Uncovering the characteristics of plastic-associated biofilm from the inland river system of Mongolia.

The occurrence and characteristics of plastic debris in aquatic and terrestrial environments have been extensively studied. However, limited information exists on the properties and dynamic behavior of plastic-associated biofilms in the environment. In this study, we collected plastic samples from an inland river system in Mongolia and extracted biofilms to uncover their characteristics using spectroscopic, isotopic, and thermogravimetric techniques. Mixtures of organic and mineral particles were detected in the extracted biofilms, revealing plastic as a carrier for exogenous substances, including contaminants, in the river ecosystem. Thermogravimetric analysis (TGA) indicated the predominant contribution of minerals primarily comprising aluminosilicate and calcite, representing approximately 80 wt% of the biofilms. Differential thermal analysis (DTA) coupled with Fourier transform infrared (FTIR) spectrometry operated at 25°C-600 °C enabled the detection of gaseous decomposition products, such as CO2, H2O, CO, and functional groups (O-H, C-H, C-O, CO, CC, and C-C), released from biopolymers in the extracted biofilms. Dehydration, dehydroxylation, and decarboxylation reactions explain the thermal properties of biofilms. The stable carbon (δ13C) and nitrogen (δ15N) isotope ratios of the biofilms demonstrated variable signatures ranging from -24.1‰ to -27.0‰ and 3.1‰-12.3‰, respectively. A significant difference in the δ13C value (p < 0.05) among the upstream, middle, and downstream research sites could be characterized by available organic carbon sources in the river environment, depending on the research sites. This study provides insights into the characteristics and environmental behavior of biofilms which are useful to elucidate the impact of plastic-associated biofilms on organic matter and material cycling in aquatic ecosystems.

Plastic-associated metal(loid)s in the urban river environments of Mongolia.

The widespread distribution of plastic debris in riverine environment is one of the major concerns of environmental pollution because of its potential impact on the aquatic ecosystem. In this study, we investigated the accumulation of metal(loid)s on polystyrene foam (PSF) plastics collected from the floodplain of the Tuul River of Mongolia. The metal(loid)s sorbed on plastics were extracted from the collected PSF via sonication after peroxide oxidation. The size-dependent association of metal(loid)s with plastics indicates that PSFs act as vectors for pollutants in the urban river environment. The mean concentrations of metal(loid)s (i.e., B, Cr, Cu, Na, and Pb) indicate a higher accumulation of the metal(loid)s on meso-sized PSFs compared with macro- and micro-sized PSFs. In addition, the images from scanning electron microscopy (SEM) indicated not only the degraded surface of plastics showing fractures, holes, and pits but also the adhered mineral particles and microorganisms on the PSFs. The interaction of metal(loid)s with plastics was probably facilitated by the physical and chemical properties of altered surface of plastics through photodegradation, followed by an increase in surface area by size reduction and/or biofilm development in the aquatic environment. The enrichment ratio (ER) of metals on PSF samples suggested the continuous accumulation of heavy metals on plastics. Our results demonstrate that the widespread plastic debris could be a carrier of hazardous chemicals in the environment. Considering that the negative impacts of plastic debris on environmental health are major concerns to be addressed, the fate and behavior of the plastics especially their interaction with pollutants in aquatic environments should be further studied.

Characterization of biofilms formed on polystyrene microplastics (PS-MPs) on the shore of the Tuul River, Mongolia.

