Gas-phase ozonolysis of the monoterpenoids (S)-(+)-carvone, (R)-(−)-carvone, (−)-carveol, geraniol and citral

Biogenic emissions of volatile organic compounds (VOCs) play a fundamental role in atmospheric chemistry. Vegetation is the most abundant natural source of VOCs, while terpenoids, as limonene, α and β pinene and mircene, top the plants emission list. Much interest has been demonstrated in oxidation and photooxidation reactions of VOCs, particularly of monoterpenoids, owing to their diversity and to uncertainties regarding their mechanism of reaction. Quantification of primary carbonylic compounds, as well as of biradical reaction components, is highly relevant to the understanding of the major reactions. In this context, taking into account both structural factors and the fact that these compounds are found in the essential oils of plants typically found in Brazil and that they may be present in the atmosphere from emission by the plants, the monoterpenoids (S)-(+)-carvone, (R)-(−)-carvone, (−)-carveol, geraniol and citral (a mixture of the isomers geranial and neral) were selected for this study.The ozonolysis reactions of the monoterpenoids were carried out under dark conditions for all experiments, due to their photochemical reactivity. The analysis of the results lets us propose a mechanism by which these reactions occur. The observed results of the ozonolysis of S and R carvone suggest that the stereochemistry of asymmetric carbon does not affect either in the yields of both formaldehyde and of OH radicals produced in the reaction, or in the reactivity of these compounds, for which the rate constants were in the scale of 10⁻⁶ s⁻¹.We found that, in the (−)-carveol's cis and trans mixture, even though the hydroxyl in the axial position—in the case of trans-(C) and cis-(D′) isomers—favors the attack by the ozone molecule on the external double bond, thus increasing the mixture's reactivity , it affects the average production of formaldehyde. The presence of geraniol and citral led to the production of formaldehyde, propanone, glyoxal, methyl–glyoxal and cyclohexanone (OH radicals) as reaction products. The influence of an electron attractor group bonded to the carbon of the double bond, on the reactivity of the double bond, could not be observed in the case of citral, due to strong interference occurring in the instrument in all experiments with this monoterpenoid. For this reason, only the kinetics of geraniol was monitored .     

Removing and recovering gas-phase elemental mercury by Cu(x)Co(3-x)O(4) (0.75< or = x < or =2.25) in the presence of sulphur compounds

The Hg(0) oxidation ability and reusability of Cu(x)Co(3-x)O(4) were investigated in an attempt to improve SO(2) anti-poisoning ability of metal oxide and produce more economic and effective sorbents for the control of Hg(0) emission from combustion processes. The influence of copper content on Cu(x)Co(3-x)O(4)'s (0.75< or = x < or =2.25) oxidation ability of Hg(0) in the presence of SO(2) was investigated. According to the X-ray diffraction, Brunauer-Emmett-Teller (BET) and mass balance analysis on mercury, we found that Cu(1.5)Co(1.5)O(4) showed the highest S(BET) and best Hg(0) oxidation ability. With continuous increase of x from 0.75 to 2.25, Cu(x)Co(3-x)O(4)'s SO(2) anti-poisoning ability increased. The analysis results of the X-ray photoelectron spectroscopy manifested that the adsorptive mercury species on spent Cu(1.5)Co(1.5)O(4) was HgO. The spent Cu(1.5)Co(1.5)O(4) could be regenerated by thermal decomposition at 673K and regenerated Cu(1.5)Co(1.5)O(4) showed higher Hg(0) oxidation ability due to Hg-doping. Regenerated enrichment Hg(0) was collected using activated carbon at an ambient temperature to eliminate the secondary pollution.     

Bioaccumulation of toxic metals (Cr, Cd, Pb and Cu) by seeds of Euryale ferox Salisb. (Makhana) W

The level of toxic metals Cr, Cd, Pb and Cu was determined in seeds, water and sediments collected from nine closed waterbodies of Darbhanga, north Bihar, used for cultivation of the edible aquatic macrophyte Euryaleferox Salisb. during harvesting season of the crop for two successive years (1996 and 1997). Seeds bioconcentrated appreciable amount of these toxic metals in the order Pb > Cr > Cu > Cd. The increased load of metal pollution due to domestic and municipal discharges threatened the habitats of the plant. The toxic metal contents in seeds were found positively correlated with the ambient concentration of metals in water and sediments. The importance of these findings has been discussed for national water resource economy of the country and human health perspectives.     

