Microplastic discharge from a wastewater treatment plant: long term monitoring to compare two analytical techniques, LDIR and optical microscopy while also assessing the removal efficiency of a bubble curtain.

In this study we compare two parallel analytical methods while also testing a microplastics mitigation method. We assess the effectiveness of a bubble curtain to reduce microplastics in a wastewater treatment plant (WWTP)-effluent canal during the course of six months (>70 samples) using two analytical techniques: laser direct infrared (LDIR) and optical microscopy (OM) covering a size range of 0.02 to 5 mm. Comparison of the two analytical strategies shows similar trends, fluctuations, and correlating particle and fibre numbers. However, absolute values of particles differ, and the strategies provide different levels of information: LDIR is capable of identifying the plastic type as well as shape, while OM cannot determine the plastic type. Furthermore LIDR has a lower size limit (10-20 µm) than OM (50 µm). While information obtained by OM in general is far less detailed it is more affordable. This research also shows that the bubble curtain pilot does not have a measurable effect on the particle concentration. Possible effects of the curtain are hidden in the temporal variations. This research also reveals that individual samples show a large variation in particle numbers, illustrating that single measurements might give a poor representation of environmental particle number.

Quantum cascade laser imaging (LDIR) and machine learning for the identification of environmentally exposed microplastics and polymers.

Monitoring of microplastics in environmental samples is relevant to the scientific world, as well as to environmental agencies and water authorities, in particular considering increasing efforts to decrease emissions and the growing concern of governments and the public. Therefore, rapid accurate detection and identification of microplastics including polymers, despite their degradation in the environment, is crucial. The degradation has a significant impact on the infrared spectra of the microplastics and can impede the identification process. This work presents a novel approach to addressing the problem of identification of weathered microplastics. A quantum cascade laser (LDIR) was used to record the infrared spectra of various polymeric particles (81,291 individual particles). Using a combination of pristine and weathered particles, two supervised machine learning (ML) models, namely Subspace k-Nearest Neighbor (Sub-kNN) and Boosted Decision Tree (BDT), were trained to recognize the spectrum characteristics of labeled particles and then used to identify unlabeled samples, with an identification accuracy of 89.7% and 77.1% using 10-fold cross validation. About 90% of the samples could be identified via the Sub-kNN or BDT models. Subsequently, a non-supervised ML model, namely, Density-based Spatial Clustering of Applications with Noise (DBSCAN), was used to cluster samples which could not be labeled from the supervised ML model. This enabled the detection of additional subgroups of microplastics. Manual labelling can then be carried out on a selection of spectra per group (e.g., centroids of each cluster), hence accelerating the identification process and allowing to add new labeled samples to the initial supervised ML. Although expert efforts are still needed, the proposed method greatly lowers labeling efforts by using the combined supervised and unsupervised learning models. In the future, the use of deep neural networks could further boost the implementation of these kinds of approaches for polymer and microplastic identification in environmental settings.

Analysis of (functionalized) fullerenes in water samples by liquid chromatography coupled to high-resolution mass spectrometry.

One of the main challenges in environmental risk assessment of fullerenes is to develop analytical methods that detect and quantify fullerenes at low concentrations. In this paper we report on the development and optimization of a highly specific, robust, and relatively simple method for the quantitative determination of C60, C70, and six functionalized fullerenes, namely, [6,6]-phenyl-C61-butyric acid methyl ester, [6,6]-phenyl-C61-butyric acid butyl ester, [6,6]-phenyl-C61-butyric acid octyl ester, [6,6]-bis(phenyl)-C61-butyric acid methyl ester, [6,6]-thienyl-C61-butyric acid methyl ester, and [6,6]-phenyl-C71-butyric acid methyl ester ([70PCBM], in different aqueous matrixes. For this method fullerenes were extracted from the aqueous phase using solid-phase extraction (SPE), with subsequent analysis on a liquid chromatography-Orbitrap mass spectrometry (LC-Orbitrap MS) system. SPE was optimized by varying different conditions to improve recovery of all fullerenes. Different SPE column materials (C18, C18e, C8, CN) were tested, and recoveries appeared to be the highest for the C18-material. Recoveries were improved by adding NaCl to the water during extraction. Very low limit of detection (LOD) values were obtained for all compounds with this method, ranging from 0.17 ng/L for [70]PCBM to 0.28 ng/L for C60, and subsequent limit of quantitation (LOQ) values of 0.57-0.91 ng/L. Recoveries for the fullerenes were on average 120% in ultrapure and drinking water. Recoveries appeared to be lower, but still acceptable (e.g., >78%), in surface water. The developed approach is promising and will be applied, for example, in (1) environmental monitoring, (2) a more in-depth study of environmental fate and transformation products, and (3) studying water treatment efficiency of C60, C70, and the various functionalized fullerenes.

