The key role of propane in a sustainable cooling sector.

Split air conditioners (ACs) are the most used appliance for space cooling worldwide. The phase-down of refrigerants with high global warming potential (GWP) prescribed by the Kigali Amendment to the Montreal Protocol has triggered a major effort to find less harmful alternative refrigerants. HFC-32 is currently the most common refrigerant to replace HFC-410A in split ACs. The GWP of HFC-32 is about one-third that of HFC-410A but still considerably higher than that of a growing number of nonfluorinated alternatives like propane with a GWP of <1, which have recently become commercially available for split ACs. Here, we show that a switch to propane as an energy-efficient and commercially available low-GWP alternative in split ACs could avoid 0.09 (0.06 to 0.12) °C increase in global temperature by the end of the century. This is significantly more than the 0.03 (0.02 to 0.05) °C avoided warming from a complete switch to HFC-32 in split ACs.

Rapid Characterization of Per- and Polyfluoroalkyl Substances (PFAS) by Ion Mobility Spectrometry-Mass Spectrometry (IMS-MS).

Per- and polyfluoroalkyl substances (PFAS) are an ensemble of persistent organic pollutants of global interest because of their associations with adverse health outcomes. Currently, environmental PFAS pollution is prolific as a result of the widespread manufacturing of these compounds and their chemical persistence. In this work, we demonstrate the advantages of adding ion mobility spectrometry (IMS) separation to existing LC-MS workflows for PFAS analysis. Using a commercially available drift tube IMS-MS, we characterized PFAS species and isomeric content in both analytical standards and environmental water samples. Molecular trendlines based on intrinsic mass and structural relationships were also explored for individual PFAS subclasses (e.g. PFSA, PFCA, etc.). Results from rapid IMS-MS analyses provided a link between mass and collision cross sections (CCS) for specific PFAS families and are linked to compositional differences in molecular structure. In addition, CCS values provide additional confidence of annotating prioritized features in untargeted screening studies for potential environmental pollutants. Results from this study show that the IMS separation provides novel information to support traditional LC-MS PFAS analyses and will greatly benefit the evaluation of unknown pollutants in future environmental studies.

Toward Comprehensive Per- and Polyfluoroalkyl Substances Annotation Using FluoroMatch Software and Intelligent High-Resolution Tandem Mass Spectrometry Acquisition.

Thousands of per- and polyfluoroalkyl substances (PFAS) exist in the environment and pose a potential health hazard. Suspect and nontarget screening with liquid chromatography (LC)-high-resolution tandem mass spectrometry (HRMS/MS) can be used for comprehensive characterization of PFAS. To date, no automated open source PFAS data analysis software exists to mine these extensive data sets. We introduce FluoroMatch, which automates file conversion, chromatographic peak picking, blank feature filtering, PFAS annotation based on precursor and fragment masses, and annotation ranking. The software library currently contains ∼7 000 PFAS fragmentation patterns based on rules derived from standards and literature, and the software automates a process for users to add additional compounds. The use of intelligent data-acquisition methods (iterative exclusion) nearly doubled the number of annotations. The software application is demonstrated by characterizing PFAS in landfill leachate as well as in leachate foam generated to concentrate the compounds for remediation purposes. FluoroMatch had wide coverage, returning 27 PFAS annotations for landfill leachate samples, explaining 71% of the all-ion fragmentation (CF2)n related fragments. By improving the throughput and coverage of PFAS annotation, FluoroMatch will accelerate the discovery of PFAS posing significant human risk.

Enantioseparation and dissipation monitoring of oxathiapiprolin in grape using supercritical fluid chromatography tandem mass spectrometry.

Oxathiapiprolin is a chiral fungicide used in China for the prevention and treatment of grape downy mildew, but its potential risk could be inaccurately assessed without distinguishing its enantiomers. In this study, an effective and sensitive chiral analytical method was first established for quantification of oxathiapiprolin enantiomers using supercritical fluid chromatography tandem mass spectrometry. Baseline separation for oxathiapiprolin enantiomers was achieved for less than 3 min by using a Lux Cellulose-2 chiral column with the resolution of 1.51. The elution order of the eluting enantiomers was identified as (-)-oxathiapiprolin and (+)-oxathiapiprolin by an optical rotation detector. The grape samples were extracted by QuEChERS method, with the average recoveries of each enantiomer in grapes were in the range of 88.1-111.8% and the relative standard deviations were less than 18.9%. The enantioselective analysis of the dissipation of oxathiapiprolin in field grape samples showed that (-)-oxathiapiprolin was dissipated faster than (+)-oxathiapiprolin. The results indicate that this proposed method could provide data support for the risk assessment of oxathiapiprolin in agricultural produces in a more accurate way.

