitoring strategy for known and unknown PFAS in highly impacted surface waters. • Non-target analysis (NTA) over a period of 29 months. • Novel data processing workflow for the identification and characterization of unknown PFAS. • Signal intensities and signal ratios of individual PFAS varied strongly over time. [ABSTRACT FROM AUTHOR]

Sensitive trace gas detection plays an important role in current challenges occurring in areas such as industrial process control and environmental monitoring. In particular, for medical breath analysis and for the detection of illegal substances, e.g., drugs and explosives, a selective and sensitive detection of trace gases in real-time is required. We report on a compact and transportable multi-component system (RES-Q-Trace) for molecular trace gas detection based on cavity-enhanced techniques in the mid-infrared (MIR). The RES-Q-Trace system can operate four independent continuous wave quantum or interband cascade lasers each combined with an optical cavity. Twice the method of off-axis cavity-enhanced absorption spectroscopy (OA-CEAS) was used, twice the method of optical feedback cavity-enhanced absorption spectroscopy (OF-CEAS), respectively. Multi-functional software has been implemented (i) for the general system control; (ii) to drive the four different laser sources and (iii) to analyze the detector signals for concentration determination of several molecular species. For the validation of the versatility and the performance of the RES-Q-Trace instrument the species NO, N2O, CH4, C2H4 and C3H6O, with relevance in the fields of breath gas analysis and the detection of explosives have been monitored in the MIR with detection limits at atmospheric pressure in the ppb and ppt range. [ABSTRACT FROM AUTHOR]

A method for quantification of a pharmaceutical peptide in human plasma was developed using gradient elution LC-ICP-MS. A membrane desolvation (MD) system was applied to remove organic solvents from the eluent prior to the detection as SO+ in the dynamic reaction cell (DRC) of the ICP-DRC-MS instrument and subsequent quantification by post-column isotope dilution (IDA). Plasma proteins were precipitated prior to analysis. Analytical figures of merit including linearity, precision, LOD, LOQ and accuracy were considered satisfactory for analysis of plasma samples. The selectivity of the developed method was demonstrated for five pharmaceutically relevant peptides: desmopressin, penetratin, substance P, PTH (1-34) and insulin. Preliminary experiments on an ICP-MS/MS system using oxygen to reduce the effect of organic solvents were also performed to compare sensitivity. The results of the study demonstrated that LC-ICP-MS post-column IDA may constitute a valuable additional tool in quantification of non-labelled peptides in the early drug development offering absolute quantification without need of species specific standards. [ABSTRACT FROM AUTHOR]

Plasmas in interaction with surfaces are of key importance in a wide range of applications, which include materials technology, microelectronics, environmental issues, and biomedicine. The intense use of plasma technological processes demands proper plasma diagnostic techniques for monitoring, controlling and optimization purposes in industrial environments. In particular, for the improvement of the efficiency of a production process, in situ diagnostic techniques with online capabilities are favorable. From the middle of the last decade a variety of phenomena in molecular non-equilibrium plasmas in which many short-lived and stable species are produced have been successfully studied with quantum cascade laser absorption spectroscopy (QCLAS) in the mid-infrared spectral range. It has been possible to determine absolute concentrations of species, temperatures, degrees of dissociation, dynamics of reaction processes and phenomena involving plasma-surface interactions using spectroscopy, thereby providing a link with chemical and kinetic modelling of the plasma. Since quantum cascade lasers (QCLs) emit near room temperature, i.e., without the need of cryogenic cooling, very compact and robust spectroscopic instruments can be designed. This has stimulated the adaptation of infrared spectroscopic techniques to industrial requirements. Recent applications of infrared absorption spectroscopy using QCLs for in situ monitoring of plasma processes in industrial environments are reviewed. Examples which emphasize the capabilities of QCLAS as plasma diagnostic technique in industrial plasma processes will be given. (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [ABSTRACT FROM AUTHOR]

Abstract: Triclocarban (TCC), triclosan (TCS) and methyl triclosan (Me-TCS) were detected in soil and the native population of earthworms of an agricultural field in Ottawa, Canada, about four years after a commercial-scale application of biosolids. In soil that received biosolids, TCC and TCS were detected at median concentrations of 13.0 and 1.5ng/g soil (d.w.), respectively, while Me-TCS, the transformation product of triclosan, was detected at a six-fold higher median concentration than its precursor. In earthworms collected at the biosolids-amended field-plot about four years post application, Me-TCS was also detected at higher concentrations (26 to 114ng/g tissue d.w.) than TCS (16–51ng/g) and TCC (4–53ng/g). These data provide evidence that not only parent compounds but also their transformation products need to be considered in faunal bioaccumulation studies. Moreover, the preliminary results for pooled earthworm samples from different ecological groups suggest that the degree of bioaccumulation of biosolids-associated contaminants may depend on the habitat and feeding behavior of the organisms. [Copyright &y& Elsevier]

