The application of profluorescent nitroxides to detect reactive oxygen species derived from combustion-generated particulate matter: Cigarette smoke – A case study

Reactive oxygen species (ROS) and related free radicals are considered to be key factors underpinning the various adverse health effects associated with exposure to ambient particulate matter. Therefore, measurement of ROS is a crucial factor for assessing the potential toxicity of particles. In this work, a novel profluorescent nitroxide, BPEAnit, was investigated as a probe for detecting particle-derived ROS. BPEAnit has a very low fluorescence emission due to inherent quenching by the nitroxide group, but upon radical trapping or redox activity, a strong fluorescence is observed. BPEAnit was tested for detection of ROS present in mainstream and sidestream cigarette smoke. In the case of mainstream cigarette smoke, there was a linear increase in fluorescence intensity with an increasing number of cigarette puffs, equivalent to an average of 101 nmol ROS per cigarette based on the number of moles of the probe reacted. Sidestream cigarette smoke sampled from an environmental chamber exposed BPEAnit to much lower concentrations of particles, but still resulted in a clearly detectible increase in fluorescence intensity with sampling time. It was calculated that the amount of ROS was equivalent to 50 ± 2 nmol per mg of particulate matter; however, this value decreased with ageing of the particles in the chamber. Overall, BPEAnit was shown to provide a sensitive response related to the oxidative capacity of the particulate matter. These findings present a good basis for employing the new BPEAnit probe for the investigation of particle-related ROS generated from cigarette smoke as well as from other combustion sources.     

Feral horses (<Emphasis Type="Italic">Equus caballus</Emphasis>) as a component of protected steppe ecosystems in the Rostovskii Nature Reserve

Vegetation was considerably trampled throughout Vodnyi Island in the Rostovskii Nature Reserve in 2007 because of a high pasture load due to feral horses (0.15 horses/ha). Calculation of the food resources on the island, with its protection as part of a nature reserve taken into account, has shown that the herd size is 3.5 times larger than the maximum allowable value.     

Pyrolysis of permethrin and formation of precursors of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) under non-oxidative conditions

This article reports the computational and experimental results of the thermal decomposition of permethrin, a potential source of dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF). We have performed a quantum chemical analysis by applying density functional theory to obtain the decomposition pathways of permethrin and the formation mechanism of dibenzofuran. We have conducted the pyrolysis experiments in a tubular reactor and identified the pyrolysis products to demonstrate the agreement between the experimental measurements and quantum chemical calculations. The initiation of the decomposition of permethrin involves principally the aromatisation of permethrin into 3-phenoxyphenylacetic acid, 2-methylphenyl ester (J) and concomitant loss of 2HCl. This rearrangement is followed by the rupture of the O–CH₂ linkage in J, with a rate constant derived from the quantum chemical results of 1 × 10¹⁵ exp(−68 kcal/mol/RT) s⁻¹ for temperatures between 700 and 1300 K. This is confirmed by finding that the rate constant for unimolecular rearrangement of permethrin into J is 1.2 × 10¹² exp(−53 kcal/mol/RT) s⁻¹ over the same range of temperatures and exceeds the direct fission rate constant at all temperatures up to 850 ± 120 °C as well as by the experimental detection of J prior to the detection of the initial products incorporating diphenyl ether, 1-methyl-3-phenoxybenzene, 3-phenoxybenzaldehyde and 1-chloromethyl-3-phenoxybenzene. As the temperature increases, we observe a rise in secondary products formed directly or indirectly (via phenol/phenoxy) including aromatics (naphthalene), biphenyls (biphenyl, 4-methyl-1,1′-biphenyl) and dibenzofuran (DF). In particular, we discover by means of quantum chemistry a direct route from 2-phenoxyphenoxy to naphthalene. We detect no polychlorinated dibenzo-p-dioxins and dibenzofurans. Unlike the case of oxidative pyrolysis [Tame, N.W., Dlugogorski, B.Z., Kennedy, E.M., 2007b. Formation of dioxins in fires of arsenic-free treated wood: Role of organic preservatives. Environ. Sci. Technol. 41, 6425–6432] where significant yields of both PCDD and PCDF were obtained, under non-oxidative conditions the thermal decomposition of permethrin does not form appreciable amounts of PCDD or PCDF and the presence of oxygen (and/or a sizable radical pool) appears necessary for the formation of dibenzo-p-dioxin itself or PCDD/F from phenol/phenoxy.     

Renewable energy sources: conflicts and opportunities in a changing landscape

Regional Environmental Change - Replacement of conventional energy sources with renewables such as solar panels and wind turbines requires adequate land. Impact assessments should be conducted to...     

