Global discharge of microplastics from mechanical recycling of plastic waste.

The increasing production of plastic products and generation of plastic waste have had increasingly negative environmental impacts. Although recycling could reduce plastic pollution, microplastics can be generated during the process of crushing plastic products during mechanical recycling. We conducted crushing tests with 13 different plastics and documented the size distribution of particles generated. We then estimated the discharge of microplastics associated with recycling and their removal in wastewater treatment plants. We estimated that the global discharge of microplastics would increase from 0.017 Mt in 2000 to 0.749 Mt in 2060. Although mechanical recycling was estimated to account for 3.1% of the total emissions of microplastics for 2017, discharges of microplastics from plastic recycling may increase, even if plastic pollution from well-known sources decreases. Non-OECD (Organization for Economic Cooperation and Development) Asia could be a major discharging region and would play a vital role in reducing discharges of microplastics. Reduction of the discharge of microplastics will require less use of plastic products and upgrading wastewater treatment in many countries.

Biomass conversion and radiocaesium (Rad-Cs) leaching behaviors of radioactive grass in anaerobic wet fermentation systems: Effects of pre-treatments.

Persistent concerns regarding environmental hazards arise from the difficulty in disposing of radioactive plant-based wastes originating from the nuclear accident at the Fukushima Daiichi Nuclear Power Plant (FNPP) in Japan in 2011. In this study, three anaerobic digestion (AD) strategies were proposed: Sole anaerobic wet fermentation, and wet fermentations with either alkaline-heat or ultrasonic pre-treatment, which were employed for long-term anaerobic treatment of a genuine radioactive grass stemming from the FNPP accident. The objectives of this work are to investigate the effects of pre-treatments on biomass conversion efficiency and to gain insight into the leaching behavior of radiocaesium (Rad-Cs) within AD processes. Experimental results indicate that by introducing alkaline-heat and ultrasonic pre-treatments to AD systems, the removal efficiencies of total solids (TS) from the raw grass increased by 60.8 % and 42.5 %, respectively, compared to sole wet fermentation. Pre-treatments have been shown to enhance the stability of AD systems, both in terms of enhancing methane production and mitigating pH fluctuations triggered by the accumulation of organic acids. Remarkably, even though the Rad-Cs leaching rate was highest when the AD system was fed with the alkaline-heat pre-treated grass, it remained unsatisfactory at only 5.77 %. We inadvertently isolated a soil-like component from the raw grass, and analyzed both its proportion in the raw grass and the radioactivity intensity. The results indicate that although the soil constituted only 9.51 % TS of the raw grass, it accounted for a significant 81.35 % of the total radioactivity. The soil, which has a pronounced affinity for ionic Cs, being mixed into the raw grass, was identified as the primary factor limiting the leaching efficiency of Rad-Cs throughout both the pre-treatment and wet fermentation phases.

[Preparation of Nanoplastic Particles as Potential Standards for the Study of Nanoplastics].

Nanoplastics (NPs) are plastic fragments that are small enough to be absorbed by organisms through ingestion or inhalation. Recent studies indicate that nanoplastics can be ubiquitous in the environment, and there are growing concerns regarding the impacts of nanoplastics on the health of humans and other organisms. However, quantitative information on nanoplastics in the environment is still very limited, and most previous toxicity studies have used only polystyrene (PS) particles because of a lack of appropriate model particles of other plastics. We developed a nanoprecipitation-based method for the preparation of nanoplastic particles of five major polymers: low-density polyethylene (LDPE), high-density polyethylene (HDPE), polypropylene (PP), polyvinyl chloride (PVC), and polystyrene. A major advantage of our method is that the nanoplastic particles are prepared without using reagents that can remain in the particles as impurities. Analysis of the prepared particles' molecular weight (Mw) distributions, crystallinities, and thermal properties revealed that their compositions and constitutions were within the general ranges for commercial products. The mechanisms underlying the formation of low-density polyethylene particles via our method were investigated by means of a simple population balance model, and particle diameter was found to be linearly correlated with the suspension density of the nanoplastic dispersion up to 0.4 mg·mL-1. Future studies should focus on improving our method to allow for precise, scale-independent production of nanoplastic particles. Methods for the preparation of labeled particles are also needed so that such particles can be used in nanoplastic risk assessments.