Persistent environmental contaminants may enter agricultural fields via the application of sewage sludge, by irrigation with treated municipal wastewater or by manuring. It has been shown that such contaminants can be incorporated into crop plants. The metabolism of the bacteriostatic agents triclocarban, triclosan, and its transformation product methyl triclosan was investigated after their uptake into carrot cell cultures. A fast metabolization of triclosan was observed and eight so far unknown phase II metabolites, conjugates with saccharides, disaccharides, malonic acid, and sulfate, were identified by liquid chromatography-mass spectrometry. Triclocarban and methyl triclosan lack a phenolic group and remained unaltered in the cell cultures. Phase I metabolization was not observed for any of the compounds. All eight triclosan conjugates identified in the cell cultures were also detected in extracts of intact carrot plants cultivated on triclosan contaminated soils. Their total amount in the plants was assessed to exceed the amount of the triclosan itself by a factor of 5. This study shows that a disregard of conjugates in studies on plant uptake of environmental contaminants may severely underestimates the extent of uptake into plants and, eventually, the potential human exposure to contaminants via food of plant origin. [ABSTRACT FROM AUTHOR]

Terahertz (THz) absorption spectroscopy has recently been developed as a diagnostic technique for measuring absolute ground-state atomic oxygen densities in plasmas. To demonstrate the validity of this approach, we present in this Letter a benchmark against a more established method. Atomic oxygen densities were measured with THz absorption spectroscopy and compared to those obtained from picosecond (ps) two-photon absorption laser induced fluorescence (TALIF) measurements on the same capacitively coupled radio frequency oxygen discharge. Similar changes in the atomic oxygen density were observed with both diagnostics when varying the applied power (20–100 W) and the gas pressure (0.7–1.3 mbar). Quantitatively, the results are in good agreement as well, especially when considering the total margin of error of the two diagnostics. For example, for a gas pressure of 1.3 mbar and an applied power of 30 W, atomic oxygen densities measured with THz absorption spectroscopy and TALIF were (7.0 ± 1.7) × 10 14 cm−3 and (5.3 ± 3.2) × 10 14 cm−3, respectively. This shows that THz absorption spectroscopy is an accurate technique that can be reliably used for real-world applications to determine atomic oxygen densities in plasmas. [ABSTRACT FROM AUTHOR]

We report on terahertz (THz) quantum-cascade lasers (QCLs) based on GaAs/AlAs heterostructures, which exhibit single-mode emission at 3.360, 3.921, and 4.745 THz. These frequencies are in close correspondence to fine-structure transitions of Al atoms, N+ ions, and O atoms, respectively. Due to the low electrical pump power of these THz QCLs, they can be operated in a mechanical cryocooler in continuous-wave mode, while a sufficient intrinsic tuning range of more than 5 GHz is maintained. The single-mode operation and the intrinsic tuning range of these THz QCLs allow for the application of these lasers as radiation sources for high-resolution absorption spectroscopy to determine the absolute densities of Al atoms, N+ ions, and O atoms in plasmas. [ABSTRACT FROM AUTHOR]

[Display omitted] • Collaborative trial of 16 laboratories on suspect and non-target screening (NTS) in fish. • Comparison of test extracts by in-house and reference methods (GC-HRMS, LC-HRMS) • Reproducibility between sample preparation methods was not significantly different. • On average, 41 % (LC-HRMS) and 37 % (GC-HRMS) of spiked compounds were identified. A collaborative trial involving 16 participants from nine European countries was conducted within the NORMAN network in efforts to harmonise suspect and non-target screening of environmental contaminants in whole fish samples of bream (Abramis brama). Participants were provided with freeze-dried, homogenised fish samples from a contaminated and a reference site, extracts (spiked and non-spiked) and reference sample preparation protocols for liquid chromatography (LC) and gas chromatography (GC) coupled to high resolution mass spectrometry (HRMS). Participants extracted fish samples using their in-house sample preparation method and/or the protocol provided. Participants correctly identified 9–69 % of spiked compounds using LC-HRMS and 20–60 % of spiked compounds using GC-HRMS. From the contaminated site, suspect screening with participants' own suspect lists led to putative identification of on average ∼145 and ∼20 unique features per participant using LC-HRMS and GC-HRMS, respectively, while non-target screening identified on average ∼42 and ∼56 unique features per participant using LC-HRMS and GC-HRMS, respectively. Within the same sub-group of sample preparation method, only a few features were identified by at least two participants in suspect screening (16 features using LC-HRMS, 0 features using GC-HRMS) and non-target screening (0 features using LC-HRMS, 2 features using GC-HRMS). The compounds identified had log octanol/water partition coefficient (K OW) values from −9.9 to 16 and mass-to-charge ratios (m / z) of 68 to 761 (LC-HRMS and GC-HRMS). A significant linear trend was found between log K OW and m / z for the GC-HRMS data. Overall, these findings indicate that differences in screening results are mainly due to the data analysis workflows used by different participants. Further work is needed to harmonise the results obtained when applying suspect and non-target screening approaches to environmental biota samples. [ABSTRACT FROM AUTHOR]