Microplastic (MP) surfaces are common sites for microbial colonization and promote biofilm formation in aquatic environments, resulting in changes to the surface properties of MPs and their interaction with pollutants. Although the diversity of microbial communities adhering to MPs has been well documented in aquatic environments, surface changes in MPs due to microbial colonization are still poorly understood. In this study, we aimed to evaluate the variations in the chemical structure and components of biofilms on the surface of polystyrene microplastics (PS-MPs) collected from the shore of the Tuul River in Mongolia, using micro-Fourier transform infrared (micro-FTIR) spectroscopy. We applied a spectral subtraction approach, and the differences in spectra between peroxide-treated and untreated PS-MP particles enabled us to obtain the structural features of biofilms that developed on the plastic surface. In addition, the surface photooxidation status of the sampled PS-MPs was calculated from the subtracted spectra of peroxide-treated and pristine PS-MPs. Various functional groups of N-containing organic substances from bacterial and fungal communities were detected in the obtained biofilm spectra. Based on the spectral characteristics, biofilm spectra were classified into four groups by applying principal component analysis (PCA). A wide range of carbonyl indices (CIs: 0.00-1.40) was found in the subtracted spectra between peroxide-treated and pristine PS-MPs, revealing that different levels of surface oxidation progressed by physical influences such as solar radiation and freeze-thaw cycles. Furthermore, lignocellulose and silicate were found on the PS-MP surface as allochthonous attachments. Considering the variation in residence time of PS-MPs, they attract plant residues and mineral particles through the development of biofilms and travel together in the river environment. Given that the dynamic behavior of MPs can be greatly affected by changes in their surfaces, further studies are needed to emphasize their link to organic matter dynamics.

Behavior and distribution of polystyrene foams on the shore of Tuul River in Mongolia.

Foamed plastic debris in aquatic systems has become one of the emerging global contaminants. In this study, the behavior of polystyrene foam (PSF) and microplastics (MPs) adhered on the PSFs were investigated on the Tuul River shore in Ulaanbaatar, the capital city of Mongolia. The micro-sized (<5 mm) PSF, which was the dominant PSF over 600 pieces in 100 m2, have accumulated along the shoreline of Tuul River. Carbonyl index (CI) was calculated to evaluate the surface oxidation of macro-sized (20-100 mm), meso-sized (5-20 mm), and micro-sized PSFs and confirm the relative aging depending on photodegradation. CI ranged from 0.00 to 1.09 in the sampled PSFs, whereby the degraded PSFs with high CI were distributed on the shore of downstream of sewer drainage. Micro-sized PSFs showed a wide range of CI and a relatively high average value of CI as compared to those of meso- and macro-sized PSFs. Most of PSFs aggregated with MPs and the adhered MPs have been ubiquitously detected from the surface of PSFs. Adhered micro-sized plastics explored from the surface of PSFs with various sizes, except for mega-sized (>100 mm) PSF, ranged from 5 to 141 items per piece of PSF fragment. The aggregates of PSFs and MPs were common status of PSFs during their transportation. The present findings, which indicated a high concentration of adhered MPs, raise an environmental concern about the widespread aquatic plastic pollution.

Distribution and composition of plastic debris along the river shore in the Selenga River basin in Mongolia.

Plastic pollution in aquatic environments is one of the most fatal environmental issues in the world. Although the distribution of plastic debris in the sea and at coasts has been addressed, the transportation of plastics through a river system is unclear but important. The distribution of plastic debris in the Selenga River system is responsible for the environmental pollution of Lake Baikal. Twelve sampling sites along the river shore of the Selenga River system have been surveyed considering the industrial activity and population density. The number of plastics significantly correlates with the population density. The higher the number of plastics is, the smaller is the average size. The size fractions of foam and film plastics show a significant relationship, suggesting that the plastic debris fragmented on-site on the river shores. The most abundant plastic debris is polystyrene foam (PSF), which is usually used for construction and packaging. Plastic debris occurs due to insufficient plastic waste management. Its distribution is affected by seasonal changes of the water level and flow rate of tributaries. Furthermore, the fragmentation of plastic debris is related to temperature changes associated with freeze and thaw cycles, solar radiation, and mechanical abrasion. Smaller microplastics with microscopic sizes were detected in PSF debris. Based on micro-Fourier transform infrared spectroscopy, these microplastics are polystyrene and polyethylene. This study proves that invisible and visible microplastics are transported together.

Dissolved organic matter distribution and its association with colloidal aluminum and iron in the Selenga River Basin from Ulaanbaatar to Lake Baikal.