Catalytic pyrolysis of biomass using fly ash leachate to increase carbon monoxide production and improve biochar properties to accelerate anaerobic digestion.

Biomass-derived biochar is attracting growing interest as an effective additive for anaerobic digestion (AD). To improve energy yield and digestion performance through an integrated process of biochar production and AD, biochar upgrading using biomass fly ash leachate as a sustainable metal catalyst was investigated. The results indicate that the bark soaked in the leachate improved the pyrolysis reactivity of biomass with CO2 and reduced the temperature at which the reaction rate reached its maximum from 943 °C to 801 °C. This resulted in a doubling of CO production during CO2-assisted pyrolysis at 800 °C. In addition, the combined use of fly ash leachate and CO2 in bark pyrolysis improved not only the porosity of the resulting biochar but also its wettability and liming potential. Moreover, biochar amended with fly ash leachate and CO2 significantly reduced the lag time in the anaerobic digestion of grease trap waste.

Size-Controlled Preparation of Polyethylene Nanoplastic Particles by Nanoprecipitation and Insights into the Underlying Mechanisms.

Plastic pollution is ubiquitous in the environment, and nanoplastics (<1 µm) are of growing concern as they pose more health risks than larger particles. However, because of a lack of appropriate model particles, studies examining the risks of polyolefin nanoplastics are very limited, despite the prevalence of these plastics in the environment. Although nanoprecipitation using organic solvents is a promising method for preparing model nanoplastic particles of polyolefins, there are currently no methods for controlling the particle size. Here, we examined how the concentration and volume of the feedstock polymer solution affect the size of polyethylene particles produced by nanoprecipitation. The mechanisms underlying the particle formation were investigated by using a simple population balance model. Increasing the concentration of the feedstock solution increased the growth rate and decreased the nucleation rate, and increasing the volume of the feedstock solution increased the growth rate, resulting in an increase in the mean particle diameter in both cases. These changes in particle diameter were linearly correlated with the suspension density of the dispersion up to a suspension density of 0.4 mg·mL-1. In addition, at these suspension densities, spherical particles were prepared without generating aggregates. Together, these results show that the diameter of polyethylene particles prepared by nanoprecipitation could be controlled according to the suspension density up to a suspension density of 0.4 mg·mL-1. This study provides a basis for the development of nanoprecipitation-based techniques for the precise, scale-independent production of model nanoplastic particles, which we hope will accelerate the risk assessment of nanoplastics.

Cross-sectional microstructural analysis to evaluate the crack growth pattern of weathered marine plastics.

Fragmentation of degraded plastics and release of smaller secondary microplastics is usually attributed to the growth of environmental stress cracks. Analysis of crack patterns derived from chemical degradation can be useful not only for assessing the cause of plastic fracture and evaluating the useful lifetime of a product, but it can also potentially provide valuable information on the generation of microplastics. However, the literature with respect to microplastics generation is generally limited to surface observations of polypropylene and polyethylene. Here, we used ion-beam milling to prepare cross-sections of fragments of 15 plastic products made from five commodity plastics (polypropylene, polyethylene, polystyrene, polyvinyl chloride, and polyethylene terephthalate) that were collected at two beaches in Japan, and then we examined the microstructures of those cross-sections by means of scanning electron microscopy and energy dispersive X-ray spectroscopy. Crack growth in the depth direction was examined to provide insights into microplastic generation behavior. In all of the polypropylene samples, and some of the low-density polyethylene and polystyrene samples, cracks with a depth exceeding 100 µm from the sample surface were observed. Considering that crack growth causes fracture of degraded plastic and microplastic release, these observations suggest the release of sharp-edged microplastics from the crack fracture surface. In contrast, in the high-density polyethylene and polyvinyl chloride samples, crack growth was limited to within 20 µm of the sample surface, suggesting the release of irregularly shaped microplastics and additive particles. The present results suggest that the degradation behavior of plastic products in the depth direction is dependent on the type of plastic.