Enantioselective residue analysis of oxathiapiprolin and its metabolite in tea and other crops by ultra-high performance liquid chromatography-tandem mass spectrometry.

Oxathiapiprolin is the first chiral piperidinyl thiazole isoxazoline fungicide developed to control downy mildew and other diseases, and there were no prior reports on its enantiomeric residue. In this study, a modified quick, easy, cheap, effective, rugged, and safe extraction and purification method followed by ultra-high performance liquid chromatography-tandem mass spectrometry determination was first developed and validated for the residue analysis of oxathiapiprolin enantiomers and its metabolite IN-E8S72 in green tea and other crops. Oxathiapiprolin enantiomers and IN-E8S72 were separated on a chiral Lux Cellulose-3 column with the use of 0.1% formic acid in acetonitrile and 5 mmol/L ammonium acetate in water as mobile phases. IN-E8S72 was eluted first, followed by (-)-oxathiapiprolin, and then (+)-oxathiapiprolin. The recoveries ranged from 53.3 to 125.3% with relative standard deviations ranging from 1.4 to 16.0%. The limits of quantification for (-)-oxathiapiprolin and (+)-oxathiapiprolin were 0.005 mg/kg in romaine lettuce, head cabbage, potato, grape, and garlic, 0.01 mg/kg in soybean and pea, and 0.025 mg/kg in green tea and dry pepper. The limits of quantification of IN-E8S72 were twice those of (-)-oxathiapiprolin. Screening results with real market samples indicated that there was no enantiomeric excess in the oxathiapiprolin residue in romaine lettuce.

Three-Dimensional NMR Spectroscopy of Fluorinated Pharmaceutical Solids under Ultrafast Magic Angle Spinning.

High-resolution solid-state analysis of multicomponent molecular systems, e.g., pharmaceutical formulations, is a great challenge. Solid-state nuclear magnetic resonance (ssNMR) spectroscopy plays a critical role in the characterization of solid dosage forms due to its capabilities of chemical identification, quantification, and structural elucidation at a molecular level. However, the low NMR sensitivity as well as the high spectral complexity and low drug loading of multicomponent products hinder an in-depth investigation of the active pharmaceutical ingredient (API) at the natural isotopic abundance. Herein, we developed two new three-dimensional (3D) ssNMR methods, including 1H-19F-1H and 19F-19F-1H correlations and successfully applied them to characterize a fluorinated drug molecule, aprepitant, and its commercial nanoparticulate formulation EMEND (Merck & Co, Inc., Kenilworth, NJ, USA). These 1H-detection methods utilize the significantly enhanced sensitivity and resolution of 1H and 19F afforded by 60 kHz ultrafast magic angle spinning (MAS) and enable the analysis of milligram samples. The 3D techniques simultaneously provide homonuclear 1H-1H and 19F-19F, and heteronuclear 1H-19F correlations of the crystalline aprepitant without interferences from other pharmaceutical components in the drug product. Moreover, our results demonstrate that 19F is a highly sensitive spin for probing molecular details of fluorinated drug substances in solid formulations, due to its high isotopic abundance, large gyromagnetic ratio, and absence of signal interference from pharmaceutical excipients, as well as for characterizing structural properties of a broad range of fluorine-containing materials.

Rapid cross-density ocean mixing at mid-depths in the Drake Passage measured by tracer release.

Diapycnal mixing (across density surfaces) is an important process in the global ocean overturning circulation. Mixing in the interior of most of the ocean, however, is thought to have a magnitude just one-tenth of that required to close the global circulation by the downward mixing of less dense waters. Some of this deficit is made up by intense near-bottom mixing occurring in restricted 'hot-spots' associated with rough ocean-floor topography, but it is not clear whether the waters at mid-depth, 1,000 to 3,000 metres, are returned to the surface by cross-density mixing or by along-density flows. Here we show that diapycnal mixing of mid-depth (∼1,500 metres) waters undergoes a sustained 20-fold increase as the Antarctic Circumpolar Current flows through the Drake Passage, between the southern tip of South America and Antarctica. Our results are based on an open-ocean tracer release of trifluoromethyl sulphur pentafluoride. We ascribe the increased mixing to turbulence generated by the deep-reaching Antarctic Circumpolar Current as it flows over rough bottom topography in the Drake Passage. Scaled to the entire circumpolar current, the mixing we observe is compatible with there being a southern component to the global overturning in which about 20 sverdrups (1 Sv = 10(6) m(3) s(-1)) upwell in the Southern Ocean, with cross-density mixing contributing a significant fraction (20 to 30 per cent) of this total, and the remainder upwelling along constant-density surfaces. The great majority of the diapycnal flux is the result of interaction with restricted regions of rough ocean-floor topography.