• 586 of the studied 2362 contaminants were detected in the Danube River Basin. • Risk assessment prioritized 12 legacy and 33 emerging contaminants. • The 33 emerging contaminants are Danube River Basin Specific Pollutants. • 20 performance indicators were checked in wastewater treatment plants. • The plants showed medium or efficient removal for 70% of the studied compounds. A state-of-the-art wide-scope target screening of 2,362 chemicals and their transformation products (TPs) was performed in samples collected within the Joint Danube Survey 4 (JDS4) performed in 2019. The analysed contaminants of emerging concern (CECs) included three major categories: plant protection products (PPPs), industrial chemicals and pharmaceuticals and personal care products (PPCPs). In total, 586 CECs were detected in the samples including 158 PPPs, 71 industrial chemicals, 348 PPCPs, and 9 other chemicals. A wide-variety of sample matrices were collected including influent and effluent wastewater, groundwater, river water, sediment and biota. Forty-five CECs (19 PPPs, 8 industrial chemicals, 18 PPCPs) were detected at levels above their ecotoxicological thresholds (lowest predicted no-effect concentration (PNEC) values) in one or more of the investigated environmental compartments, indicating potential adverse effects on the impacted ecosystems. Among them 12 are legacy substances; 33 are emerging and qualify as potential Danube River Basin Specific Pollutants (RBSPs). Moreover, the efficiency of the wastewater treatment plants (WWTPs) was evaluated using 20 selected performance indicator chemicals. WWTPs showed effective removal (removal rate ≥80%) and medium removal (removal rate 25–80%) for 6 and 8 of the indicator chemicals, respectively. However, numerous contaminants passed the WWTPs with a lower removal rate. Further investigation on performance of WWTPs is suggested at catchment level to improve their removal efficiency. WWTP effluents are proven to be one of the major sources of contaminants in the Danube River Basin (DRB). Other sources include sewage discharges, industrial and agricultural activities. Continuous monitoring of the detected CECs is suggested to ensure water quality of the studied area. [Display omitted] [ABSTRACT FROM AUTHOR]

Low-pressure rf plasmas have been applied for etching of ultra-low-k SiCOH wafers using an Oxford Plasmalab System 100. In pure CF plasmas, SiCOH layers have been etched for different power values. Using quantum cascade laser absorption spectroscopy in the mid-infrared spectral range, the correlation of online and in situ measured concentrations of two etching products, CO and SiF, with the ex situ determined etching rates has been studied. The concentration of SiF was found to range between 0.6 and 1.4 × 10 molecules cm. In contrast the concentrations of CO were measured to be only about 50 % of the SiF density with 7 × 10 molecules cm in maximum. The production rate of SiF, determined from the time behavior of its concentration after plasma ignition, was found to be between 1 and 5 × 10 cm s. The etching rates varied between 2 and 7 nm s. Both parameters increase nearly linearly with the applied rf power. It was found that for power values of up to 1.1 kW, the etching rate depends nearly linearly on the in situ monitored concentrations of both etching products. Therefore, the concentration of the etching products can be directly used as a measure of the etching rate. [ABSTRACT FROM AUTHOR]

Trace gas sensing in the mid-infrared using quantum cascade lasers (QCLs) promises high specificity and sensitivity. We report on the performance of a simple cavity enhanced absorption spectroscopy (CEAS) sensor using a continuous wave external-cavity QCL at 7.4 μm. A noise-equivalent absorption coefficient αmin of 2.6 × 10-8 cm-1 in 625 s was achieved, which corresponds to a detection limit of 6 ± 1 ppb of CH4 in 15 millibars air for the R(3) transition at 1327.074 cm-1. This is the highest value of noise-equivalent absorption and among the longest effective path length (1780 m) reported to date with QCL-based CEAS. [ABSTRACT FROM AUTHOR]