Identification and quantification of additive-derived chemicals in beached micro-mesoplastics and macroplastics.

Although marine plastic debris are expected to retain various chemical additives, little is known about the additives that are retained. We conducted a screening analysis of additives in 261 macroplastic and micro-mesoplastic debris from two beaches. We detected 52 chemicals-antioxidants, phthalates, ultraviolet stabilizers, hindered amine light stabilizers, and flame retardants-and quantified the concentrations of 15 of them. Comparison of the concentrations of Irgafos 168, an antioxidant stabilizer, among sample categories indicated that leaching had occurred from micro-mesoplastics. Differences in diffusion rates between polymer types may explain faster leaching from polyethylene than polypropylene. The significant amounts of Irgafos 168 retained in even micro-mesoplastics indicated the importance of plastics as a vector of additives. This study provides fundamental data needed to assess the risks to organisms from exposure to plastic additives and to understand the effect of stabilizers on the aging behavior of marine plastics.

Optimized production conditions and activation of biochar for effective promotion of long-chain fatty acid degradation in anaerobic digestion.

Engineered biochar production and utilization in anaerobic digestion (AD) potentially overcome its limited application to the treatment of slowly degradable or inhibitory substrates. Here an attempt was made to develop an optimized biochar production procedure for use in AD to stimulate palmitic acid biodegradation via direct interspecies electron transfer (DIET). The electrical conductivity of biochar was greatly increased with an elevated pyrolysis temperature and K2CO3 activation, and the conductivity reached a comparable level (0.6-1.4 S/cm) to that of carbon black at 800 °C. In addition, the K2CO3 activation greatly improved biochar wettability. When using K2CO3-activated biochar produced at 800 °C, the maximum methane production rate from palmitic acid was 1.3 times that of a control without biochar addition.

Mechanical recycling of plastic waste as a point source of microplastic pollution.

Plastic pollution has become one of the most pressing environmental issues. Recycling is a potential means of reducing plastic pollution in the environment. However, plastic fragments are still likely released to the aquatic environment during mechanical recycling processes. Here, we examined the plastic inputs and effluent outputs of three mechanical recycling facilities in Vietnam dealing with electronic, bottle, and household plastic waste, and we found that large quantities of microplastics (plastics <5 mm in length) are generated and released to the aquatic environment during mechanical recycling without proper treatment. Comparisons with literature data for microplastics in wastewater treatment plant effluents and surface water indicated that mechanical recycling of plastic waste is likely a major point source of microplastics pollution. Although there is a mismatch between the size of the microplastics examined in the present study and the predicted no-effect concentration reported, it is still possible that microplastics generated at facilities pose risks to the aquatic environment because there might be many plastic particulates smaller than 315 µm, as suggested by our obtained size distributions. With mechanical recycling likely to increase as we move to a circular plastics economy, greater microplastics emissions can be expected. It is therefore an urgent need to fully understand not only the scale of microplastic generation and release from plastic mechanical recycling but also the environmental risk posed by microplastics in the aquatic environment.

Enhanced anaerobic digestion of tar solution from rice husk thermal gasification with hybrid upflow anaerobic sludge-biochar bed reactor.

