Comparative Thermodynamic Study on the Contribution of the Autocondensation and Copolymerization Reactions for the Tannins of the Subspecies of Acacia nilotica

Autocondensation and copolymerization reactions of the Acacia nilotica subspecies tomentosa (Ant) and the subspecies adansonii (Ana) tannins extracts solutions have been studied at several pH values by thermomechanical analyzer. Results of chemical analysis of these tannins revealed that the studied tannins, Ant and Ana contained high percentages of extractable tannins (54 and 57 %) for and polyphenolic materials (78 and 80 %) respectively. Different hardeners such as paraformaldehyde, Urea and pMDI were added at different ratios and their polycondensation reactions was studied and compared with their autocondensation ones. The aim was to evaluate the tannins suitability for the production of commercially and technically viable tannin adhesives with reduced Formaldehyde emission for wood products and to study the interference between the autocondensation and the copolymerization reaction. The obtained results of autocondensation reaction for both of the tannins studied showed that the best Young’s modulus values for Ant (3,500 and 2,750 MPa) and Ana (2,650 and 2,620 MPa) were obtained at pH 5 and 7. The Young’s modulus values obtained by the tannins Ant were higher than those achieved by Ana. This indicates that the Ant is more reactive than Ana. These results were also in line with results achieved by the gel time for both of the tannins. Gel time results indicate that the reactivity of both tannins increased towards alkalinity with Ana being more reactive at alkaline pH. Addition of 8 % of paraformaldehyde was adversely affecting the autocondensation reactions, as the best Young’s modulus values were achieved at pH 4 for Ant tannins. As for Ana the higher Young’s modulus values (2,000 and 2,310 MPa) were achieved at pH 5 and 7. This indicates that autocondensation reaction was contributed to the final network of the copolymerization reaction. When smaller ratio of paraformaldehyde and Urea (5 %) was added to Ant tannins it favors the autocondensation reaction and the best Young’s modulus values were obtained at pH 5 and 7. Addition of pMDI (10–30 %) was found to decrease the temperature of copolymerization and the obtained Young’s modulus values by Ant were lower than those obtained by autocodensation reaction. Best Young’ modulus values were obtained by Ant at pH 5 and 7. Ana gave the best Young’s modulus values at pH 4 and 5 indicating that the autocondensation appears to depress the copolymerization reactions. The obtained results by both reactions were very important from technical and economical point of view as they concluded that it is very possible to produce adhesives system with zero emission depending on the tannins autocondensation reaction and pH values. Reduction of formaldehyde emission was also possible upon addition of smaller amount of paraformaldehyde and Urea.     

Biodegradability of Epoxidized Soybean Oil Based Thermosets in Compost Soil Environment

In this study, bio-thermoset from epoxidized soybean oil (ESO) was prepared in the presence of methylhexahydrophthalic anhydride curing agent and 2-ethyl-4-methylimidazole catalyst. The crosslink densities of the synthesized ESO are ranged from 0.109 × 10^?3 to 0.308 × 10^?3 mol/cm³. The ESO bio-thermosets were exposed to the soil-burial test for 8 months. Weight change and morphology of the degraded ESO specimens were assessed. It was found that the weight loss of ESO was governed by the materials compositions, crosslink density and the soil-burial exposure time. The 3 mm thickness ESO bio-thermosets with crosslink density of 0.109 × 10^?3 mol/cm³ had fully biodegraded after soil-burial for 6 months. In addition, 16S rDNA sequencing was carried out to identify the soil microorganisms. It was suggested that Comamonas sp., Bacillus sp., Streptomyces sp. and Acinetobacter sp. are the possible soil microbes that degrade the ESO bio-thermosets in the compost soil environment.     

Water quality assessment of the Tubarão River through chemical analysis and biomarkers in the Neotropical fish Geophagus brasiliensis

The Tubarão River rises in Santa Catarina, Brazil, and has been historically affected by coal mining activities around its springhead. To evaluate its water conditions, an investigation regarding a possible decontamination gradient associated with the increased river flow toward the estuary, as well as the influence of seasonality over this gradient was performed through a series of biomarkers (vitellogenin, comet assay, lipid peroxidation, protein carbonylation, gluthatione, gluthatione S-transferase, acetylcholinesterase, light microscopy in liver, and scanning electron microscopy in gills) and chemical analysis (polycyclic aromatic hydrocarbons (PAHs) in bile and metal analysis in sediment) in the cichlid Geophagus brasiliensis. Two collections (summer and winter) were made in four distinct sites along the river, while sediments were sampled between those seasons. As expected, the contamination linked exclusively to mining activities was not observed, possibly due to punctual inputs of contaminants. The decontamination gradient was not observed, although seasonality seemed to have a critical role in the responses of biomarkers and availability of contaminants. In the summer, the fish presented higher histopathological damages and lower concentrations of PAHs, while in the winter they showed both higher genetic damage and accumulation of PAHs. The Tubarão suffers impacts from diverse activities, representing health risks for wild and human populations.     

