Microplastics in Arctic waters of the Finnish Sámi area.

We explored the presence of microplastics in the Finnish Arctic Sámi home area. A dialogue between Indigenous knowledge and scientific field work produced data about microplastics in remote wilderness aquatic ecosystems. Methods included geographical Indigenous knowledge analysis, water sampling with fraction filtration, and imaging Fourier transform infrared spectroscopy. The MPs found were small; the mean particle size was 126 ± 121 µm. Particle concentrations of MPs in freshwater and marine samples varied between 45 and 423 MPs m-3 and the most common polymer types were polyethylene, polypropylene, and polyethylene terephthalate. In conclusion, because microplastics are present even in the wilderness areas, their abundance should be monitored to assess plastic pollution in the relatively pristine Arctic environments. Sámi Indigenous knowledge proved to be a beneficial and important initiator, because locals recognize the possible sources and transport pathways of plastic litter, and practical sampling sites in the complex freshwater systems of the area.

Preparation of synthetic micro- and nano plastics for method validation studies.

Microplastic (MP) pollution is a persisting global problem. Accurate analysis is essential in quantifying the effects of microplastic pollution and develop novel technologies that reliably and reproducibly measure microplastic content in various samples. The most common methods for this are FTIR and Raman spectroscopy. Coloured, standardized beads are often used for method validation tests, which limits the conclusions to a very specific case rarely observed in the natural environment. This study focuses on the preparation of reference micro- and nanoplastics via cryogenic milling and shows their use for FTIR and Raman method validation studies. MPs can now be reproducibly milled from various plastics, offering the advantages of a better representation of MPs in real environment. Moreover, this study highlights issues with the current detection methods, up to now considered as the most reliable ones for MP detection and identification. Such issues, e.g. misidentification, will need to be addressed in the future. Additionally, milled MPs were used in experiments with commercial high-resolution imaging device, enabling a possible in-situ optical detection of microplastics. These experiments represent a step forward in understanding MPs in a water sample and provide a basis for a more accurate detection and identification directly from water, which would considerably reduce the time of analysis.

Exposure protocol for ecotoxicity testing of microplastics and nanoplastics.

Despite the increasing concern about the harmful effects of micro- and nanoplastics (MNPs), there are no harmonized guidelines or protocols yet available for MNP ecotoxicity testing. Current ecotoxicity studies often use commercial spherical particles as models for MNPs, but in nature, MNPs occur in variable shapes, sizes and chemical compositions. Moreover, protocols developed for chemicals that dissolve or form stable dispersions are currently used for assessing the ecotoxicity of MNPs. Plastic particles, however, do not dissolve and also show dynamic behavior in the exposure medium, depending on, for example, MNP physicochemical properties and the medium's conditions such as pH and ionic strength. Here we describe an exposure protocol that considers the particle-specific properties of MNPs and their dynamic behavior in exposure systems. Procedure 1 describes the top-down production of more realistic MNPs as representative of MNPs in nature and particle characterization (e.g., using thermal extraction desorption-gas chromatography/mass spectrometry). Then, we describe exposure system development for short- and long-term toxicity tests for soil (Procedure 2) and aquatic (Procedure 3) organisms. Procedures 2 and 3 explain how to modify existing ecotoxicity guidelines for chemicals to target testing MNPs in selected exposure systems. We show some examples that were used to develop the protocol to test, for example, MNP toxicity in marine rotifers, freshwater mussels, daphnids and earthworms. The present protocol takes between 24 h and 2 months, depending on the test of interest and can be applied by students, academics, environmental risk assessors and industries.

Detecting different amorphous - Amorphous phase separation patterns in co-amorphous mixtures with high resolution imaging FTIR spectroscopy.