The Selenga River Basin (Mongolia and Russia) has suffered from heavy metal contamination by placer gold mining and urban activities in recent decades. The objectives of this study were to provide the first distribution data of dissolved organic matter (DOM) and humic substances (HS) in this data-scarce region, and to investigate their association with dissolved and colloidal metals. Two sampling campaigns were conducted in August of 2013 and 2014. A constant proportion of HS (%HS; coefficient of variation of 2%) was observed from the headwater of Tuul River to the end of the delta before Lake Baikal, spanning > 1000 km in distance. The relationships were determined as [HS] = 0.643 × [DOM] (R2 = 0.996, P < 0.001), and this value (%HS = 64.3) is recommended as an input parameter for metal speciation modeling based on samples collected from the rivers. The DOM and metal (Al and Fe) concentrations in samples doubled through the Zaamar Goldfield mining area, but the influence was mitigated by mixing with the larger Orkhon River, which has better water quality. Metals were mainly present as colloids and had a strong positive correlation with DOM (Al r = 0.81, P < 0.01; Fe r = 0.61, P < 0.01), suggesting that DOM sustains colloidal Al and Fe in solution and they are co-transported in the Selenga River Basin. Land use changes affect water quality and metal speciation and therefore have major implications for the fate of metals.

Mechanism of cadmium biosorption from aqueous solutions using calcined oyster shells.

The physicochemical properties of oyster shell-derived adsorbents prepared by calcination at different temperatures were characterized by elemental analysis, specific surface area, particle size distribution, X-ray diffraction, and scanning electron microscopy. The pH value in natural oyster shell increased from 9 to 12.7 following calcination above 750 °C. All of the oyster shell-derived adsorbents exhibited a BET surface area that ranged from 1.8 to 64.6 m(2)/g. Clearly, the proportion of particles within the ranges 25-50 µm and 50-100 µm increased after calcination, regardless of calcination temperature. The adsorption equilibrium and kinetics of cadmium (Cd) were investigated, and the mechanisms of sorption discussed. Experimental equilibrium data were fitted to a Langmuir adsorption isotherm model. Most Cd adsorption occurred during the initial hours of contact time, and a pseudo-second-order kinetic model best fitted the adsorption process. Cd sorption profiles indicated an initial, low Cd sorption region (25.25-32.36 mg/g) that was associated with calcination temperatures of up to 650 °C for 2 h, and a second region that contributed to high Cd sorption from 750 °C, with the maximum sorption capacity reaching a value of 1666.67 mg/g at 900 °C. The high Cd-removal capacity of oyster shell-derived adsorbents above 750 °C is attributed to their enhanced specific surface area, their material porosity, the bulk precipitation of Cd hydroxide and otavite on shell fragments, the formation of ettringite as a secondary precipitate, and ion exchange via Ca ions. This study highlights the effectiveness of calcined oyster shells in Cd removal from highly contaminated water and wastewater.

Size and shape of soil humic acids estimated by viscosity and molecular weight.

Ultrafiltration fractions of three soil humic acids were characterized by viscometry and high performance size-exclusion chromatography (HPSEC) in order to estimate shapes and hydrodynamic sizes. Intrinsic viscosities under given solute/solvent/temperature conditions were obtained by extrapolating the concentration dependence of reduced viscosities to zero concentration. Molecular mass (weight average molecular weight (M (w)) and number average molecular weight (M (n))) and hydrodynamic radius (R(H)) were determined by HPSEC using pullulan as calibrant. Values of M (w) and M (n) ranged from 15 to 118 x 10(3) and from 9 to 50 x 10(3) (g mol(-1)), respectively. Polydispersity, as indicated by M (w)/M (n), increased with increasing filter size from 1.5 to 2.4. The hydrodynamic radii (R(H)) ranged between 2.2 and 6.4 nm. For each humic acid, M (w) and [eta] were related. Mark-Houwink coefficients calculated on the basis of the M (w)-[eta] relationships suggested restricted flexible chains for two of the humic acids and a branched structure for the third humic acid. Those structures probably behave as hydrated sphere colloids in a good solvent. Hydrodynamic radii of fractions calculated from [eta] using Einstein's equation, which is applicable to hydrated sphere colloids, ranged from 2.2 to 7.1 nm. These dimensions are fit to the size of nanospaces on and between clay minerals and micropores in soil particle aggregates. On the other hand, the good agreement of R(H) values obtained by applying Einstein's equation with those directly determined by HPSEC suggests that pullulan is a suitable calibrant for estimation of molecular mass and size of humic acids by HPSEC.