A monitoring and data analysis method for microplastics in marine sediments.

In Europe, policy frameworks demand the monitoring of microplastics in marine sediments. Here we provide a monitoring and data analysis method for microplastic particles designed to be used in the context of Marine Strategy Framework Directive (MSFD) and OSPAR policy frameworks. Microplastics were analysed in marine sediments at four different locations in Dutch coastal and transitional waters using replicate sampling to investigate micro-spatial variation. Particle size distribution followed a power law with slope 3.76. Thirteen polymers were identified, with their composition varying between sediments near densely populated West coast areas versus the more rural Wadden Sea area. We quantify differences in the micro-spatial variation of microplastic concentrations between locations using the relative standard error of the mean (RSEM). This metric provides an opportunity to optimize the sensitivity of trend detection in microplastic monitoring networks by selecting locations with relatively low micro-spatial variation. We provide a method to optimize the number of replicate samples for a given location using its relationship with the RSEM. Two replicate samples appear to be cost-effective for relatively homogenous locations, whereas more heterogenous locations require four replicates.

Sorption behavior of charged and neutral polar organic compounds on solid phase extraction materials: which functional group governs sorption?

Numerous polar anthropogenic organic chemicals have been found in the aqueous environment. Solid phase extraction (SPE) has been applied for the isolation of these from aqueous matrices, employing various materials. Nevertheless, little is known about the influence of functional groups on the sorption of the solutes onto these materials. Therefore, the sorption interactions of (charged) polar organic solutes to neutral (HLB), cation-exchanging (MCX, WCX), and anion-exchanging (MAX, WAX) OASIS polymers have been studied. For neutral solutes HLB has the highest capacity and affinity. Van der Waals interaction, rather than hydrogen bonding, appears to be the predominant factor determining sorption. For charged molecules, MCX and MAX show by far the highest affinity and capacity. Adsorption is already efficient at low concentrations and the maximum sorption capacity equals the amount of charged functional groups on the material. The results from this study allow semiquantitative predictions if a solute will adsorb on one of the OASIS materials and which functional groups govern adsorption.

Fate of microplastics in the drinking water production.

Microplastics are ubiquitous and consequently enter drinking water treatment plants. Knowledge of the microplastic fate in drinking water production is still very limited, although explorative studies have shown tap water contains low contents of microplastics. In this study, we measure microplastic concentrations in drinking water sources and assess the effectiveness of various drinking water treatment facilities to reduce the microplastic concentrations in water to gain insight into the fate of microplastics. Two analytical techniques, laser direct infrared spectroscopy (LDIR) and optical microscopy, have been applied to cover the particle size range from 20 µm to 5 mm. In total five different drinking water sites were investigated using four different types of raw water (groundwater, surface water, dune filtrate and riverbank filtrate) for drinking water production. This research shows that drinking water treatment removes the majority of microplastics and that concentration of microplastics larger than 20 µm in tap water is less than 2 microplastics particles per litre. Between the different raw water sources it is found that groundwater had by far the lowest microplastics concentrations (< 1.000 microplastics per m3) and the highest concentration was found in riverine water, up to 460.000 particles per m3, specifically in the Lek Canal () (a canal connected to the river Rhine). On average the most abundant plastics found are polyamide (PA, 33%), polyethylene terephthalate (PET, 15%), rubbers (10%), polyethylene (PE, 10%) and chlorinated polyethylene (CPE, 7%). This study also showed that natural treatment steps, such as dune infiltration and sedimentation, remove microplastics effectively. However, this may introduce an adverse effect where microplastics potentially accumulate in the sediment and environment.

Riverine microplastic and microbial community compositions: A field study in the Netherlands.

Plastic pollution in aquatic environments, particularly microplastics (<5 mm), is an emerging health threat. The buoyancy, hydrophobic hard surfaces, novel polymer carbon sources and long-distance transport make microplastics a unique substrate for biofilms, potentially harbouring pathogens and enabling antimicrobial resistance (AMR) gene exchange. Microplastic concentrations, their polymer types and the associated microbial communities were determined in paired, contemporaneous samples from the Dutch portion of the river Rhine. Microplastics were collected through a cascade of 500/100/10 µm sieves; filtrates and surface water were also analysed. Microplastics were characterized with infrared spectroscopy. Microbial communities and selected virulence and AMR genes were determined with 16S rRNA-sequencing and qPCR. Average microplastic concentration was 213,147 particles/m3; polyamide and polyvinylchloride were the most abundant polymers. Microbial composition on 100-500 µm samples differed significantly from surface water and 10-100 µm or smaller samples, with lower microbial diversity compared to surface water. An increasingly 'water-like' microbial community was observed as particles became smaller. Associations amongst specific microbial taxa, polymer types and particle sizes, as well as seasonal and methodological effects, were also observed. Known biofilm-forming and plastic-degrading taxa (e.g. Pseudomonas) and taxa harbouring potential pathogens (Pseudomonas, Acinetobacter, Arcobacter) were enriched in certain sample types, and other risk-conferring signatures like the sul1 and erm(B) AMR genes were almost ubiquitous. Results were generally compatible with the existence of taxon-selecting mechanisms and reduced microbial diversity in the biofilms of plastic substrates, varying over seasons, polymer types and particle sizes. This study provided updated field data and insights on microplastic pollution in a major riverine environment.

