The sorption of two phthalate esters (PAEs) and phenanthrene (PHE) by different natural organic matter fractions (NOMs) was examined. The surface area of the NOMs correlated positively with the starting decomposition temperature (SDT), implying increased number of micropores with the rise of condensation. Sorption of PHE on nonhydrolyzable carbons (NHCs) and other NOMs was respectively dependent on aromatic and aliphatic C contents. Likely physical blocking of the aliphatic moieties and input of black carbon materials led to elevated sorption capacity for PHE of aromatic domains in the NHCs. Sorption of PAEs by NOMs excluding NHCs was jointly regulated by hydrophobic partitioning and H-bonding interactions. The SDT of the NOMs correlated negatively with the Koc when SDT ≥304 °C, likely because the highly condensed domains may impair the availability of amorphous moieties for sorption. This study highlights the influence of domain accessibility of NOMs on sorption of hydrophobic organic contaminants.

The perdurability of plastics in the environment is one of the major concerns of plastic pollution and, as a consequence, oceans are accumulating large amounts of plastic. The degradation of conventional and biobased materials was evaluated through a laboratory experiment for a year simulating four different conditions in the marine environment. The water column environmental compartment was simulated under euphotic and aphotic (with and without light availability) conditions. The seafloor environmental compartment was simulated with sediment under non-polluted and polluted conditions. By combining weight loss (%), spectroscopic and thermal analyses, the degradation patterns regarding the polymer structure were assessed. The studied biobased materials were polylactic acid (PLA) based materials and showed higher degradability than conventional ones. The weight loss of conventional materials was not influenced by the water column or sediment, while in PLA-based materials, the degradation rates were ca. 5 times greater in the sediment than in the water column. The absorbance (Abs) value at 3400 cm⁻¹ for polyethylene terephthalate (PET), and carbonyl (CO) index for PET and PLA could be useful to detect early signs of degradation. The crystallization index could be a useful parameter to discriminate degradation stages. The obtained results highlight the different degradability rates of materials depending on the specific environmental marine conditions.

The sorption of PAH on 12 different sediments was investigated and was correlated to their corresponding organic matter (OM) content and quality. For this purpose, the OM was precisely characterized using thermal analysis consisting in the successive combustion and quantification of the increasingly thermostable fractions of the OM. Simultaneously, the water-exchangeable fraction of the sorbed PAH defined as the amount of PAH freely exchanged between the water and the sediment (by opposition to the PAH harshly sorbed to the sediments particles) was determined using a passive sampler methodology recently developed. The water concentrations, when the sediment-water system is equilibrated, were also assessed which allows the determination of the sediment-water distribution coefficients without artifacts introduced by the non water-exchangeable fraction of PAH. Hence, the present study provides the distribution coefficients of PAH between the water and 4 different OM fractions combusted at a specific temperature range. The calculated distribution coefficients demonstrate that the sedimentary OM combusted at the intermediate temperature range (between 300 °C and 450 °C) drives the reversible sorption of PAH while the inferred sorption to the OM combusted at a lower and higher temperature range does not dominate the partitioning process.

Microplastics are ubiquitous in the marine environment but characterizing them in marine organisms is challenging. Herein we describe a method to detect, identify, and quantify microplastics in marine mussels (Mytilus edulis) using thermal gravimetric analysis – Fourier Transform infrared spectroscopy – gas chromatography mass spectrometry (TGA-FTIR-GC/MS) after extracting and isolating the microplastics using chemical digestion, density separation, and filtration. Combining the three instrumental techniques adds discriminatory power as temperature profiles, chromatograms, and vibrational and mass spectra differ among common plastics. First, we tested several digestion schemes after spiking the mussels with plastics commonly found in the marine environment, including polyethylene (PE), polystyrene (PS), polypropylene (PP) and polyvinyl chloride (PVC). KOH (10%, w/v) was the most suitable reagent, providing good recoveries (>97%) without degrading the microplastics. We show that the technique TGA-FTIR-GC/MS can be optimized to readily determine both the type (polymer) and amount (mass) of microplastics in the sample. Applied to 100 mussels from each of six locations along the coast of China, we found an average of 0.58 mg of plastic per kg of tissue (range 0.16–1.71 mg/kg), with PE being the most abundant type of plastic measured. Among the coastal cities, mussels from Dalian had the highest microplastic content. Overall, we demonstrate that the method is a powerful technique to quantify masses of microplastics in marine mussels, a species commonly used as a bioindicator of pollution, and may be applied to other biota as well.