Many active pharmaceutical ingredients (API) in development suffer from low aqueous solubilities. Instead of the crystal form, the amorphous state can be used to improve the API's apparent solubility. However, the amorphous state has a higher Gibb's free energy and is inherently unstable and tends to transform back to the more stable crystal form. In co-amorphous mixtures, phase separation needs to occur before there can be crystallization. The aim of this study was to devise a method to study amorphous-amorphous phase separation with high resolution imaging Fourier transform infrared (FTIR) spectroscopy with seven 1:1 M ratio API-API binary mixtures being examined. The binary mixtures were amorphized by melt-quenching and stored above their glass transition temperature (Tg) to monitor their phase separation. Thermodynamic properties (crystallization tendency, melting point (Tm) and Tg) of these mixtures were measured with differential scanning calorimetry (DSC) to verify the amorphization method and to assess the optimal storage temperature. The phase separation was examined with FTIR imaging in the transmission mode. Furthermore, measurements with two pure APIs were performed to ensure that the alterations occurring in the spectra were caused by phase separation not storage stress. In addition, the reproducibility of the imaging FTIR spectrometer was verified. The spectra were analyzed with principal component analysis (PCA) and a characteristic peak comparison method. Scatter-plots were produced from the amount of phase separated pixels in the measurement area as a way of visualizing the progress of phase separation. The results indicated that imaging with FTIR spectroscopy can produce reproducible results and the progress of phase separation can be detected as either a sigmoidal or as a start-to-finish linear pattern depending on the substances.

Irradiation Induced Biochemical Changes in Human Mandibular Bone: A Raman Spectroscopic Study.

Understanding the biochemical changes in irradiated human mandible after radiotherapy of cancer patients is critical for oral rehabilitation. The underlying mechanism for radiation-associated changes in the bone at the molecular level could lead to implant failure and osteoradionecrosis. The study aimed to assess the chemical composition and bone quality in irradiated human mandibular bone using Raman spectroscopy. A total of 33 bone biopsies from 16 control and 17 irradiated patients were included to quantify different biochemical parameters from the Raman spectra. The differences in bone mineral and matrix band intensities between control and irradiated groups were analyzed using unpaired Student's t-test with statistical significance at p < 0.05. Findings suggest that the intensity of the phosphate band is significantly decreased and the carbonate band is significantly increased in the irradiated group. Further, the mineral crystallinity and carbonate to phosphate ratio are increased. The mineral to matrix ratio is decreased in the irradiated group. Principal component analysis (PCA) based on the local radiation dose and biopsy time interval of irradiated samples did not show any specific classification between irradiation sub-groups. Irradiation disrupted the interaction and bonding between the organic matrix and hydroxyapatite minerals affecting the bone biochemical properties. However, the normal clinical appearance of irradiated bone would have been accompanied by underlying biochemical and microscopical changes which might result in radiation-induced delayed complications.

Chemical composition and particle size influence the toxicity of nanoscale plastic debris and their co-occurring benzo(α)pyrene in the model aquatic organisms Daphnia magna and Danio rerio.

Little is known about how particle chemical composition and size might influence the toxicity of nanoscale plastic debris (NPD) and their co-occurring chemicals. Herein, we investigate the toxicity of 3 × 1010 particles/L polyethylene (PE, 50 nm), polypropylene (PP, 50 nm), polystyrene (PS, 200 and 600 nm), and polyvinyl chloride (PVC, 200 nm) NPD and their co-occurring benzo(a)pyrene (BaP) to Daphnia magna and Danio rerio. During the 21 days of exposure to PE 50 nm and PS 200 nm, the number of broods produced by D. magna decreased compared to other treatments. Exposure to BaP alone did not produce any effects on the reproduction of the daphnids, however, the mixture of BaP with PS (200 or 600 nm) or with PE (50 nm) reduced the number of broods. Exposure of D. rerio embryos to PE 50 nm, PS 200 nm, and PS 600 nm led to a delay in the hatching. The presence of PS 200 nm and PVC 200 nm eliminated the effects of BaP on the hatching rate of zebrafish. Our findings suggest that data generated for the toxicity of one type of NPD, e.g. PVC or PS may not be extrapolated to other types of NPD.

Validation of an imaging FTIR spectroscopic method for analyzing microplastics ingestion by Finnish lake fish (Perca fluviatilis and Coregonus albula).

