Polybrominated diphenyl ethers (PBDEs) are toxic chemicals widely distributed in the environment, but few studies are available on their potential toxicity to rice at metabolic level. Therefore we exposed ten rice (Oryza sativa) varieties to 2,2′,4,4′-tetrabromodiphenyl ether (BDE-47), a predominant congener of PBDEs, in hydroponic solutions with different concentrations. Two varieties that showed different biological effects to BDE-47, YY-9 and LJ-7, were screened as sensitive and tolerant varieties according to changes of morphological and physiological indicators. Metabolic research was then conducted using gas chromatography−mass spectrometry combined with diverse analyses. Results showed that LJ-7 was more active in metabolite profiles and adopted more effective antioxidant defense machinery to protect itself against oxidative damages induced by BDE-47 than YY-9. For LJ-7, the contents of 13 amino acids and 24 organic acids, especially l-glutamic acid, beta-alanine, glycolic acid and glyceric acid were up-regulated significantly which contributed to scavenging reactive oxygen species. In the treatment of 500 μg/L BDE-47, the contents of these four metabolites increased by 33.6-, 19.3-, 10.6- and 10.2-fold, respectively. The levels of most saccharides (such as d-glucose, lactulose, maltose, sucrose and d-cellobiose) also increased by 1.7–12.4 fold which promoted saccharide-related biosynthesis metabolism. Elevation of tricarboxylic acid cycle and glyoxylate and dicarboxylate metabolism enhanced energy-producing processes. Besides, the contents of secondary metabolites, chiefly polyols and glycosides increased significantly to act on defending oxidative stress induced by BDE-47. In contrast, the levels of most metabolites decreased significantly for YY-9, especially those of 13 amino acids (by 0.9%–67.1%) and 19 organic acids (by 7.8%–70.0%). The positive metabolic responses implied LJ-7 was tolerant to BDE-47, while the down-regulation of most metabolites indicated the susceptible nature of YY-9. Since metabolic change might affect the yield and quality of rice, this study can provide useful reference for rice cultivation in PBDEs-polluted areas.

PM1 aerosol, collected during winter campaign in urban area situated close to a large automobile factory, was analysed on content of selected organic compounds, namely monosaccharide anhydrides, diterpenoids (including retene and resin acids), n-alkanes (including pristane and phytane), polycyclic aromatic hydrocarbons (including picene), monosaccharides, disaccharides, polyols, hopanes and steranes.Monosaccharide anhydrides (MAs, markers for biomass burning) were the most abundant organic compounds (the mean sum of concentration of 513 ng m−3). The sum of MAs constituted in average 70.0% of the mass of all analysed organic compounds and 1.91% of the PM1 mass. Diterpenoids, markers for softwood combustion, were the second most abundant analysed organic compounds (the mean concentration of 119 ng m−3). The mean concentrations of other studied organic compounds were smaller, namely saccharides 31.6 ng m−3, n-alkanes, including isoprenoids 35.3 ng m−3, PAHs 15.6 ng m−3 and hopanes, including one sterane 1.54 ng m−3.Combustion of solid fuels (coal and wood) for household heating was the dominant emission source of carbonaceous aerosols sampled during the campaign. The composition of aerosols collected in the studied locality was affected by local emissions and also by regional transport of polluted air from small villages nearby Mladá Boleslav.Two unit risks (WHO and CalEPA) were applied for the estimation of carcinogenic risk of PAHs exposure. The computed lifetime cancer risk at the studied locality during the campaign period was 1.93 × 10−4 (WHO unit risk) and 2.43 × 10−6 (CalEPA unit risk) on average. However, the real cancer risk for the lifetime exposure (70 years) is lower at the studied locality because our measurement lasted only 2 weeks in winter when the concentrations of PAHs were higher than in other seasons of the year.

In this study, wastes originating at each production station during refrigerator manufacturing were identified and classified based on a waste tree. A mass balance study revealed a total waste production factor of 0.046 kg/kg of a product of which 75.3%, 23.9%, and 0.8% were non-hazardous wastes (NHWs), packaging wastes (PWs), and hazardous wastes (HWs), respectively. Wastes produced during refrigerator manufacturing were grouped under 35 different waste codes. Waste codes that contributed more than 5% by weight were 15 02 02 (contaminated absorbent material), 15 01 10 (contaminated packaging), 16 02 13 (electronic cards), 07 02 14 (polyol) and 08 05 01 (isocyanates), 19 08 13 (treatment sludge), 16 02 15 (capacitors), and 13 01 13 (hydraulic oil) for HWs, 12 01 01 (ferrous metal), and 16 02 16 (components) for NHWs, and, finally, 15 01 03 (wooden), 15 01 01 (paper&cardboard), and 15 01 02 (plastic) for PWs over 5 years. Scrap costs were used as a surrogate to determine production stages that generated high amounts of metal and plastic wastes. Logarithmically, increasing and decreasing trends were observed for PWs and NHWs over the study period, respectively. HW amounts did not exhibit a statistically significant trend. Twenty-eight BATs (best available techniques) were identified that could be applied in refrigerator manufacturing for waste minimization and management. Among those, 8 of them were proposed for further improvement for waste management in the facility.