Is there evidence for man-made nanoparticles in the Dutch environment?

Only very limited information is available on measured environmental concentrations of nanoparticles. In this study, several environmental compartments in The Netherlands were probed for the presence of nanoparticles. Different types of water were screened for the presence of inorganic (Ag, Au, TiO2) and organic nanoparticles (C60, C70, [6,6]-phenyl-C61-butyric acid octyl ester, [6,6]-phenyl-C61-butyric acid butyl ester, [6,6]-phenyl-C61-butyric acid methyl ester, [6,6]-bis-phenyl-C61-butyric acid methyl ester, [6,6]-phenyl-C71-butyric acid methyl ester, [6,6]-thienyl-C61-butyric acid methyl ester). Air samples were analysed for the presence of nanoparticulate Mo, Ag, Ce, W, Pd, Pt, Rh, Zn, Ti, Si, B as well as Fe and Cu. ICP-MS, Orbitrap-HRMS, SEM and EDX were used for this survey. Water samples included dune and bank filtrates, surface waters and ground waters as well as influents, effluents and sludge of sewage treatment plants (STPs), and surface waters collected near airports and harbours. Air samples included both urban and rural samples. C60 was detected in air, sewage treatment plants, influents, effluents and sludge, but in no other aqueous samples despite the low detection limit of 0.1ng/L. C70 and functionalised fullerenes were not detected at all. In STP sludge and influent the occurrence of Ag and Au nanoparticles was verified by SEM/EDX and ICP-MS. In air up to about 25m% of certain metals was found in the nanosize fraction. Overall, between 1 and 6% of the total mass from metals in the air samples was found in the size fraction <100nm.

Analytical assessment about the simultaneous quantification of releasable pharmaceutical relevant inorganic nanoparticles in tap water and domestic waste water.

For pharmaceutical applications, the use of inorganic engineered nanoparticles is of growing interest while silver (Ag) and gold (Au) are the most relevant elements. A few methods were developed recently but the validation and the application testing were quite limited. Therefore, a routinely suitable multi element method for the identification of nanoparticles of different sizes below 100 nm and elemental composition by applying asymmetric flow field flow fraction (AF4) - inductively coupled plasma mass spectrometry (ICPMS) is developed. A complete validation model of the quantification of releasable pharmaceutical relevant inorganic nanoparticles based on Ag and Au is presented for the most relevant aqueous matrices of tap water and domestic waste water. The samples are originated from locations in the Netherlands and it is of great interest to study the unwanted presence of Ag and Au as nanoparticle residues due to possible health and environmental risks. During method development, instability effects are observed for 60 nm and 70 nm Ag ENPs with different capping agents. These effects are studied more closely in relation to matrix effects. Besides the methodological aspects, the obtained analytical results and relevant performance characteristics (e.g. measuring range, limit of detection, repeatability, reproducibility, trueness, and expanded uncertainty of measurement) are determined and discussed. For the chosen aqueous matrices, the results of the performance characteristics are significantly better for Au ENPs in comparison to Ag ENPs; e.g. repeatability and reproducibility are below 10% for all Au ENPs respectively maximal 27% repeatability for larger Ag ENPs. The method is a promising tool for the simultaneous determination of releasable pharmaceutical relevant inorganic nanoparticles.

Size and concentration determination of (functionalised) fullerenes in surface and sewage water matrices using field flow fractionation coupled to an online accurate mass spectrometer: method development and validation.

In order to assess the environmental risks of a compound it is imperative to have suitable and reliable techniques for its determination in environmental matrices. In this paper, we focused on a method development for the recently introduced online coupling of a field flow fractionation (FFF) system to an Orbitrap-HRMS, that allows the simultaneous size and concentration determination of different aqueous fullerene aggregates and their concentrations in different size fractions. A 0.05% NH4OH solution in water was identified as the best carrier liquid for the analysis of the three different aqueous fullerene suspensions (C60 [60], [6,6]-phenyl-C61 butyric acid methyl ester ([60]PCBM) and [6,6]-(bis)phenyl-C61 butyric acid methyl ester ([60]bisPCBM)). The multi-angle light scattering (MALS) data received after employing the ammonia solution was consistent with both the theory and calibration using well defined Au and latex particles. The LODs obtained using Orbitrap HRMS detection were 0.1 µg L(-1) for an injection volume of 100 µL which are significantly better than the LODs obtained by using UV (20 µg L(-1)) and MALS detectors (5 µg L(-1)). However, these LODs can be further improved as in theory there is no limit to the amount of sample that can be injected into the FFF. Environmental samples (river and sewage water) were spiked with fullerenes and the fractograms obtained for these samples revealed that the matrix does affect the size of fullerene aggregates. Information on the size distribution can be useful for the risk assessment of these particles.