Despite the ubiquitousness of microplastics, knowledge on the exposure of freshwater fish to microplastics is still limited. Moreover, no standard methods are available for analyzing microplastics, and the quality of methods used for the quantification of ingested microplastics in fish should be improved. In this study, we studied microplastic ingestion of common wild freshwater fish species, perch (Perca fluviatilis) and vendace (Coregonus albula). Further, our aim was to develop and validate imaging Fourier-transform infrared spectroscopic method for the quantification of ingested microplastics. For this purpose, enzymatically digested samples were measured with focal plane array (FPA) based infrared microscope. Data was analyzed with siMPle software, which provides counts, mass estimations, sizes, and materials for the measured particles. Method validation was conducted with ten procedural blanks and recovery tests, resulting in 75% and 77% recovery rates for pretreatment and infrared imaging, respectively. Pretreatment caused contamination principally by small <100 µm microplastics. The results showed that 17% of perch and 25% of vendace had ingested plastic. Most of the fish contained little or no plastics, while some individuals contained high numbers of small particles or alternatively few large particles. Perch from one sampling site out of five had ingested microplastics, but vendace from all sampling sites had ingested microplastics. The microplastics found from fish were mostly small: 81% had particle size between 20 and 100 µm, and most of them were polyethylene, polypropylene, and polyethylene terephthalate. In conclusion, the implemented method revealed low numbers of ingested microplastics on average but needs further development for routine monitoring of small microplastics.

Particle balance and return loops for microplastics in a tertiary-level wastewater treatment plant.

Microplastics (MPs) from households, stormwater, and various industries are transported to wastewater treatment plants (WWTPs), where a high proportion of them are captured before discharging their residuals to watersheds. Although recent studies have indicated that the removed MPs are mainly retained in wastewater sludge, sludge treatment processes have gained less attention in MP research than water streams at primary, secondary, and tertiary treatments. In this study, we sampled 12 different process steps in a tertiary-level municipal WWTP in central Finland. Our results showed that, compared to the plant influent load, three times more MPs circulated via reject water from the sludge centrifugation back to the beginning of the treatment process. Fibrous MPs were especially abundant in the dewatered sludge, whereas fragment-like MPs were observed in an aqueous stream. We concluded that, compared to the tertiary effluent, sludge treatment is the major exit route for MPs into the environment, but sludge treatment is also a return loop to the beginning of the process. Our sampling campaign also demonstrated that WWTPs with varying hydraulic conditions (such as the one studied here) benefit from disc filter-based tertiary treatments in MP removal.

The pursuit of resin-dentin bond durability: Simultaneous enhancement of collagen structure and polymer network formation in hybrid layers.

OBJECTIVE: Imperfect polymer formation as well as collagen's susceptibility to enzymatic degradation increase the vulnerability of hybrid layers over time. This study investigated the effect of new dimethyl sulfoxide (DMSO)-containing pretreatments on long-term bond strength, hybrid layer quality, monomer conversion and collagen structure. METHODS: H3PO4-etched mid-coronal dentin surfaces from extracted human molars (n = 8) were randomly treated with aqueous and ethanolic DMSO solutions or following the ethanol-wet bonding technique. Dentin bonding was performed with a three-step etch-and-rinse adhesive. Resin-dentin beams (0.8 mm2) were stored in artificial saliva at 37 °C for 24 h and 2.5 years, submitted to microtensile bond strength testing at 0.5 mm/min and semi-quantitative SEM nanoleakage analysis (n = 8). Micro-Raman spectroscopy was used to determine the degree of conversion at different depths in the hybrid layer (n = 6). Changes in the apparent modulus of elasticity of demineralized collagen beams measuring 0.5 × 1.7 × 7 mm (n = 10) and loss of dry mass (n = 10) after 30 days were calculated via three-point bending and precision weighing, respectively. RESULTS: DMSO-containing pretreatments produced higher bond strengths, which did not change significantly over time presenting lower incidence of water-filled zones. Higher uniformity in monomer conversion across the hybrid layer occurred for all pretreatments. DMSO-induced collagen stiffening was reversible in water, but with lower peptide solubilization. SIGNIFICANCE: Improved polymer formation and higher stability of the collagen-structure can be attributed to DMSO's unique ability to simultaneously modify both biological and resin components within the hybrid layer. Pretreatments composed of DMSO/ethanol may be a viable-effective alternative to extend the longevity of resin-dentin bonds.