Organic and elemental carbon were measured both in daily PM10 and PM2.5 and in 6 h range time PM2.5 samples collected from September 2015 to October 2015 in a coastal rural site near Brindisi in the Apulia region (Italy), in order to determine factors affecting the carbonaceous aerosol variations. Carbon content (total carbon TC) represented a considerable fraction for both PM10 and PM2.5. In particular, in PM10 samples, organic carbon (OC) varied from 1.06 to 18.32 μg m⁻³ with a mean concentration of 5 ± 4 μg m⁻³ and EC varied from 0.11 to 0.88 μg m⁻³ with a mean value of 0.41 ± 0.19 μg m⁻³. In PM2.5 samples, OC varied from 0.54 to 12.91 μg m⁻³ with a mean concentration of 3.5 ± 2.8 μg m⁻³ and EC varied from 0.11 to 0.85 μg m⁻³ with a mean value of 0.35 ± 0.18 μg m⁻³. The highest values for both parameters were recorded when the air masses were coming from NE Europe and when Saharan Dust events were recognized. The results show that OC and EC exhibited higher concentrations during the night hours, suggesting that stable atmosphere and lower mixing conditions play important roles for the accumulation of air pollutants and promote condensation or adsorption of semivolatile organic compounds. In samples from a Saharan Dust event and in samples with the lowest and the highest OCₛₑc, ATR-FTIR analysis allowed us to identify organic functional groups including the non-acid organic hydroxyl C–OH group (e.g., sugars, anhydrosugars, and polyols), carbonyl C=O group, carboxylic acid COOH group, aromatic and aliphatic unsaturated C=C–H group, aliphatic saturated C–C–H group, and amine NH₂ group. Some inorganic ions were also identified: carbonates, sulfate, silicate, and ammonium. The dusty samples are mainly characterized by the presence of carbonate and hydrogen sulfate ions and by kaolinite (absorption at 914 and 1010 cm⁻¹), while in samples with air masses coming from the NE, OC is mainly characterized by aliphatic and aromatic C–H and O–H and N–H groups (absorptions in the range 3500–2700 cm⁻¹) and by the presence of organonitrate, aromatic amide and amine, and carboxylic acids (absorptions at 1630 and 1770–1700 cm⁻¹). Graphical abstract ᅟ

Renewable resources are playing a key role on the synthesis of biodegradable polyols. Moreover, the incorporation of covalently linked additives is increasing in importance in the polyurethane (PU) market. In this work, previously epoxidized grape seed oil and methyl oleate were transformed into phosphorylated biopolyols through an acid-catalyzed ring-opening hydrolysis in the presence of H₃PO₄. The formation of phosphate polyesters was confirmed by FT-IR and ³¹P-NMR. However, the synthesis of a high-quality PU rigid foam was not possible using exclusively these polyols attending to their low hydroxyl value. In that way, different rigid PU foams were prepared from the phosphorylated biopolyols and the commercial polyol Alcupol R4520. It was observed that phosphorylated biopolyols can be incorporated up to a 57 wt.% in the PU synthesis without significant structural changes with respect to the commercial foam. Finally, thermogravimetric and EDAX analyses revealed an improvement of thermal stability by the formation of a protective phosphorocarbonaceous char layer.

Polyether-based polyurethanes (PBP) are extremely problematic polymers due to their long persistence in the environment. Moreover, the assessment of PBP biodegradation remains biased due to the inability of conventional methods to determine how their diverse subunits are degraded. To improve our knowledge of PBP biodegradation, we used Raman spectroscopy to identify patterns of PBP biodegradation. Specifically, PBP biodegradation was assessed using a microbial inoculum isolated from an industrial soil in which polyurethanes have been buried for 40 years. During a 28-day biodegradation assay, the PBP biodegradation level reached 27.5 % (w/w), in addition to undergoing profound alteration of the PBP composition as identified by chemical analyses. After microbial degradation, Raman analyses revealed the disappearance of the polymer’s amorphous region, which contains a high polyol content, whereas the isocyanate-rich crystalline regions were preserved. The use of Raman spectroscopy appears to be a particularly useful tool to enhance our assessment of polymer biodegradation.