Intermolecular Interaction in Methylene Halide (CH2F2, CH2Cl2, CH2Br2 and CH2I2) Dimers.

The intermolecular interaction in difluoromethane, dichloromethane, dibromomethane, and diiodomethane dimers has been investigated using high level quantum chemical methods. The potential energy curve of intermolecular interaction along the C⋯C bond distance obtained using the coupled-cluster theory with singles, doubles, and perturbative triples excitations CCSD(T) were compared with values given by the same method, but applying the local (LCCSD(T)) and the explicitly correlated (CCSD(T)-F12) approximations. The accuracy of other theoretical methods-Hartree-Fock (HF), second order Møller-Plesset perturbation (MP2), and dispersion corrected DFT theory-were also presented. In the case of MP2 level, the canonical and the local-correlation cases combined with the density-fitting technique (DF-LMP2)theories were considered, while for the dispersion-corrected DFT, the empirically-corrected BLYP-D and the M06-2Xexchange-correlation functionals were applied. In all cases, the aug-cc-pVTZ basis set was used, and the results were corrected for the basis set superposition error (BSSE) using the counterpoise method. For each molecular system, several dimer geometries were found, and their mutual orientations were compared with the nearest neighbor orientations obtained in recent neutron scattering studies. The nature of the intermolecular interaction energy was discussed.

Polybrominated Diphenyl Ethers (PBDEs) in Sediments of the Huron-Erie Corridor.

Polybrominated diphenyl ethers (PBDEs) were measured in 182 sediments from the Huron-Erie Corridor, North America. The median (5-95 percentile) Corridor ∑PBDE concentration was 1.03 ng/g dry wt (0.25-13.48 ng/g dry wt). Dry weight ∑PBDEs were elevated in U.S. waters of the Detroit River (US DR) and lowest in Canadian waters of Lake St. Clair (CA LSC). Sediment total organic carbon (TOC) explained some of the variation in ∑PBDEs, particularly in upstream waterbodies except for the Detroit River where local sources were apparent in the US DR and TOC-dilution occurred in CA DR. Canadian Federal Sediment Quality guidelines were exceeded at 19 stations, 14 occurring in the US DR. ∑Hazard Quotients (∑HQ) had a median (5-95 percentile) Corridor value of 0.46 (ND to 2.27). By strata, 43.2% of US DR stations had ∑HQ's greater than 1 while 21.3% of US SCR stations exceeded a value of 1.

Exposing the Origins of Irreproducibility in Fluorine NMR Spectroscopy.

Fluorine chemistry has taken a pivotal role in chemical reaction discovery, drug development, and chemical biology. NMR spectroscopy, arguably the most important technique for the characterization of fluorinated compounds, is rife with highly inconsistent referencing of fluorine NMR chemical shifts, producing deviations larger than 1 ppm. Herein, we provide unprecedented evidence that both spectrometer design and the current unified scale system underpinning the calibration of heteronuclear NMR spectra have unintentionally led to widespread variation in the standardization of 19 F NMR spectral data. We demonstrate that internal referencing provides the most robust, practical, and reproducible method whereby chemical shifts can be consistently measured and confirmed between institutions to less than 30 ppb deviation. Finally, we provide a comprehensive table of appropriately calibrated chemical shifts of reference compounds that will serve to calibrate 19 F spectra correctly.

Quaternary Ammonium Polyamidoamine Dendrimer Modified Quantum Dots as Fluorescent Probes for p-Fluorophenoxyacetic Acid Detection in Aqueous Solution.