Tar generated as a by-product during biomass gasification contains a high concentration of refractory organic matters. In this study, a hybrid upflow anaerobic sludge-biochar bed reactor was established for tar treatment, and the methane yield was 120-154 NmL-CH4/g-CODinf, 20-30% higher than the control reactor. COD removal and methane production significantly decreased in both reactors when the influent tar concentration was doubled from 4954 mg-COD/L to 9964 mg-COD/L. When the influent concentration was reduced, the biochar packed reactor showed a faster recovery. Batch tests confirmed that higher tar concentration inhibited methane production and induced longer lagphase. Biochar addition effectively relieved the inhibition and prolonged the retention of organic matters. SEM observation and 16S rRNA analysis suggested that biochar also acted as the microbe's carrier, and promoted the growth of some microbes. The results of this study provide new ideas for tar treatment.

Preparation of Nanoscale Particles of Five Major Polymers as Potential Standards for the Study of Nanoplastics.

Nanoplastics are likely ubiquitous in the environment, and their potential toxic effects are a concern. However, quantitative information about the distribution of nanoplastics is still lacking, and toxicity tests are limited to a few select polymers because of the lack of appropriate standard materials, which should be nanoscale particles with standardizable morphologies, properties comparable to those of commercial polymers, and no impurities. Here, a precipitation-based method for preparing spherical nanoscale particles without the introduction of impurities is developed. The similarity of the molecular weight distributions, crystallinities, and thermal properties of five major polymers prepared using this method-low-density polyethylene, high-density polyethylene, polypropylene, polyvinyl chloride, and polystyrene-to those of commercial polymers indicate their potential for use as standard nanoplastic particles. This study provides a fundamental approach for the synthesis of standard nanoplastic particles that will facilitate quantification of the concentrations of nanoplastics in the environment and tests of their toxicity, which are required to assess the risks associated with exposure to them.

Direct measurements and modeling of congener group specific vapor pressure for chlorinated paraffins.

Chlorinated Paraffins (CPs) are a complex group of manmade chemicals detected widely in the environment. To predict their environmental fate and effects, it is important to understand their physical-chemical properties including vapor pressure. In this study, the first direct measurements of the vapor pressure for CP congener groups (C10-16Cl4-11) are presented. Vapor pressure was measured above three industrial CP mixtures with different congener distributions between 20 and 50 °C using a gas saturation method. The measured saturated vapor pressure (P∗) decreased with increasing carbon chain length and Cl content. ΔHvap ranged between 73 and 122 kJ mol-1, consistent with data from the literature and model prediction. The experimental log P∗ at 25 °C agreed well with predictions from an empirical regression model in the literature (R2 = 0.97; RSME = 0.25) and with those predicted from the COSMO-RS-trained fragment contribution model (R2 = 0.95; RSME = 0.35). A new empirical model was calibrated with the P∗ data for 35 congener groups measured in this study. Predicted log P∗ values correlate well with field-measured gas/particle partition coefficients and may therefore be used for estimating the environmental fate and pathways of a broad range of CPs in the environment.

Comparison of decabromodiphenyl ether degradation in long-term operated anaerobic bioreactors under thermophilic and mesophilic conditions and the pathways involved.

Anaerobic digestion of decabromodiphenyl ether was carried out and compared in two continuously stirred anaerobic bioreactors for 210 days under thermophilic and mesophilic conditions. Results show that the degradation of decabromodiphenyl ether followed the first-order reaction kinetics, which exhibited a higher removal rate in the thermophilic reactor when compared to the mesophilic one, reaching its maximum of 1.1 µg·day-1. The anaerobic digestion of decabromodiphenyl ether was found to involve the replacement of bromines from polybrominated diphenyl ether by hydrogen atoms, gradually forming nona-, octa- and hepta-brominated diphenyl ether, respectively. Under the thermophilic condition, the reactors were dominated by Bacillus sp. and Methanosarcina sp. with high bioactivity and high concentrations of debromination microorganisms.

Use of comprehensive target analysis for determination of contaminants of emerging concern in a sediment core collected from Beppu Bay, Japan.