Concentrations and distributions of 18 organochlorine pesticides listed in the Stockholm Convention in surface sediments from the Liaohe River basin,China

Organochlorine pesticides (OCPs) were analyzed in 26 surface sediment samples from the Liaohe River basin, and the distributions of and potential environmental risks posed by OCPs in the basin were evaluated. Eighteen OCPs listed in the Stockholm Convention were determined using isotope-dilution gas chromatography–high resolution mass spectrometry. This is the first study of hexachlorobenzene (HCB) in the Liaohe River basin sediments. The total OCP concentrations were 0.39–68.06 ng g^?1 dry weight. The total α-, β-, γ-, and δ-hexachlorocyclohexane (HCH), the total dichlorodiphenyltrichloroethane (DDT – p,p′-dichlorodiphenyldichloroethane (DDD), p,p′-dichlorodiphenyldichloroethylene (DDE), o,p^'-DDT, and p,p′-DDT), and the HCB concentrations in the sediment samples were 0.1–28.48 ng g^?1 (mean 4.01 ng g^?1), 0.08–6.52 ng g^?1 (mean 3.07 ng g^?1), and 0.18–24.8 ng g^?1 (mean 4.38 ng g^?1), respectively. The HCB concentrations were higher than the concentrations of the other OCPs, and the HCHs and HCB together were the dominant OCPs. β-HCH was the most abundant HCH isomer. The concentrations of DDTs and other OCPs were relatively low, and the (DDE+DDD)/DDT ratios (>0.5) and DDD/DDE ratios (<1) indicated that no recent DDT inputs had occurred in the Liaohe River system. The main sources of HCHs were probably the historical production and agricultural use of HCH in the study area. The DDT and HCH concentrations were generally below or similar to the concentrations that have been found in other parts of the world. An ecotoxicological evaluation indicated that HCHs in surface sediments pose slight risks to human and ecological health in the Liaohe River basin.     

Gas-phase and semivolatile organic emissions from a modern nonroad diesel engine equipped with advanced aftertreatment

ABSTRACT

U.S. Tier 4 Final and Euro Stage IV and V regulations for nonroad compression-ignition engines have led to the development of exhaust aftertreatment technologies optimized for nonroad engines and duty cycles. In this study, several aftertreatment configurations consisting of state-of-the-art diesel oxidation catalysts (DOCs), diesel particulate filters (DPFs), copper (Cu) zeolite– and vanadium-based selective catalytic reduction (SCR) catalysts, and ammonia oxidation (AMOX) catalysts are evaluated using both nonroad transient (NRTC) and steady (8-mode NRSC) cycles in order to understand both component- and system-level effects of diesel aftertreatment on gas-phase, semivolatile, and particle-phase and particle-bound unregulated organic emissions. Organic emissions reported in this work include total hydrocarbon (THC), n-alkanes, branched alkanes, saturated cycloalkanes, aromatics, aldehydes, ketones, hopanes, steranes, and soluble organic fraction (SOF). Brake-specific emissions are reported for four configurations, including engine-out, DOC+CuZ-SCR+AMOX, V-SCR+AMOX, and DOC+DPF+CuZ-SCR+AMOX, and conversion of engine-out emissions is reported for the three aftertreatment configurations. Mechanisms responsible for the reduction of organic species are discussed in detail. This summary of emissions from a current nonroad diesel engine equipped with advanced aftertreatment can be used to more accurately model the impact of anthropogenic emissions on the atmosphere with tools such as the U.S. Environmental Protection Agency’s Motor Vehicle Emissions Simulator (MOVES2014a) model.

Implications: Anthropogenic emissions are a source of significant human health and environmental risk. This study, focused on the treatment of exhaust emissions from a modern nonroad diesel engine with a variety of aftertreatment configurations, examines the impact that human industrial activity can have on air pollution. In particular, we focus on the remediation of gas-phase and semivolatile organic emissions by emission reduction technologies. This detailed summary of emissions from a current nonroad diesel engine equipped with advanced aftertreatment can be used to more accurately model the impact of anthropogenic emissions on the atmosphere with tools such as the U.S. Environmental Protection Agency’s MOVES2014a model.     