Pd-catalysed cross coupling of terminal alkynes to diynes in the absence of a stoichiometric additive.

An efficient, room temperature procedure for the cross-coupling of a range of terminal alkynes, using standard Sonogashira cross-coupling conditions (Pd/Cu) is presented. At higher reaction temperatures, head-to-tail or head-to-head dimerisation affords 1,3- and 1,4-disubstituted enynes, respectively as minor products.

Sample preparation for combined chemical analysis and in vitro bioassay application in water quality assessment.

The combination of in vitro bioassays and chemical screening can provide a powerful toolbox to determine biologically relevant compounds in water extracts. In this study, a sample preparation method is evaluated for the suitability for both chemical analysis and in vitro bioassays. A set of 39 chemicals were spiked to surface water, which were extracted using Oasis MCX cartridges. The extracts were chemically analyzed by liquid chromatography linear ion trap Orbitrap analysis and recoveries appeared to be on average 61% Compounds with logK(ow) values in the range between 0 and 4 are recovered well using this method. In a next step, the same extracts were tested for genotoxic activity using the Comet assay and Ames fluctuation test and for specific endocrine receptor activation using a panel of CALUX assays, for estrogenic (ER), androgenic (AR), glucocorticoid (GR), progestagenic (PR), and thyroidogenic (TR) agonistic activities. The results of the genotoxicity assays indicated that spiked genotoxic compounds were preserved during sample preparation. The measured responses of the GR CALUX and ER CALUX assays were similar to the predicted responses. The measured responses in the AR CALUX and PR CALUX assays were much lower than expected from the analytical concentration, probably due to antagonistic effects of some spiked compounds. Overall, the presented sample preparation method seems to be suitable for both chemical analysis and specific in vitro bioassay applications.

Removal of charged micropollutants from water by ion-exchange polymers -- effects of competing electrolytes.

A wide variety of environmental compounds of concern, e.g. pharmaceuticals or illicit drugs, are acids or bases that may predominantly be present as charged species in drinking water sources. These charged micropollutants may prove difficult to remove by currently used water treatment steps (e.g. UV/H(2)O(2), activated carbon (AC) or membranes). We studied the sorption affinity of some ionic organic compounds to both AC and different charged polymeric materials. Ion-exchange polymers may be effective as additional extraction phases in water treatment, because sorption of all charged compounds to oppositely charged polymers was stronger than to AC, especially for the double-charged cation metformin. Tested below 1% of the polymer ion-exchange capacity, the sorption affinity of charged micropollutants is nonlinear and depends on the composition of the aqueous medium. Whereas oppositely charged electrolytes do not impact sorption of organic ions, equally charged electrolytes do influence sorption indicating ion-exchange (IE) to be the main sorption mechanism. For the tested polymers, a tenfold increased salt concentration lowered the IE-sorption affinity by a factor two. Different electrolytes affect IE with organic ions in a similar way as inorganic ions on IE-resins, and no clear differences in this trend were observed between the sulphonated and the carboxylated cation-exchanger. Sorption of organic cations is five fold less in Ca(2+) solutions compared to similar concentrations of Na(+), while that of anionic compounds is three fold weaker in SO(4)(2-) solutions compared to equal concentrations of Cl(-).

Phosphabarrelene-modified Rh-catalysts: a new and selective route towards hydroxy-functionalized bicyclic imidazoles via tandem reactions.

8-Hydroxy-6-methyl-5,6,7,8-tetrahydroimidazo[1,2-a]pyridine was formed selectively in high yields from N-(beta-methallyl)imidazole by a tandem hydroformylation-cyclization sequence, representing a novel one-pot catalytic synthesis of bicyclic imidazole derivatives.

Ion-tagged pi-acidic alkene ligands promote Pd-catalysed allyl-aryl couplings in an ionic liquid.

Ionic pi-acidic alkene ligands based on chalcone and benzylidene acetone frameworks have been "doped" into ionic liquids to provide functional reaction media for Pd-catalysed cross-couplings of a cyclohexenyl carbonate with aryl siloxanes that allow simple product isolation, free from Pd (<50 ppm) and ligand contamination.