In recent years, concern about the release of anthropogenic organic micropollutants referred to as contaminants of emerging concern (CECs) has been growing. The objective of this study was to find potential CECs by means of an analytical screening method referred to as comprehensive target analysis with an automated identification and quantification system (CTA-AIQS), which uses gas and liquid chromatography combined with mass spectrometry (GC-MS and LC-QTOF-MS). We used CTA-AIQS to analyze samples from a sediment core collected in Beppu Bay, Japan. With this method, we detected 80 compounds in the samples and CTA-AIQA could work to useful tool to find CECs in environmental media. Among the detected chemicals, three PAHs (anthracene, chrysene, and fluoranthene) and tris(isopropylphenyl)phosphate (TIPPP) isomers were found to increase in concentration with decreasing sediment depth. We quantified TIPPP isomers in the samples by means of targeted analysis using LC-MS/MS for confirmation. The concentration profiles, combined with previous reports indicating persistent, bioaccumulative, and toxic properties, suggest that these chemicals can be categorized as potential CECs in marine environments.

Bioleaching and removal of radiocesium in anaerobic digestion of biomass crops: Effect of crop type on partitioning of cesium.

Cultivation of biomass crops for energy production is a promising land-use for farmland abandoned owing to radionuclide fallout. However, radionuclides in soil are easily taken up in the crop. To understand phase partitioning of radiocesium Cs (RCs) during anaerobic digestion (AD) of crops, semi-continuous AD experiments were carried out using two types of RCs-contaminated crops. Analysis of fractionated digestate effluent revealed that AD of the crops released RCs into the water phase (up to 82 %), and the efficiency of RCs solubilization depended on crop biodegradability. Adsorption treatment for removal of RCs from the water phase of the digestate indicated a water-zeolite partition coefficient of 0.287 L/g. The efficiency of removal from the water phase was 90 % at an adsorbent dose of 30 g/L.

Liquid chromatography-electrospray ionization-tandem mass spectrometry for the determination of short-chain chlorinated paraffins in mixed plastic wastes.

Wastes containing short-chain chlorinated paraffins (SCCPs) at concentrations above the Basel Convention low persistent organic pollutant content (LPC) values must be destroyed or irreversibly transformed in an environmentally-sound manner. Here, we developed a novel liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MSMS) method for determining the concentrations of SCCPs in mixed plastic wastes. Major SCCP homologues were identified with good separation and peak width by using a low-hydrophobicity cyano-propyl column and a mobile phase consisting of water and methanol containing ammonium acetate. Precursor ion peaks corresponding to the formation of stable SCCP homologue-adducts were observed, followed by two intense product ion peaks corresponding to separation of the adduct into acetate and the homologue. The formulation of a novel calibration standard with known SCCP homologue percentage composition supported the development of our novel mass spectrometric technique. The results obtained with the LC-ESI-MSMS system were quantitatively and qualitatively comparable with those obtained with a high-resolution mass spectrometry (HRMS) coupled to gas chromatography (GC) system. Homologue concentrations determined by LC-ESI-MSMS were significantly correlated with those determined by GC-HRMS in samples of commercial chlorinated paraffin mixture and mixed plastic waste, respectively. As a complementary technique to the highly accurate, but less versatile GC-HRMS approaches, the SCCP analysis by LC-ESI-MSMS is a practical way to identify mixed plastic wastes containing SCCPs at concentrations higher than the Basel Convention's LPC value.

Simple solvatochromic spectroscopic quantification of long-chain fatty acids for biological toxicity assay in biogas plants.

Oily organic waste is a promising feedstock for anaerobic co-digestion. Free long-chain fatty acids (LCFAs) produced from lipids can inhibit methanogenic consortia, so optimal control of LCFA concentration is the key to successful operation of co-digestion. Most LCFAs are present in the solid phase, making them difficult to be detected and monitored. This study proposes a simple and easy method for detecting LCFAs in both the liquid and solid phases of anaerobic digestate by combining liquid-liquid extraction followed by solid-phase extraction (SPE) and spectrophotometric analysis. The extraction procedure successfully removed impurities that interfere with the absorbance spectrum and ensured high recovery rates of LCFAs. The utility of the pretreatment used for the extraction was discussed using thermodynamic analysis and calculations of phase equilibrium for the solvent extraction system. The absorbance spectrum shift of pyridinium N-phenolate betaine (PNPB) dye-stained solution showed a good correlation with LCFA concentration and enabled highly sensitive measurements. Good quantification was demonstrated in experiments using various digestate samples obtained from the laboratory, pilot, and full-scale reactors.