As a global pollutant, microplastics have attracted attention from the public and researchers. However, the lack of standard and time-saving methods for analysis has become one of the bottlenecks in microplastics research. Here, we demonstrate TGA coupled to FTIR to identify and quantify certain microplastics in environment. Samples were pyrolyzed in TGA and the pyrolysis gases were analyzed by FTIR. Combining TGA and FTIR data adds discriminatory power as temperature profiles and absorption spectra differ among several common plastics. To quantify on a mass basis, we calibrated on characteristic IR peaks at temperatures of maximum weight loss for individual polymers. The method can distinguish PVC, PS and was validated by spiking samples with known quantities of microplastics. The result of field sample experiments showed that TGA-FTIR can be used to identify and quantify PVC and PS in bivalves, seawater and soil. And the method may be applicable to environmental samples.

In this study, a chabazite-rich tuff (CHA) from the Bala deposit of Ankara region (Turkey) and its modified forms (CuCHA, AgCHA, FeCHA, and HCHA samples) were investigated at 273 and 298 K using volumetric apparatus up to 100 kPa. The chabazite samples were characterized by using thermal analysis (TG-DTG-DTA), X-ray diffraction (XRD), X-ray fluorescence (XRF), scanning electron microscopy with detector X-ray energy dispersive (SEM-EDX), Fourier transform infrared (FT-IR), and N₂ adsorption methods. It was found that natural chabazite is composed of predominantly chabazite with small amounts of clinoptilolite and erionite. XRD showed that there are major structural changes to Fe- and H-exchanged chabazite samples. Capacity of chabazites for CH₄ ranged from 0.168 and 1.341 mmol/g. Among all the modified forms, it was observed that Ag form of chabazite zeolite had the greatest methane adsorption capacity at both temperatures.

The effect of styrene-divinylbenzene copolymer functionalization by carboxylic acid groups on the adsorption of p-nitrophenol (p-NP) from aqueous solutions was investigated. The adsorption capacity of p-NP onto the functionalized copolymer (CP-F) was compared with that of the precursor copolymer, the chloromethylated styrene-divinylbenzene copolymer (CP-N). The two copolymers were characterized by Fourier transform infrared (FTIR) spectroscopy, thermal analysis (DSC-TG), specific surface area and particle size measurements, pore size distribution, scanning electron microscopy (SEM), and elemental analysis (EDX). The adsorption of p-NP was substantially enhanced after the polymer functionalization, and it was demonstrated that hydrogen bonding is principally responsible for the high adsorption capacity of CP-F in comparison with CP-N. The adsorption kinetics of p-NP adsorption onto CP-F was well described by the pseudo-second-order model. From the four investigated isotherms, Langmuir, Freundlich, Redlich-Peterson, and Sips, the equilibrium data were better described by the Sips model. The maximum adsorption capacity of the CP-F polymer resulting from the Sips isotherm was 243.37 mg g⁻¹. The capacity of regeneration and reuse of the CP-F polymer was evaluated in three consecutive cycles of adsorption-desorption.