The wide use of pesticide p-fluorophenoxyacetic acid has caused the serious environmental contaminant. A novel fluorescent probe for sensitive detection of p-fluorophenoxyacetic acid in aqueous solutions based on 3.0G quaternary ammonium polyamidoamine (PAMAM) dendrimer modified quantum dots (QDs) (PAMAM@QDs) was reported. Through the solvent-evaporation method, quaternary ammonium PAMAM was employed to modify the QDs. Poloxamer 188 was used to improve the solubility and stability. The resultant PAMAM@QDs dispersed well in water. Fluorescence (FL) spectroscopic study showed that the FL intensity of the PAMAM@QDs was enhanced in the presence of p-fluorophenoxyacetic acid. Under optimal conditions, the enhanced FL intensity as a function of concentration matched very well in the range of 1 ~ 200 µg/mL of p-fluorophenoxyacetic acid, while the lower limits of detection were found to be 0.16 µg/mL. These results show that PAMAM@QDs is a promising luminescent probe for the detection of pesticides.

Fate and transport of furrow-applied granular tefluthrin and seed-coated clothianidin insecticides: Comparison of field-scale observations and model estimates.

The transport of agricultural insecticides to water bodies may create risk of exposure to non-target organisms. Similarly, widespread use of furrow-applied and seed-coated insecticides may increase risk of exposure, yet accessible exposure models are not easily adapted for furrow application, and only a few examples of model validation of furrow-applied insecticides exist using actual field data. The goal of the current project was to apply an exposure model, the Pesticide in Water Calculator (PWC), to estimate the concentrations of two in-furrow insecticides applied to maize: the granular pyrethroid, tefluthrin, and the seed-coated neonicotinoid, clothianidin. The concentrations of tefluthrin and clothianidin in surface runoff water, sampled from a field in central Illinois (USA), were compared to the PWC modeled pesticide concentrations in surface runoff. The tefluthrin concentrations were used to optimize the application method in the PWC, and the addition of particulate matter and guttation droplets improved the models prediction of clothianidin concentrations. Next, the tefluthrin and clothianidin concentrations were calculated for a standard farm pond using both the optimized application method and the application methods provided in PWC. Estimated concentrations in a standard farm pond varied by a factor of 100 for tefluthrin and 50 for clothianidin depending on the application method used. The addition of guttation droplets and particulate matter to the model increased the annual clothianidin concentration in a standard farm pond by a factor of 1.5, which suggested that these transport routes should also be considered when assessing neonicotinoid exposure.

Determination of oxathiapiprolin concentration and dissipation in grapes and soil by ultrahigh-performance liquid chromatography-tandem mass spectrometry.

BACKGROUND: The residue concentrations and dissipation rate of a new oxathiapiprolin fungicide in grapes and soil were investigated to provide an evaluation for the safe use of oxathiapiprolin in grapes. Pesticide residue was extracted by acetonitrile, then purified by solid-phase extraction with an Envi-Carb cartridge and determined by ultrahigh-performance liquid chromatography-tandem mass spectrometry. RESULTS: The fortified recoveries ranged from 85.2% to 99.0%, with relative standard deviations of 1.7-4.5%. The limit of quantitation for oxathiapiprolin in grapes and soil was 0.002 mg kg-1 . The mean initial deposits of oxathiapiprolin in grapes were 0.345-0.565 mg kg-1 , with half-lives of 8.6-9.2 days. The mean initial deposits of oxathiapiprolin in soil were 0.078-0.273 mg kg-1 , with half-lives of 7.6-12.0 days. The oxathiapiprolin residue in grapes and soil was 0.002-0.022 mg kg-1 and 0.002-0.123 mg kg-1 when sampling 14 days after application, respectively. CONCLUSION: The residue in the grapes was less than 0.01 mg kg-1 when sampling 28 days after application, which suggested that the application rate of 20 mg a.i. kg-1 for this fungicide should be used to ensure that treated grapes can be considered safe for humans to consume when sampling 28 days after the final application. © 2016 Society of Chemical Industry.

Perfluoroalkylphosphinic Acids in Northern Pike (Esox lucius), Double-Crested Cormorants (Phalacrocorax auritus), and Bottlenose Dolphins (Tursiops truncatus) in Relation to Other Perfluoroalkyl Acids.