Phenol nitration upon oxidation of nitrite by Mn(III,IV) (hydr)oxides

An interesting aspect of the chemistry of nitrite is the possibility for this compound to interact with other environmental factors and many oxidising species, which results in the oxidation of nitrite to nitrogen dioxide. This is a potentially interesting process that can lead to the formation of nitroaromatic compounds in the environment. In previous papers we have shown that nitrite can interact with dissolved Fe(III) and nitrate under irradiation, Fenton and heterogeneous photo-Fenton reagents, and semiconductor oxides such as TiO2, alpha-Fe2O3, and beta-FeOOH under irradiation. This paper reports on the interaction between nitrite/nitrous acid and the Mn(III,IV) (hydr)oxides beta-MnO2 and gamma-MnOOH, both in neutral solution under irradiation and in acidic conditions in the dark. beta-MnO2 and gamma-MnOOH originate from the oxidation of Mn(II) and play a key role in the redox cycling of manganese in the environment. These Mn(III,IV) (hydr)oxides show some photocatalytic activity, and they can act as thermal oxidants at acidic pH. The photoinduced oxidation of nitrite and the thermal oxidation of nitrous acid by Mn(III,IV) (hydr)oxides yield nitrogen dioxide and lead to the formation of nitrophenols in the presence of phenol. These processes can take place at the water-sediment or water-colloid interface in natural waters and on the surface of atmospheric particulate. Furthermore, the phenol/gamma-MnOOH/HNO2 system in dark acidic solution is an interesting model due to the formation of phenoxyl radical upon phenol monoelectronic oxidation by gamma-MnOOH. The kinetics of nitrophenol generation under such conditions indicates that phenol nitration is unlikely to take place upon reaction between phenoxyl and *NO2 and suggests a solution to a literature debate on the subject.     

Tolerance to,and avoidance of,hypoxia by the penaeid shrimp (Metapenaeus ensis)

Aquatic hypoxia caused by eutrophication may lead to mass mortality of valuable living resources such as fish and shrimp. However, there is little information on the hypoxic tolerance of penaeid shrimp, and whether they are able to avoid hypoxia. In laboratory experiments, LC50, LT50 and heart beats per minute were determined for juvenile Metapenaeus ensis at 0.5, 1.0, 2.0 and 6.0 mg O2 l(-1). The 8-h LC50, for DO was 0.77 mg O2 l(-1), while the LT50 at 0.5 mg O2 l(-1) was 399 min. Heart beat rate significantly declined when DO fell below 1.0 mg O2 l(-1). When confronted with a gradient of dissolved oxygen, M. ensis were able to avoid hypoxic areas and move to oxygenated water. M. ensis appeared to be sensitive to hypoxia, and their ability to detect and avoid hypoxia may enhance their survival in habitats where hypoxia may occur.     

Behavioral and metabolic effects of sublethal doses of two insecticides,chlorpyrifos and methomyl,in the Egyptian cotton leafworm, <Emphasis Type="Italic">Spodoptera littoralis</Emphasis> (Boisduval) (Lepidoptera: Noctuidae)

Insecticides have long been used as the main method in limiting agricultural pests, but their widespread use has resulted in environmental pollution, development of resistances, and biodiversity reduction. The effects of insecticides at low residual doses on both the targeted crop pest species and beneficial insects have become a major concern. In particular, these low doses can induce unexpected positive (hormetic) effects on pest insects, such as surges in population growth exceeding what would have been observed without pesticide application. Methomyl and chlorpyrifos are two insecticides commonly used to control the population levels of the cotton leafworm Spodoptera littoralis, a major pest moth. The aim of the present study was to examine the effects of sublethal doses of these two pesticides, known to present a residual activity and persistence in the environment, on the moth physiology. Using a metabolomic approach, we showed that sublethal doses of methomyl and chlorpyrifos have a systemic effect on the treated insects. We also demonstrated a behavioral disruption of S. littoralis larvae exposed to sublethal doses of methomyl, whereas no effects were observed for the same doses of chlorpyrifos. Interestingly, we highlighted that sublethal doses of both pesticides did not induce a change in acetylcholinesterase activity in head of exposed larvae.     