Removal of phthalates from aqueous solution by different adsorbents: a short review

This work presents a short review of adsorptive materials proposed and tested for removing phthalates from an aqueous environment. The objective is not to present an exhaustive review of all the types of adsorbents used, but to focus on selected types of "innovative" materials. Examples include modified activated carbon, chitosan and its modifications, β-cyclodextrin, and specific types of biomass, such as activated sludge from a wastewater treatment plant, seaweed and microbial cultures. Data from the literature do not confirm the existence of a broad-spectral adsorbent with high sorption efficiency, low production costs and environmentally friendly manufacture. According to the coefficients of Freundlich's isotherm, the most promising adsorbent of those mentioned in this work appears to be the biomass of activated sludge, or extracellular polysaccharides extracted from it. This material benefits from steady production, is cheap and readily available. Nevertheless, before putting it in practice, the treatment and adaptation of this raw material has to be taken into consideration.     

Assessment of the interrelation between photooxidation and biodegradation of selected polyesters after artificial weathering

Three commercially available biodegradable polymers, two different aromatic-aliphatic copolyesters and polylactic acid, intended for the fabrication of agricultural mulching films, in addition to other applications, were subjected to a series of tests with the aim of studying the relationship between their photooxidation and biodegradation. Photooxidation resulted in the rearrangement of polymeric chains, in the case of both copolyesters the events led to polymeric chain crosslinking and the formation of insoluble polymeric gel. The tendency was significantly more pronounced for the copolyester with the higher content of the aromatic constituent. As regards polylactic acid photochemical reactions were not accompanied by crosslinking but instead provoked chain scissions. A biodegradation experiment showed that, despite marked structural changes, the extent of photooxidation was not the decisive factor, which significantly modified the rate of biodegradation in all three materials investigated. The specific surface area of the sample specimens was shown to be more important.     

Preparation and Characterization of Hydrogel Based on Poly(vinyl alcohol) Cross-Linked by Different Cross-Linkers Used to Dry Organic Solvents

Poly(vinyl alcohol) (PVA) hydrogels were chemically cross-linked with/without different cross-linkers such as glutaraldehyde and epichlorohydrin, in the presence of a catalyst, or activator (potassium hydroxide) to produce three types of hydrogels. The structures of PVA and the prepared gel types were determined by FTIR spectroscopy, the mechanical and thermal properties, of these hydrogels were examined. The effects of different pH values and temperatures on the swelling properties of the prepared gels were examined. From the obtained results, it was found that, the low concentration of the cross-linker produced hydrogel with moderate properties, but in absence of the cross-linker, the obtained hydrogel exhibited good properties and can be used as friendly environmentally moisture absorbents from the organic solvents. The insolubility and swelling properties of gels were tested in these solvents. The results indicated that these hydrogels can be used as moisture absorbents and solvent dryers.     

Comprehensive assessment of toxic metals in urban and suburban street deposited sediments (SDSs) in the biggest metropolitan area of China

A set of toxic metals, i.e. As, Hg, Pb, Cd, Cu, Zn, Ni and Cr, in urban and suburban SDSs were investigated comparatively in the biggest metropolitan area of China, Shanghai. Results showed that all of the metals except As were accumulated greatly, much higher than background values. Geo-accumulation index indicated that metal contamination in urban SDSs was generally heavier than that in suburban SDSs. Potential ecological risk index demonstrated that overall risks caused by metals were considerable. Cd contributed 52% to the overall risk. Multivariate statistical analysis revealed that in urban SDSs, Zn, Ni, Cd, Pb, Cu and Cr were related to traffic and industry; coal combustion led to elevated levels of Hg; soil parent materials controlled As contents. In suburban SDSs, Pb, Cu, As and Cd largely originated from traffic pollution; Zn, Ni and Cr were associated with industrial contaminants; Hg was mainly from domestic solid waste.     

Determination of the insecticide diflubenzuron in mushrooms by kinetic method and high-performance liquid chromatographic method

In the present study, a new sensitive and simple kinetic-spectrophotometric method for the determination of the insecticide diflubenzuron [1-(4-chlorophenyl)-3-(2,6-diflubenzoil)urea] is proposed. The method is based on the inhibited effect of diflubenzuron on the oxidation of sulphanilic acid (SA) by hydrogen peroxide in phosphate buffer in presence Cu(II) ion. Diflubenzuron was determined with linear calibration graph in the interval from 0.31 to 3.1 μg mL?1 and from 3.1 to 31.0 μg mL?1. The optimized conditions yielded a theoretical detection limit of 0.18 μg mL?1 corresponding to 0.036 mg kg(-1)mushroom sample based on the 3S(b) criterion. The RSD is 5.03-1.83 % and 2.81-0.71 % for the concentration interval of diflubenzuron 0.31-3.1 μg mL?1 and 3.1-31.0 μg mL?1, respectively. The reaction was followed spectrophotometrically at 370 nm. The kinetic parameters of the reaction are reported, and the rate equations are suggested. The developed procedure was successfully applied to the rapid determination of diflubenzuron in spiked mushroom samples of different mushroom species. The HPLC method was used like a comparative method to verify results.