Perfluoroalkyl phosphinic acids (PFPIAs) are perfluoroalkyl acids (PFAAs) that are used for their surfactant properties in a variety of applications, resulting in their presence in environmental waters; however, they have not been widely studied in biota. A survey of PFPIAs was conducted in fish, dolphins, and birds from various locations in North America. Northern pike (Esox lucius) were collected at two locations in 2011 near Montréal Island in the St. Lawrence River, Canada, double-crested cormorants (Phalacrocorax auritus) were collected from bird colonies in the Great Lakes in 2010-2012, and bottlenose dolphins (Tursiops truncatus) from Sarasota Bay, FL and Charleston Harbor, SC were sampled in 2004-2009. PFPIAs had a detection frequency of 100% in all animals. This is the first report of PFPIAs in fish, dolphin, and bird plasma. Total PFPIA levels (mean ± standard deviation, 1.87 ± 2.17 ng/g wet weight (ww), range of 0.112-15.3 ng/g ww) were 1-2 orders of magnitude lower than those of perfluoroalkyl carboxylates (PFCA) and perfluoroalkanesulfonates (PFSA) in the same samples. The predominant congeners were 6:8 PFPIA (cormorants and pike) and 6:6 PFPIA (dolphins). Total PFPIAs in cormorants from Hamilton Harbour (5.02 ± 2.80 ng/g ww) were statistically higher than in other areas and taxonomic groups. The ubiquity of PFPIAs warrants further research on sources and effects of these unique compounds.

Hydrofluorocarbon (HFC) Emissions in China: An Inventory for 2005-2013 and Projections to 2050.

Many hydrofluorocarbons (HFCs) that are widely used as substitutes for ozone-depleting substances (now regulated under the Montreal Protocol) are very potent greenhouse gases (GHGs). China's past and future HFC emissions are of great interest because China has emerged as a major producer and consumer of HFCs. Here, we present for the first time a comprehensive inventory estimate of China's HFC emissions during 2005-2013. Results show a rapid increase in HFC production, consumption, and emissions in China during the period and that the emissions of HFC with a relatively high global warming potential (GWP) grew faster than those with a relatively low GWP. The proportions of China's historical HFC CO2-equivalent emissions to China's CO2 emissions or global HFC CO2-equivalent emissions increased rapidly during 2005-2013. Using the "business-as-usual" (BAU) scenario, in which HFCs are used to replace a significant fraction of hydrochlorofluorocarbons (HCFCs) in China (to date, there are no regulations on HFC uses in China), emissions of HFCs are projected to be significant components of China's and global future GHG emissions. However, potentials do exist for minimizing China's HFC emissions (for example, if regulations on HFC uses are established in China). Our findings on China's historical and projected HFC emission trajectories could also apply to other developing countries, with important implications for mitigating global GHG emissions.

Persistent organic pollutants in Baltic herring (Clupea harengus)-an aspect of gender.

Persistent organic pollutants (POPs) are monitored regularly in water, sediment, and biota in the Baltic Sea. Lipophilic substances are measured in remarkable concentrations especially in the fatty parts of fish, such as herring (Clupea harengus). However, less lipophilic POPs, e.g. perfluorinated compounds (PFCs), can also be detected. For the first time to our knowledge, this study provides a broad range of contaminant concentrations simultaneously measured in filet, liver, and gonads of both sexes of Baltic herring. We analysed organochlorines, polybrominated diphenyl ethers (PBDEs), and PFCs in mature autumn-spawning individuals and found distinct organ pollutant pattern for all POPs in both sexes. POP concentrations found in the gonads of both sexes indicate that not only females but also males tend to reduce contaminants via reproduction. However, sex-dependent differences could be identified for hexachlorobenzene, PBDEs, and were most remarkable for PFCs. This transfer of contaminants to the gonads in both male and female herring is being underestimated, as it may directly affect the general reproduction success as well as the healthy development of the next generation. Hence, the accumulation of contaminants in the gonads should be considered one possible threat to a healthy wildlife as its achievement is stated by the Baltic Sea Action Plan. Inclusion of a periodic monitoring of POP concentrations in gonads of fish may be an important bioeffect measure to assess the environmental status of biota in the Baltic Sea.

Levels of Contamination by Perfluoroalkyl Substances in Honey from Selected European Countries.

Perfluoroalkyl substances (PFASs) are man-made chemicals manufactured for numerous applications. The aim of this study was to assess the levels of 10 PFASs in selected types of honey samples from selected eastern, northern and southern European countries. A total of 26 samples of honey were analyzed. PFCAs (perfluoroalkyl carboxylic acids) were detected in almost all (92 %) analyzed samples in the range of 0.124-0.798 ng g(-1) ww (wet weight). The average concentrations of particular PFCAs (ng g(-1) ww) in honey samples increased in the following order: perfluorononanoic acid (0.164) < perfluorooctanoic acid (0.189) < perfluoroheptanoic acid (0.271) < perfluorodecanoic acid (0.278). Amongst perfluoroalkane sulfonates, only perfluorohexane sulfonate (PFHxS) was identified in four of 26 analyzed samples, and its concentrations ranged from 0.080 to 0.191 ng g(-1) ww. Italian eucalyptus honey contained the highest total content of PFASs (0.878 ng g(-1) ww). Samples originating from an industrial region of Poland showed 20 % higher concentrations of PFCAs compared to those from non-industrial regions.

