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Hyporheic zones (HZs) are dynamic and complex transition regions between rivers and aquifers which are thought to play an important role in the attenuation of environmental micropollutants. Non-steady state and small-scale hyporheic processes which affect micropollutants in the HZ are poorly characterized due to limitations in existing analytical methodologies. In this work we developed a method for high spatio-temporal resolution analysis of polar organic micropollutants (POMs) in hyporheic pore- and surface waters by combining (semi-) automatic low volume sampling techniques with direct-injection ultra-high performance liquid chromatography tandem mass spectrometry. The method is capable of quantifying 25 parent compounds and 18 transformation products (TPs) using only 0.4 mL of water and few preparation steps. Application of the method to both surface and pore water revealed significant (i.e. > an order of magnitude) differences in POM concentrations over small time and spatial scales (i.e. < a few hours and tens of cm, respectively). Guanylurea, a TP of the antidiabetic drug metformin was detected at unprecedentedly high concentrations. Collectively, this method is suitable for in situ characterization of POMs at high spatial and temporal resolution and with minimal disturbance of natural flow paths and infiltration of surface water.

Many transformation products (TPs) from organic micropollutants are not included in routine environmental monitoring programs due to limited knowledge of their occurrence and fate. An efficient method to identify and prioritize critical compounds in terms of environmental relevance is needed. In this study, we applied a strategic screening approach based on a case-control concept to identify TPs formed along wastewater-impacted rivers. Time-integrated samples were collected over one week at both ends of a river stretch downstream of a wastewater treatment plant (WWTP) outfall and were analyzed by ultrahigh performance liquid chromatography interfaced with quadrupole time-of-flight mass spectrometry (UHPLC-QToF-MS/MS). The screening procedure of the high-resolution MS (HRMS) datasets consisted of three major steps: (i) screening for parent compounds (PCs) attenuated along the stretch; (ii) prediction of potential TPs from these PCs; and (iii) screening for TPs from this list with an increasing trend along the stretch. In total, 32 PCs decreased along the investigated river stretches. From these PCs, eight TPs had increasing concentrations along the studied stretches and could be tentatively identified. The identification of one TP (benzamide) was confirmed by its corresponding reference standard, while no standards were available for the remaining TPs.

RATIONALE: Knudsen effusion mass spectrometry (KEMS) shows improved performance with the "restricted collimation" method of Chatillon and colleagues, which consists of two apertures between the Knudsen cell orifice and the ionizer. These apertures define the shape and position of the molecular beam independently of the sample and effusion orifice and as a result reduce background and improve sampling from the Knudsen cell.Modeling of the molecular beam in restricted collimation allows optimization of the apertures’ diameters and spacing. METHODS:Knudsen flow is easily simulated with a Monte Carlo method. In this study a Visual Basic for Excel (VBA) code is developed to simulate the molecular beam originating from a vaporizing condensed phase in a Knudsen cell and passing through the cell orifice and the two apertures. RESULTS: The code is able to calculate the transmission coefficient through the cell orifice, through the cell orifice and the first aperture, and through the cell orifice and first and second apertures. Also calculated are the angular distributions of the effusate density emerging from the cell and average number of collisions with the orifice walls. CONCLUSIONS: This code allows the geometry (aperture spacing and diameters) of the sampling system to be optimized for maximum transmission. The calculated effusate distributions and low average number of orifice wall collisions illustrated the advantages of restricted collimation. Calculated transmission factors are also compared to literature values calculated via the analytical method of Chatillon and colleagues.

A considerable knowledge gap exists with respect to the fate and environmental relevance of transformation products (TPs) of polar organic micropollutants in surface water. To narrow this gap we investigated the fate of 20 parent compounds (PCs) and 11 characteristic TPs in four wastewater-impacted rivers. Samples were obtained from time-integrated active sampling as well as passive sampling using polar organic chemical integrative samplers (POCIS). Seventeen out of the 20 PCs were detected in at least one of the rivers. All the PCs except acesulfame, carbamazepine, and fluconazole were attenuated along the studied river stretches, with the largest decrease found in the smallest river which had an intense surface water-pore water exchange. Seven TPs were detected, all of which were already present directly downstream of the WWTP outfall, suggesting that the WWTPs were a major source of TPs to the recipients. For anionic compounds, attenuation was the highest in the two rivers with the lowest discharge, while the pattern was not as clear for neutral or cationic compounds. For most compounds the results obtained from active sampling were not significantly different from those using POCIS, demonstrating that the cost and labor efficient POCIS is suitable to determine the attenuation of organic micropollutants in rivers.