Degradation of chlordecone and beta-hexachlorocyclohexane by photolysis, (photo-)fenton oxidation and ozonation

Intensive use of chlorinated pesticides from the 1960s to the 1990s has resulted in a diffuse contamination of soils and surface waters in the banana-producing areas of the French West Indies. The purpose of this research was, for the first time, to examine the degradation of two of these persistent pollutants – chlordecone (CLD) and beta-hexachlorocyclohexane (β-HCH) in 1 mg L^?1 synthetic aqueous solutions by means of photolysis, (photo-) Fenton oxidation and ozonation processes. Fenton oxidation is not efficient for CLD and yields less than 15% reduction of β-HCH concentration in 5 h. Conversely, both molecules can be quantitatively converted under UV-Vis irradiation reaching 100% of degradation in 5 h, while combination with hydrogen peroxide and ferrous iron does not show any significant improvement except in high wavelength range (>280 nm). Ozonation exhibits comparable but lower degradation rates than UV processes. Preliminary identification of degradation products indicated that hydrochlordecone was formed during photo-Fenton oxidation of CLD, while for β-HCH the major product peak exhibited C₃H₃Cl₂ as most abundant fragment.     

Persistent organic pollutants (PCB, DDT, HCH, HCB & BDE) in eels (Anguilla anguilla) in Scotland: Current levels and temporal trends

Eels are an ideal biomonitor for persistent organic pollutants (POPs) because of their high lipid content, longevity and tendency to remain within a defined range during their freshwater life phase. This study investigated concentrations of POPs in eels (Anguilla anguilla) from 30 sites across Scotland, including polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (BDEs), DDT (and metabolites), hexachlorocyclohexanes (α, β, γ-HCH), hexachlorobenzene (HCB), hexachlorobutadiene (HCBD) and pentachlorobenzene. Despite its EU-wide ban ∼30 years ago, DDT and its derivatives were detected in almost all samples. PCB 153 and 138 were the most widely detected PCB congeners, while BDE 47 was the dominant BDE. Pentachlorobenzene was not detected, while HCBD was detected once only. α-HCH, β-HCH and HCB concentrations were very low (generally <3 μg/kg or below detection). When compared with 1986 and 1995 data, the results revealed considerable decreases in p,p′-DDE concentrations. More drastic reductions were evident for γ-HCH, reflecting the tightening restrictions on pesticide use imposed over the previous decades.     

Radionuclides, heavy metals and fluorine incidence at Tapira phosphate rocks, Brazil, and their industrial (by) products

Inorganic phosphate fertilizers may contain radionuclides, heavy metals and fluorine. This paper presents the possible environmental hazards from Tapira phosphate rocks and their (by) products (Brazil) utilized as phosphate fertilizers. The activity concentration of 238U, 234U, 226Ra and 40K in Tapira phosphate rocks is within the world range for these rock types. The 232Th activity concentration is higher than the mean reported in phosphate rocks. A value of 2184 nGy h(-1) was obtained for the exposure dose rate in Tapira phosphate deposit area, which is indicative of a high background radiation area. The flotation-separation process causes the incorporation of no more than 9%, 11% and 24% of radionuclides, heavy metals and fluorine, respectively, into the phosphate concentrate. The radionuclides and heavy metals existing in phosphate fertilizers applied in Brazilian crops according to the recommended rates, do not raise their concentration in soils to harmful levels.     

Solid-state conformations and absolute configurations of (+) and (-) alpha-, beta-, and gamma-hexabromocyclododecanes (HBCDs)

Hexabromocyclododecanes (HBCDs) are high production volume chemicals used as flame retardants for plastics and textiles. They are currently produced in quantities exceeding 20,000 t/y. Despite this fact, the correct stereochemistry of most HBCDs is still not known. Six stereocenters are formed during bromination of cyclododecatrienes, resulting in mixtures of different stereoisomers. Considering all elements of symmetry, 16 different stereoisomers including six pairs of enantiomers as well as 4 meso forms are possible theoretically. Recently, we isolated 8 of the 16 possible stereoisomers from a technical HBCD mixture and assigned their relative configurations. Herein, we report on the isolation of 6 enantiomerically pure alpha-, beta-, and gamma-HBCDs, obtained from preparative chiral-phase liquid chromatography, and we present their absolute configurations, which were determined from X-ray diffraction analysis. The absolute configuration of (-) alpha-HBCD was found to be (1R,2R,5S,6R,9R,10S), while the one of (+) beta-HBCD is assigned to (1S,2S,5S,6R,9S,10R), whereas the one of (-) gamma-HBCD corresponds to (1S,2S,5S,6R,9R,10S). The given structural information allows the unambiguous identification of the six most important HBCD stereoisomers, which typically account for more than 95% of technical HBCDs. In addition, we compared the solid-state conformations of racemic and enantiomerically pure alpha-, beta-, and gamma-HBCDs. In all cases, vicinal dibromides adopted a synclinal (sc) conformation with torsion angles of 69+/-6 degrees. A unique structural motive was common to all examined HBCD solid-state conformations. This conserved structure was described as an extended triple turn consisting of an arrangement of three pairs of synclinal and two antiperiplanar torsion angles.     