Matrix normalized MALDI-TOF quantification of a fluorotelomer-based acrylate polymer.

The degradation of fluorotelomer-based acrylate polymers (FTACPs) has been hypothesized to serve as a source of the environmental contaminants, perfluoroalkyl carboxylates (PFCAs). Studies have relied on indirect measurement of presumed degradation products to evaluate the environmental fate of FTACPs; however, this approach leaves a degree of uncertainty. The present study describes the development of a quantitative matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry method as the first direct analysis method for FTACPs. The model FTACP used in this study was poly(8:2 FTAC-co-HDA), a copolymer of 8:2 fluorotelomer acrylate (8:2 FTAC) and hexadecyl acrylate (HDA). Instead of relying on an internal standard polymer, the intensities of 40 poly(8:2 FTAC-co-HDA) signals (911-4612 Da) were normalized to the signal intensity of a matrix-sodium cluster (659 Da). We termed this value the normalized polymer response (P(N)). By using the same dithranol solution for the sample preparation of poly(8:2 FTAC-co-HDA) standards, calibration curves with coefficient of determinations (R(2)) typically >0.98 were produced. When poly(8:2 FTAC-co-HDA) samples were prepared with the same dithranol solution as the poly(8:2 FTAC-co-HDA) standards, quantification to within 25% of the theoretical concentration was achieved. This approach minimized the sample-to-sample variability that typically plagues MALDI-TOF, and is the first method developed to directly quantify FTACPs.

Physical and Biological Release of Poly- and Perfluoroalkyl Substances (PFASs) from Municipal Solid Waste in Anaerobic Model Landfill Reactors.

A wide variety of consumer products that are treated with poly- and perfluoroalkyl substances (PFASs) and related formulations are disposed of in landfills. Landfill leachate has significant concentrations of PFASs and acts as secondary point sources to surface water. This study models how PFASs enter leachate using four laboratory-scale anaerobic bioreactors filled with municipal solid waste (MSW) and operated over 273 days. Duplicate reactors were monitored under live and abiotic conditions to evaluate influences attributable to biological activity. The biologically active reactors simulated the methanogenic conditions that develop in all landfills, producing ∼140 mL CH4/dry g refuse. The average total PFAS leaching measured in live reactors (16.7 nmol/kg dry refuse) was greater than the average for abiotic reactors (2.83 nmol/kg dry refuse), indicating biological processes were primarily responsible for leaching. The low-level leaching in the abiotic reactors was primarily due to PFCAs ≤C8 (2.48 nmol/kg dry refuse). Concentrations of known biodegradation intermediates, including methylperfluorobutane sulfonamide acetic acid and the n:2 and n:3 fluorotelomer carboxylates, increased steadily after the onset of methanogenesis, with the 5:3 fluorotelomer carboxylate becoming the single most concentrated PFAS observed in live reactors (9.53 nmol/kg dry refuse).

Alternative and Legacy Perfluoroalkyl Substances: Differences between European and Chinese River/Estuary Systems.

The production and use of long-chain perfluoroalkyl substances (PFASs) must comply with national and international regulations. Driven by increasingly stringent regulations, their production has been outsourced to less regulated countries in Asia. In addition, the fluoropolymer industry started to use fluorinated alternatives, such as 2,3,3,3-tetrafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)propanoic acid (HFPO-DA). Between August 2013 and September 2014, we investigated the occurrence and distribution of HFPO-DA and legacy PFASs in surface waters of the following river/estuary systems: the Elbe and Rhine Rivers in Germany, the Rhine-Meuse delta in The Netherlands, and the Xiaoqing River in China. Distinct differences were revealed among the study areas; notably, the Chinese samples were highly polluted by an industrial point source discharging mainly perfluorooctanoic acid (PFOA). This particular point source resulted in concentrations more than 6000 times higher than an industrial point source observed in the Scheur River, where HFPO-DA was the dominant compound with a concentration of 73.1 ng/L. Moreover, HFPO-DA was detected in all samples along the coastline of the North Sea, indicating that the compound may be transported from the Rhine-Meuse delta into the German Bight via the water current. To the best of our knowledge, the fluorinated alternative, HFPO-DA, was detected for the first time in surface waters of Germany and China.