Occurrence of the antibiotic sulfamethoxazole (SMX) in the aquatic environment is of concern due to its potential to induce antibiotic resistance in pathogenic bacteria. While degradation of SMX can occur by numerous processes, the environmental fate of its transformation products (TPs) remains poorly understood. In the present work, biodegradation of SMX photo-TPs was investigated in a water/sediment system. Photo-TPs were produced by exposing SMX to artificial sunlight for 48 h. The resulting mixture of 8 photo TPs was characterized using a combination of ultra-high performance liquid chromatography coupled to high-resolution mass spectrometry and tandem mass spectrometry, and then used in biodegradation experiments. Significant differences in transformation among SMX photo-TPs were observed in the water/sediment system, with four photo-TPs displaying evidence of biodegradation (dissipation half-lives [DT50] of 39.7 d for 3-amino-5-methylisoxazole, 12.7 d for 4-nitro-sulfamethxoazole, 7.6 d for an SMX isomer and 2.4 d for [C10H13N3O4S]), two displaying primarily abiotic degradation (DT50 of 31 d for sulfanilic acid and 74.9 d for 5-methylisoxazol-3-yl-sulfamate), and two photo TPs behaving largely recalcitrantly. Remarkably, TPs previously reported to be photo-stable also were persistent in biodegradation experiments. The most surprising observation was an increase in SMX concentrations when the irradiated solution was incubated, which we attribute to back-transformation of certain photo TPs by sediment bacteria (85% from 4-nitro-sulfamethoxazole). This process could contribute to exposure to SMX in the aquatic environment that is higher than one would expect based on the fate of SMX alone. The results highlight the importance of considering TPs along with their parent compounds when characterizing environmental risks of emerging contaminants.

Although diclofenac ranks among the most frequently detected pharmaceuticals in the urban water cycle, its environmental transformation reactions remain imperfectly understood. Biodegradation-induced changes in N-15/N-14 ratios (epsilon(N) = -7.1 parts per thousand +/- 0.4 parts per thousand) have indicated that compound-specific isotope analysis (CSIA) may detect diclofenac degradation. This singular observation warrants exploration for further transformation reactions. The present study surveys carbon and nitrogen isotope fractionation in other environmental and engineered transformation reactions of diclofenac. While carbon isotope fractionation was generally small, observed nitrogen isotope fractionation in degradation by MnO2 (epsilon(N) = -7.3 parts per thousand +/- 0.3 parts per thousand), photolysis (epsilon(N) = +1.9 parts per thousand +/- 0.1 parts per thousand), and ozonation (epsilon(N) = +1.5 parts per thousand +/- 0.2 parts per thousand) revealed distinct trends for different oxidative transformation reactions. The small, secondary isotope effect associated with ozonation suggests an attack of O-3 in a molecular position distant from the N atom. Model reactants for outer-sphere single electron transfer generated large inverse nitrogen isotope fractionation (epsilon(N) = +5.7 parts per thousand +/- 0.3 parts per thousand), ruling out this mechanism for biodegradation and transformation by MnO2. In a river model, isotope fractionation-derived degradation estimates agreed well with concentration mass balances, providing a proof-of-principle validation for assessing micropollutant degradation in river sediment. Our study highlights the prospect of combining CSIA with transformation product analysis for a better assessment of transformation reactions within the environmental life of diclofenac.