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.     

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.     

Application of 15N–18O double stable isotope tracer technique in an agricultural nonpoint polluted river of the Yangtze Delta Region

One strategy to combat nitrate (NO₃-N) contamination in rivers is to understand its sources. NO₃-N sources in the East Tiaoxi River of the Yangtze Delta Region were investigated by applying a ¹⁵N–¹⁸O dual isotope approach. Water samples were collected from the main channel and from the tributaries. Results show that high total N and NO₃-N are present in both the main channel and the major tributaries, and NO₃-N was one of the most important N forms in water. Analysis of isotopic compositions (δ ¹⁸O, δD) of water suggests that the river water mainly originated from three tributaries during the sampling period. There was a wide range of δ ¹⁵N-NO₃ (?1.4 to 12.4 ‰) and a narrow range of δ ¹⁸O-NO₃ (3.7 to 9.0 ‰) in the main channel waters. The δ ¹⁵N and δ ¹⁸O-NO₃ values in the upper, middle, and lower channels along the river were shifted as 8.2, 3.5, and 9.5 ‰, and 9.0, 4.2, and 6.0 ‰, respectively. In the tributary South Tiao, the δ ¹⁵N and δ ¹⁸O-NO₃ values were as high as 9.5 and 7.0 ‰, while in the tributaries Mid Tiao and North Tiao, NO₃-N in most of the samples had relatively low δ ¹⁵N and δ ¹⁸O-NO₃ values from 2.3 to 7.5 ‰ and 4.7 to 7.0 ‰, separately. Our results also suggest that the dual isotope approach can help us develop the best management practice for relieving NO₃-N pollution in the rivers at the tributary scale.     

Adsorption-desorption characteristics of mercury in paddy soils of China

Mercury (Hg) has received considerable attention because of its association with various human health problems. Adsorption-desorption behavior of Hg at contaminated levels in two paddy soils was investigated. The two representative soils for rice production in China, locally referred to as a yellowish red soil (YRS) and silty loam soil (SLS) and classified as Gleyi-Stagnic Anthrosols in FAO/UNESCO nomenclature, were respectively collected from Jiaxin County and Xiasha District of Hangzhou City, Zhejiang Province. The YRS adsorbed more Hg(2+) than the SLS. The characteristics of Hg adsorption could be described by the simple Langmuir adsorption equation (r2 = 0.999 and 0.999, P < 0.01, respectively, for the SLS and YRS). The maximum adsorption values (Xm) that were obtained from the simple Langmuir model were 111 and 213 mg Hg(2+) kg(-1) soil, respectively, for the SLS and YRS. Adsorption of Hg(2+) decreased soil pH by 0.75 unit for the SLS soil and 0.91 unit for the YRS soil at the highest loading. The distribution coefficient (kd) of Hg in the soil decreased exponentially with increasing Hg(2+) loading. After five successive desorptions with 0.01 mol L(-1) KCl solution (pH 5.4), 0 to 24.4% of the total adsorbed Hg(2+) in the SLS soil was desorbed and the corresponding value of the YRS soil was 0 to 14.4%, indicating that the SLS soil had a lower affinity for Hg(2+) than the YRS soil at the same Hg(2+) loading. Different mechanisms are likely involved in Hg(2+) adsorption-desorption at different levels of Hg(2+) loading and between the two soils.     

Photolysis of 14C-sulfadiazine in water and manure

Photolysis of 14C-sulfadiazine in aqueous solution under simulated sunlight followed first-order kinetics. The impact of H2O2, humic acid, fulvic acid and acetone to enhance the photodegradation of sulfadiazine (SDZ) was studied. Six photoproducts, 4-OH-SDZ, 5-OH-SDZ, N-formyl-SDZ, 4-[2-iminopyrimidine-1(2H)-yl] aniline, 2-aminopyrimidine, and aniline were identified. Extrusion of SO2 was found to be the main degradation process during irradiation. These photoproducts can occur in water and soil upon sunlight exposure, when soil is treated with SDZ contained in manure. Due to photodegradation the experimental half-life of the SDZ in water was 32h and in the presence of photosensitizers the half-life values were 19.3-31.4h, 17.2-31.4h, 12.6-29.8h, and 3.8-30.7h for H2O2, humic acid, fulvic acid, and acetone, respectively depending on the concentration of the photosensitizers. The presence of photosensitizers markedly reduced SDZ persistence, indicating that indirect photolytic processes are important factors governing the photodegradation of SDZ in aqueous environments. Investigation revealed further persistence behavior of SDZ in manure. The half-life value of SDZ in manure was 158h.