Fibrous mats of polymer/clay were obtained by electrospinning method, and their capacity for heavy metals removal from water was evaluated. Four different fibrous mats were prepared from a corresponding polymer/clay solutions. The precursor materials employed were poly-ε-caprolactone, polyvinyl alcohol polymers, kaolin, and metakaolin clays. Raw materials and the prepared fiber mats characterization were carried out using scanning electron microscopy, Fourier transformed infrared spectroscopy, X-ray diffraction, termogravimetric analysis, differential thermal analysis, and differential scanning calorimetry. Elemental composition of the materials was obtained using energy-dispersive X-ray spectroscopy. The environmental applications of polymer/clay materials were tested for water treatment by heavy metals (cadmium (Cd⁺²), chromium (Cr⁺³), copper (Cu⁺²), and lead (Pb⁺²)) sorption. Kinetic adsorption studies were conducted employing heavy metal solutions with initial concentration of 200 mg/L, and the amount of heavy metal adsorbed and kinetics parameters was determined using inductively coupled plasma-optical emission spectroscopy (ICP-OES). According to the kinetic data, the adsorption process of Cd⁺², Cr⁺³, Cu⁺², and Pb⁺² onto polymer/clay is favorable for the prepared materials and they follow a pseudo-first-order model according to the kinetic analysis. Additionally, the intraparticle diffusion was evaluated by applying the Morris and Weber model; in order to investigate the contribution of film resistance to the kinetics of the heavy metals adsorption, the adsorption kinetic data was further analyzed by Boyd’s film-diffusion model.

The occurrence of heavy metals in the natural aquatic systems arising from anthropogenic sources is an issue of global and environmental concern because of their extremely harmful effects to living beings even in rather low concentrations. The synthesis and ring-opening metathesis polymerization (ROMP) of novel norbornene dicarboximides bearing highly aromatic pendant groups, specifically, N-4-tritylphenyl-norbornene-5,6-dicarboximide (2a) and N-2,4,6-(triphenyl)phenyl-norbornene-5,6-dicarboximide (2b), their hydrogenation and further polymer sulfonation to render them adsorbents for the uptake of heavy metal ions from water is reported in this study. The macromolecules were characterized by means of FT-IR, ¹H NMR, and thermal analysis, among others. A thoroughly kinetic and isothermal study of adsorption in single and ternary aqueous solutions of Pb²⁺, Cd²⁺, and Ni²⁺ was performed considering several experimental variables for instance initial metal concentration, contact time and solution pH. In general, the experimental data were adjusted more efficiently to the pseudo-second order kinetic model and to the Freundlich isotherm model, respectively. The maximum removal amounts were found to be 55.7 mg/g for Pb²⁺, 33.9 mg/g for Cd²⁺, and 10.2 mg/g for Ni²⁺ in the sulfonated trityl-bearing polymer 5a while those found for the sulfonated triphenyl-bearing polymer 5b were 31.5 mg/g for Pb²⁺, 26.6 mg/g for Cd²⁺, and 7.0 mg/g for Ni²⁺, respectively. The higher heavy metal removal capacity of polymer 5a was attributed to its also higher degree of sulfonation. The outcomes indicate that these novel sulfonic acid containing polymer-based adsorbents are effective for the uptake of heavy metallic elements from water.

In this work, different analytical techniques (thermal analysis, ¹³C cross-polarization magic angle spinning (CPMAS) NMR and Fourier transform infrared (FT-IR) spectroscopy) have been used to study the organic matter changes during the co-composting of pig slurry with cotton gin waste. To ensure the validity of the findings, the composting process was developed in different scenarios: under experimental pilot plant conditions, using the static pile system, and under real conditions on a pig farm, using the turning pile system. Also, the thermal stability index (R1) was determined before and after an extraction with water, to evaluate the effect of eliminating water-soluble inorganic salts on the thermal analysis. The results of the thermal methods showed the degradation of the most labile organic matter during composting; R1 increased during composting in all piles, without any influence of the presence of water-soluble inorganic ions in the sample. The NMR showed a decrease in the abundance of the carbohydrate molecules and an increase in the aliphatic materials during composting, due to a concentration effect. Also, FT-IR spectroscopy was a useful technique to study the trends of polysaccharides and nitrate, as indicators of organic matter transformations during composting.