Towards the Development of Portable and In Situ Optical Devices for Detection of Micro and Nanoplastics in Water: A Review on the Current Status.

The prevalent nature of micro and nanoplastics (MP/NPs) on environmental pollution and health-related issues has led to the development of various methods, usually based on Fourier-transform infrared (FTIR) and Raman spectroscopies, for their detection. Unfortunately, most of the developed techniques are laboratory-based with little focus on in situ detection of MPs. In this review, we aim to give an up-to-date report on the different optical measurement methods that have been exploited in the screening of MPs isolated from their natural environments, such as water. The progress and the potential of portable optical sensors for field studies of MPs are described, including remote sensing methods. We also propose other optical methods to be considered for the development of potential in situ integrated optical devices for continuous detection of MPs and NPs. Integrated optical solutions are especially necessary for the development of robust portable and in situ optical sensors for the quantitative detection and classification of water-based MPs.

Sediment trapping - An attempt to monitor temporal variation of microplastic flux rates in aquatic systems.

Sediment trapping as a tool to monitor microplastic influx was tested in an urban boreal lake basin. The one-year-long trap monitoring consisted of 5-month and 7-month periods representing growing season and winter season (including the spring flood event), respectively. Sediment accumulation rate (SAR), and organic content were determined, highest SAR - 14.5 g/m2/d - was measured during the winter period. Microplastics were extracted from the sediment applying heavy-liquid density separation method and collected under a microscope for further identification with FTIR spectroscopy. PE was identified as the most abundant synthetic polymer type, while PP and PET are also present. The annual microplastic flux rate is 32 400 pieces/m2/year, and highest accumulation does not coincide with the highest SAR, but occurs during the growing season. Changes in the microplastic accumulation rates are related to seasonal conditions. Highest microplastic concentration with respect to dry sediment weight (10 200 pieces/kg) was observed in a growing season sample, while highest concentration with respect to sediment volume (1800 pieces/l) was observed during winter. This finding underlines the problems related to reporting microplastic concentrations in various units. The results highlight that sediment trap monitoring is an efficient tool for monitoring microplastic accumulation rate in aquatic environments and provides an opportunity to better understand and define processes controlling microplastic accumulation.

Plastic debris composition and concentration in the Arctic Ocean, the North Sea and the Baltic Sea.

Neuston samples were collected with a Manta trawl in the rim of the Arctic Ocean, in the Northern Atlantic Ocean and the Baltic Sea at eleven coastal and open-sea locations. All samples contained plastics identified by FTIR microscopy. Altogether, 110 microplastics pieces were classified according to size, shape, and polymer type. The concentrations at the locations were generally low (x̅ = 0.06, SD ± 0.04 particles m-3) as compared to previous observations. The highest concentrations were found towards the Arctic Ocean, while those in the Baltic Sea were generally low. The most abundant polymer type was polyethylene. Detected particle types were mainly fragments. The number of films and fibers was very low. The mean particle size was 2.66 mm (SD ± 1.55 mm). Clustering analyses revealed that debris compositions in the sea regions had characteristic differences possibly reflecting the dependences between compositions, drifting distances, sinking rates, and local oceanographic conditions.

Microplastics accumulate to thin layers in the stratified Baltic Sea.

