Acute toxicity of polybrominated diphenyl ethers (PBDEs) for turbot (<Emphasis Type="Italic">Psetta maxima</Emphasis>) early life stages (ELS)

Background, aim and scope  

The environmental presence of polybrominated diphenyl ethers (PBDEs), among which BDE-47 and BDE-99 are particularly abundant, makes toxicity data necessary to assess the hazard risk posed by PBDE to aquatic organisms. This study examines the effects of BDE-47 and BDE-99 on embryo-larval stages of the marine flatfish turbot.     

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.     

PCDDs/PCDFs in ambient air (<1 fg m−3) – The CTDEP long term sampling (30 d) method

The Connecticut Department of Environmental Protection (CTDEP) commenced monitoring for PCDDs/PCDFs (polychlorinated dibenzodioxins and polychlorinated dibenzofurans) in ambient air in 1987 and adopted the long term (30 d) sampling approach in 1993. The CTDEP method represents the first use of isotopically labeled PCDDs/PCDFs as field surrogates to monitor the behavior of native PCDDs/PCDFs present in actual ambient air samples. This feature first introduced in 1987 was later adopted by US EPA in revisions to sampling methods for PCDDs/PCDFs in ambient air (EPA Method TO9A) as well as development of EPA Reference Method 23 for measurement of PCDDs/PCFDs in stationary source emissions. Results are provided here for a total of twenty-three (23) samples (reported as pairs) representing twelve (12) 30 d sampling events conducted at a site located in metropolitan Hartford CT. Samples were collected in winter months during calendar years 2002–2008. PCDDs/PCDFs concentration data (pg m⁻³) are reported as both congener sums (Cl₄–Cl₈) and 2378-substitued congeners. Total PCDDs/PCDFs concentrations for these twelve (12) sampling events ranged from 0.68 pg m⁻³ (2003) to 4.18 pg m⁻³ (2004) with a mean concentration of 2.04 pg m⁻³.Method performance was monitored through use of collocated samples, in field isotopically labeled compounds, isotopically labeled laboratory applied internal standards and field blank samples. Method performance consistently exceeded goals established in USEPA Method TO9A for these same parameters. Average recoveries of in field labeled PCDDs/PCDFs ranged from 97.5% to 104.2%. Average (mean) recoveries for each of the ten (10) isotopically labeled internal standards ranged from 77.0% (¹³C-OCDF) to 95.5% (¹³C-2,3,7,8-TCDF). Method precision defined as % RPD data for collocated sampler pairs ranged from 8% to 14% for PCDDs and from 5% to 12% for PCDFs. The mean RPD for all PCDDs/PCDFs combined is 9.6%. Field monitoring results demonstrate method sensitivity for all PCDDs/PCDFs congeners and 2378-substituted congeners to be well below concentrations typically found for these compounds in ambient air (all reported data represent measured concentrations). Quantities (pg) found in field blanks represent the major determinant to achieving further enhancements in method sensitivity for selected congeners (OCDD < 42 fg m⁻³; 1,2,3,4,6,7,8-HpCDD < 5.7 fg m⁻³; and 1,2,3,4,6,7,8-HpCDF < 2.1 fg m⁻³). The CTDEP method represents a highly sensitive and reliable technique for monitoring of PCDDs/PCDFs congeners and other persistent organic pollutants (POPs) at ultra trace levels in ambient air (fg m⁻³).     

Sensitized photodegradation of adsorbed polychlorobiphenyls (PCB's)

Polychlorobiphenyls (PCB's) adsorbed on silica gel or montmorillonite were degraded mainly to less chlorinated biphenyls by U.V. irradiation (λ = 254 nm). The photodegradation was considerably enhanced by adding triethylamine to the system. The sensitizing effect can be ascribed, like in solution, to the formation of a charge-transfer complex confirmed by fluorescence quenching experiments.     