Time series of hexabromocyclododecane transfers from flame-retarded curtains to attached dust.

While the production and new use of hexabromocyclododecane (HBCD) mostly ceased after being listed as a persistent organic pollutant under the Stockholm Convention in 2013, its emission from treated products in use to indoor environments still deserves attention. To examine the transfer of HBCD diastereomers to dust on the surface of flame-retarded curtains and to better characterize the potential of treated fabrics to be sources of HBCD in dust, we carried out a series of 196-day experiments using two types of curtains and attached dusts. Concurrently, the physicochemical properties (vapor pressure, water solubility, and octanol-water partition coefficient) of the HBCD diastereomers were measured. HBCD diastereomers migrated from curtains to dust with half-saturation times of about 20-50 days. By day 196, mean HBCD concentrations in dust had reached 13-290 µg/g, depending on the types of curtains and dusts. The composition of HBCD, dominated by γ-HBCD in the curtains, was dominated by α-HBCD in the post-experiment dusts, probably because of the higher vapor pressure of α-HBCD compared to γ-HBCD. The initial HBCD contents of the two curtains were comparable, but the concentrations and profiles of HBCD diastereomers in the post-experiment dusts differed markedly, probably because differences between the texture and/or surface finishing of the treated fabrics affected HBCD transfer to the attached dust.

Anaerobic degradation of deca-brominated diphenyl ether contaminated in products: Effect of temperature on degradation characteristics.

In this study, a 200-day deca-brominated diphenyl ether (deca-BDE) degradation activity experiment was carried out, using consumer-use curtain material as the substrate. During the degradation process, polybrominated diphenyl ether (PBDE) products with fewer bromine atoms were gradually generated by the debromination of deca-BDE. The influences of temperature, initial substrate dosing mass, and pH were also investigated. Interestingly, thermophilic conditions proved more beneficial for deca-BDE degradation than mesophilic conditions. The results also demonstrate that the debromination rate increased with the initial deca-BDE dosing mass, and that pH 7 was the most suitable for the reaction.

Distribution characteristics of poly-brominated diphenyl ethers between water and dissolved organic carbon from anaerobic digestate: Effects of digestion conditions.

It is becoming increasingly urgent to investigate the partition coefficients (expressed as log KDOC values) of polybrominated diphenyl ethers (PBDEs) in dissolved organic carbon (DOC) present in wastewater. In the current study, after 72 h of equilibration, the concentrations of four common PBDEs were measured in the presence of four DOC solutions from two laboratories and two full-scale anaerobic digestion plants. Sixteen log KDOCs were determined by calculation and unit conversion. The results for the laboratory samples, such as log KDOCs for 2,2',4,4',5,5'-hexabromodiphenyl ether being 6.38 and 5.46 at different reaction temperatures during the cultivate procedure, suggest that a thermophilic environment promotes the solubility of PBDEs to a greater extent than mesophilic conditions. DOC composition directly influences the solubility of PBDEs, even at the same cultivating temperature: the highest log KDOCs for 2,2',4,4',5,6'-hexabromodiphenyl ether were 6.71 and 6.33 in different full-scale plant digestates. A linear regression with an R2 of 0.9863 was used to construct a model describing the potential relationship between log KDOC and the composition of DOC, which includes proteins, polysaccharides and lipids, and which takes into account the positions of bromine atoms, for use in predicting the log KDOC values of PBDEs in different water systems.