In the Baltic Sea, water is stratified due to differences in density and salinity. The stratification prevents water from mixing, which could affect sinking rates of microplastics in the sea. We studied the accumulation of microplastics to halocline and thermocline. We sampled water with a 100 µm plankton net from vertical transects between halo- and thermocline, and a 30 L water sampler from the end of halocline and the beginning of thermocline. Thereafter, microplastics in the whole sample volumes were analyzed with imaging Fourier transform infrared spectroscopy (FTIR). The plankton net results showed that water column between halo- and thermoclines contained on average 0.92 ± 0.61 MP m-3 (237 ± 277 ng/m-3; mean ± SD), whereas the 30 L samples from the end of halocline and the beginning of thermocline contained 0.44 ± 0.52 MP L-1 (106 ± 209 ng L-1). Hence, microplastics are likely to accumulate to thin layers in the halocline and thermocline. The vast majority of the found microplastics were polyethylene, polypropylene and polyethylene terephthalate, which are common plastic types. We did not observe any trend between the density of microplastics and the sampling depth, probably because biofilm formation affected the sinking rates of the particles. Our results indicate the need to sample deeper water layers in addition to surface waters at least in the stratified water bodies to obtain a comprehensive overview of the abundance of microplastics in the aquatic environment.

Raman imaging of amorphous-amorphous phase separation in small molecule co-amorphous systems.

Many new active pharmaceutical ingredients (API) undergoing development have low permeabilities or low aqueous solubilities. However, the amorphous state is usually more soluble than its crystalline counterpart. The amorphous state has a higher Gibb's free energy, which can improve the apparent solubility but decrease the stability since the amorphous state tends to transform to the more stable crystalline form. Before recrystallization, a co-amorphous binary mixture's ingredients have to undergo a phase separation. The aim of this study was to obtain a better understanding of the amorphous-amorphous phase separation in co-amorphous binary mixtures and test the suitability of imaging Raman spectroscopy for detecting this phenomenon. To study the phase separation, we prepared three different 50:50 mass ratio binary mixtures of APIs: paracetamol-terfenadine, (PAR-TRF), paracetamol-indomethacin (PAR-IMC) and terfenadine-indomethacin (TRF-IMC). The binary mixtures were amorphized with melt-quenching and stored above their glass transition temperature (Tg) to monitor their phase separation. Thermal degradation was determined with a high performance liquid chromatography (HPLC) method to ensure that melt-quenching did not cause any thermal degradation of the molecules. Thermodynamic attributes (crystallization tendency, melting point (Tm) and Tg) were measured with differential scanning calorimetry (DSC) to ensure that the co-amorphous systems transformed to the amorphous state and remained amorphous after cooling and reheating. Phase separation was studied from the surface and cross-section (CS) with Raman imaging to examine if it occurred more on the surface than in the bulk. The Raman spectra were analyzed with principal component analysis (PCA) and Contour plots were produced from the PCA-score values to visualize concentration differences in the mixtures. The results showed that API vs API concentrations increased as a function of time in both surface and CS images before crystallization. This suggests that Raman imaging is a suitable technique to detect the phase separation phenomena in small molecule co-amorphous binary mixtures.

Microplastic concentrations, size distribution, and polymer types in the surface waters of a northern European lake.

We examined microplastic concentrations, size distributions, and polymer types in surface waters of a northern European dimictic lake. Two sampling methods, a pump sieving water onto filters with different pore sizes (20, 100, and 300 µm) and a common manta trawl (333 µm), were utilized to sample surface water from 12 sites at the vicinity of potential sources for microplastic emissions. The number and polymer types of microplastics in the samples were determined with optical microscopy and µFTIR spectroscopy. The average concentrations were 0.27 ± 0.18 (mean ± SD) microplastics/m3 in manta trawled samples and 1.8 ± 2.3 (>300 µm), 12 ± 17 (100-300 µm) and 155 ± 73 (20-100 µm) microplastics/m3 in pump filtered samples. The majority (64%) of the identified microplastics (n = 168) were fibers, and the rest were fragments. Materials were identified as polymers commonly used in consumer products, such as polyethylene, polypropylene, and polyethylene terephthalate. Microplastic concentrations were high near the discharge pipe of a wastewater treatment plant, harbors, and snow dumping site. PRACTITIONER POINTS: Samples were taken with a manta trawl (333 µm) and a pump filtration system (300/100/20 µm) With pump filtration, small 20-300 µm particles were more common than >300 µm particles The average concentration of manta trawled samples was 0.27 ± 0.18 (mean ± SD) microplastics/m3 FTIR analysis revealed PE, PP, PET, and PAN to be the most common polymers.