The hyporheic zone—the transition region beneath and alongside the stream bed—is a central compartment for attenuation of organic micropollutants in rivers. It provides abundant sorption sites and excellent conditions for biotransformation. We used a bench-scale flume to study the fate of 19 parent pharmaceuticals (PPs) and the formation of 11 characteristic transformation products (TPs) under boundary conditions similar to those in hyporheic zones. The persistence of PPs ranged from readily degradable with a dissipation half-life (DT50) as short as 1.8 days (acetaminophen, ibuprofen) to not degradable (chlorthalidone, fluconazole). The temporal and spatial patterns of PP and TP concentrations in pore water were heterogeneous, reflecting the complex hydraulic and biogeochemical conditions in hyporheic zones. Four TPs (carbamazepine-10,11-epoxide, metoprolol acid, 1-naphthol, and saluamine) were exclusively formed in the sediment compartment and released to surface water, highlighting their potential to be used as indicators for characterizing hyporheic transformation of micropollutants in streams. The accumulation of certain TPs over the experimental period illustrates that we might face a peak of secondary contamination by TPs far from the point of release of the original contaminants into a stream. Such TPs should be considered as priority candidates for a higher-tier environmental risk assessment.

It is challenging to measure the persistence of chemicals under field conditions. In this work, two approaches for measuring persistence in the field were compared: the chemical mass balance approach, and a novel chemical benchmarking approach. Ten pharmaceuticals, an X-ray contrast agent, and an artificial sweetener were studied in a Swedish lake. Acesulfame K was selected as a benchmark to quantify persistence using the chemical benchmarking approach. The 95% confidence intervals of the half-life for transformation in the lake system ranged from 780-5700 days for carbamazepine to <1-2 days for ketoprofen. The persistence estimates obtained using the benchmarking approach agreed well with those from the mass balance approach (1-21% difference), indicating that chemical benchmarking can be a valid and useful method to measure the persistence of chemicals under field conditions. Compared to the mass balance approach, the benchmarking approach partially or completely eliminates the need to quantify mass flow of chemicals, so it is particularly advantageous when the quantification of mass flow of chemicals is difficult. Furthermore, the benchmarking approach allows for ready comparison and ranking of the persistence of different chemicals., AuthorCount:5

Chemical benchmarldng was used to investigate the temporal variation of the persistence of chemical contaminants in a Swedish lake. The chemicals studied included 12 pharmaceuticals, an artificial sweetener, and an X-ray contrast agent. Measurements were conducted in late spring, late autumn, and winter. The transformation half-life in the lake could be quantified for 7 of the chemicals. It ranged from several days to hundreds of days. For 5 of the chemicals (bezafibrate, climbazole, diclofenac, furosemide, and hydrochlorothiazide), the measured persistence was lower in late spring than in late autumn. This may have been caused by lower temperatures and/or less irradiation during late autumn. The seasonality in chemical persistence contributed to changes in chemical concentrations in the lake during the year. The impact of seasonality of persistence was compared with the impact of other important variables determining concentrations in the lake: chemical inputs and water flow/dilution. The strongest seasonal variability in chemical concentration in lake water was observed for hydrochlorothiazide (over a factor of 10), and this was attributable to the seasonality in its persistence.

Multimedia fate and transport models are used to evaluate the long range transport potential (LRTP) of organic pollutants, often by calculating their characteristic travel distance (CTD). We calculated the CTD of several polycyclic aromatic hydrocarbons (PAHs) and metals using two models: the OECD P-OV& LRTP Screening Tool (The Tool), and ELPOS. The absolute CTDs of PAHs estimated with the two models agree reasonably well for predominantly particle-bound congeners, while discrepancies are observed for more volatile congeners. We test the performance of the models by comparing the relative ranking of CTDs with the one of experimentally determined travel distances (ETDs). ETDs were estimated from historical deposition rates of pollutants to peat bogs in Eastern Canada. CTDs and ETDs of PAHs indicate a low LRTP. To eliminate the high influence on specific model assumptions and to emphasize the difference between the travel distances of single PAHs, ETDs and CTDs were analyzed relative to the travel distances of particle-bound compounds. The ETDs determined for PAHs, Cu, and Zn ranged from 173 to 321 km with relative uncertainties between 26% and 46%. The ETDs of two metals were shorter than those of the PAHs. For particle-bound PAHs the relative ETDs and CTDs were similar, while they differed for Chrysene., AuthorCount:4