Water-soluble organic compounds (WSOCs), represented by anhydro-saccharides, dicarboxylic acids, and polyols, were analyzed by gas chromatography interfaced to mass spectrometry in extracts from 103 PM₁ and 22 PM₂.₅ filter samples collected in an urban background and road site in Barcelona (Spain) and an urban background site in Los Angeles (USA), respectively, during 1-month intensive sampling campaigns in 2010. Both locations have similar Mediterranean climates, with relatively high solar radiation and frequent anti-cyclonic conditions, and are influenced by a complex mixture of emission sources. Multivariate curve resolution-alternating least squares analyses were applied on the database in order to resolve differences and similarities in WSOC compositions in the studied sites. Five consistent clusters for the analyzed compounds were obtained, representing primary regional biomass burning organic carbon, three secondary organic components (aged SOC, isoprene SOC, and α-pinene SOC), and a less clear component, called urban oxygenated organic carbon. This last component is probably influenced by in situ urban activities, such as food cooking and traffic emissions and oxidation processes.

We report on the facile and low-temperature one-pot chemical synthesis of lightly doped Zn₁₋ₓ Cu ₓ O and hybrid Au–Zn₁₋ₓ Cu ₓ O photocatalysts with low Cu molar content (0 < x < 0.7%) using 1,3-propanediol polyol simultaneously as solvent, reducing and a stabilizing agent, without any final thermal treatment. The photocatalysts have been characterized by X-ray diffraction, N₂ adsorption study, UV–vis diffuse reflectance spectroscopy, inductively coupled plasma optical emission spectroscopy, and transmission electron microscopy. The lightly doped hybrid Au–Zn₁₋ₓ Cu ₓ O photocatalysts consisted in faceted quasi-spherical large-size Au nanoparticle cores surrounded by closely packed small-size Zn₁₋ₓ Cu ₓ O nanoparticles. Taking the photocatalytic degradation of Diuron under solar light as liquid-phase test reaction, the lightly doped Au–Zn₁₋ₓ Cu ₓ O hybrid photocatalysts with optimized x = 0.09% Cu content showed strongly enhanced photocatalytic activity when compared to the bare ZnO counterpart. The observed 16-fold higher degradation rate constant resulted jointly from the light doping of ZnO with Cu to form Zn₁₋ₓ Cu ₓ O photocatalyst and further from the addition of gold nanoparticles allowing interfacial oxide-to-metal electron transfer within the hybrid Au–Zn₁₋ₓ Cu ₓ O photocatalyst.

Among the phytotechnologies used for the reclamation of degraded mining sites, phytoextraction aims to diminish the concentration of polluting elements in contaminated soils. However, the biomass resulting from the phytoextraction processes (highly enriched in polluting elements) is too often considered as a problematic waste. The manganese-enriched biomass derived from native Mn-hyperaccumulating plants of New Caledonia was presented here as a valuable source of metallic elements of high interest in chemical catalysis. The preparation of the catalyst Eco-Mn₁and reagent Eco-Mn₂derived from Grevillea exul exul and Grevillea exul rubiginosa was investigated. Their unusual polymetallic compositions allowed to explore new reactivity of low oxidative state of manganese—Mn(II) for Eco-Mn₁and Mn(IV) for Eco-Mn₂. Eco-Mn₁was used as a Lewis acid to catalyze the acetalization/elimination of aldehydes into enol ethers with high yields; a new green and stereoselective synthesis of (−)-isopulegol via the carbonyl-ene cyclization of (+)-citronellal was also performed with Eco-Mn₁. Eco-Mn₂was used as a mild oxidative reagent and controlled the oxidation of aliphatic alcohols into aldehydes with quantitative yields. Oxidative cleavage was interestingly noticed when Eco-Mn₂was used in the presence of a polyol. Eco-Mn₂allowed direct oxidative iodination of ketones without using iodine, which is strongly discouraged by new environmental legislations. Finally, the combination of the properties in the Eco-Mn catalysts and reagents gave them an unprecedented potential to perform sequential tandem oxidation processes through new green syntheses of p-cymene from (−)-isopulegol and (+)-citronellal; and a new green synthesis of functionalized pyridines by in situ oxidation of 1,4-dihydropyridines.