Degradation of poly (lactic acid) and nanocomposites by <Emphasis Type="Italic">Bacillus licheniformis</Emphasis>

Background, aim, and scope  

The disposal problem due to non-degradable petroleum-based plastics has raised the demand for biodegradable polymers. The degradation of poly (lactic acid) (PLA) has been studied for several years, but the understanding of involved mechanisms is still incomplete. Based on our previous studies, and it is hypothesized an enzymatic involvement, the aim of this study was to continue investigations on the degradation of PLA and its nanocomposites by Bacillus licheniformis.     

Enhancement of in vitro high-density polyethylene (HDPE) degradation by physical,chemical, and biological treatments

Partially degraded high-density polyethylene (HDPE) was collected from plastic waste dump yard for biodegradation using fungi. Of various fungi screened, strain MF12 was found efficient in degrading HDPE by weight loss and Fourier transform infrared (FT-IR) spectrophotometric analysis. Strain MF12 was selected as efficient HDPE degraders for further studies, and their growth medium composition was optimized. Among those different media used, basal minimal medium (BMM) was suitable for the HDPE degradation by strain MF12. Strain MF12 was subjected to 28S rRNA sequence analysis and identified as Aspergillus terreus MF12. HDPE degradation was carried out using combinatorial physical and chemical treatments in conjunction to biological treatment. The high level of HDPE degradation was observed in ultraviolet (UV) and KMnO₄/HCl with A. terreus MF12 treatment, i.e., FT10. The abiotic physical and chemical factors enhance the biodegradation of HDPE using A. terreus MF12.     

Organochlorinated pesticides, PCBs, dioxins, and PBDEs in grey mullets (Liza ramada) and allis shads (Alosa alosa) from the Vilaine estuary (France)

This study aimed to compare the contamination levels of various organohalogenated compounds in two migratory fish species in the Vilaine River in western France. Organochlorinated pesticides, polychlorinated biphenyls (PCBs), dioxins (polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDDs/Fs)), and polybrominated diphenyl ethers (PBDEs) were analyzed in two diadromous species from the Vilaine estuary, the grey mullet (Liza ramada)—an amphihaline species, and the allis shad (Alosa alosa)—an anadromous species. Fish were collected in spring 2004 and spring 2005, upstream and downstream of the Arzal Dam. PCB contamination varied from 27 to 200 ng?g^?1 dry weight (d.w.). PCDDs/Fs, expressed in toxicity equivalent quantity (TEQ) varied from 0.4 to 2.8 pg?g^?1 d.w. Dioxins and dioxin-like PCBs expressed in total TEQ varied from 1.4 to 18.8 pg?g^?1 d.w. PBDE47 was present at around 2–10 ng?g^?1 d.w. and concentrations of the insecticide dichlorodiphenyltrichloroethane breakdown product p,p′-dichlorodiphenylchloroethylene varied from 1 to 14 ng?g^?1 d.w. For both species, specimens collected upstream were more contaminated. The grey mullet specimens were less contaminated than the allis shad when taken downstream of the dam but were more contaminated upstream. The allis shads presented intermediate contaminant concentrations with a less pronounced difference between upstream and downstream specimens. However, it is thought that shads do not feed when they spawn in the upstream parts of rivers, which should modify the contaminant concentrations. However, measurements in upstream shad samples show an unexpected increase of the contamination, which remains unexplained.     

苯胺-2,4-二氨基酚共聚物对水中Cr(Ⅵ)吸附性能的研究

利用化学氧化法合成了苯胺-2,4-二氨基酚的共聚物,并通过静态吸附实验研究了该材料对水中Cr(Ⅵ)的吸附性能.研究表明,该共聚物对废水中Cr(Ⅵ)的去除效果显著,该吸附过程为自发吸热反应,符合Langmuir单层吸附模型;其动力学行为符合准二级动力学方程.溶液pH值对吸附性能影响较大,pH 3～6范围内吸附效果较好.吸...