Possible involvement of frontier (π) electrons in the metabolism of poly-chlorinated biphenyls (PCBs)

The electron density, at each carbon atom, of the highest occupied π orbital of thirteen polychlorinated biphenyl (PCB) and one polychlorinated dibenzofuran (PCDF) molecules were calculated and the result was compared with their in vitro and/or in vivo metabolism. We noted that 1. the carbon position at which the frontier electron density was highest was most readily hydroxylated or sulfonated, 2. if the carbon with the highest frontier (π) electrons was occupied by chlorine, either a replacement occurred or the carbon with the next highest electron density was activated for metabolism, 3. due to steric hinderance ‘ortho’ carbons in PCBs were least preferred for such reactions inspite of possessing favorable electron density, 4. this was applicable to both phenobarbitol (PB) - type and 3-methyl cholanthrene (3 MC) - type PCB inducers. Frontier (π) electron density could be an easy guide for understanding the metabolic products of persistent and toxic environmental pollutants in vitro or in vivo and in understanding their environmental fate.     

Effects of 4-methylbenzylidene camphor (4-MBC) on neuronal and muscular development in zebrafish (<Emphasis Type="Italic">Danio rerio</Emphasis>) embryos

The negative effects of overexposure to ultraviolet (UV) radiation in humans, including sunburn and light-induced cellular injury, are of increasing public concern. 4-Methylbenzylidene camphor (4-MBC), an organic chemical UV filter, is an active ingredient in sunscreen products. To date, little information is available about its neurotoxicity during early vertebrate development. Zebrafish embryos were exposed to various concentrations of 4-MBC in embryo medium for 3 days. In this study, a high concentration of 4-MBC, which is not being expected at the current environmental concentrations in the environment, was used for the purpose of phenotypic screening. Embryos exposed to 15 μM of 4-MBC displayed abnormal axial curvature and exhibited impaired motility. Exposure effects were found to be greatest during the segmentation period, when somite formation and innervation occur. Immunostaining of the muscle and axon markers F59, znp1, and zn5 revealed that 4-MBC exposure leads to a disorganized pattern of slow muscle fibers and axon pathfinding errors during the innervation of both primary and secondary motor neurons. Our results also showed reduction in AChE activity upon 4-MBC exposure both in vivo in the embryos (15 μM) and in vitro in mammalian Neuro-2A cells (0.1 μM), providing a possible mechanism for 4-MBC-induced muscular and neuronal defects. Taken together, our results have shown that 4-MBC is a teratogen and influences muscular and neuronal development, which may result in developmental defects.     

Phytoremediation of a sulphonated azo dye Green HE4B by <Emphasis Type="Italic">Glandularia pulchella</Emphasis> (Sweet) Tronc. (Moss Verbena)

Purpose  

The dyes and dye stuffs present in effluents released from textile dyeing industries are potentially mutagenic and carcinogenic. Phytoremediation technology can be used for remediating sites contaminated with such textile dyeing effluents. The purpose of the work was to explore the potential of Glandularia pulchella (Sweet) Tronc. to decolorize different textile dyes, textile dyeing effluent, and synthetic mixture of dyes.     

Assessment of trace metal contamination in the sea cucumber (<Emphasis Type="Italic">Holothuria tubulosa</Emphasis>) and sediments from the Dardanelles Strait (Turkey)

This study was performed to determine the concentrations of some trace metals (Cd, Cu, Pb, Ni, Zn, and Fe) in Holothuria tubuosa (Gmelin, 1788) belonging to Echinoderm species and in sediments that they live at three different stations (Gelibolu, Umur Bey/Lapseki, and Dardanos) on Dardanelles Strait between April 2013 and March 2014. The mean trace metal concentrations determined in H. tubulosa and sediment were as follows: Cd 0.18 mg/kg, Cu 2.43 mg/kg, Pb 2.09 mg/kg, Ni 14.58 mg/kg, Zn 16.86 mg/kg, and Fe 73.46 mg/kg and Cd 0.70 mg/kg, Cu 5.03 mg/kg, Pb 14.57 mg/kg, Ni 27.15 mg/kg, Zn 54.52 mg/kg, and Fe 3779.9 mg/kg, respectively. It was detected that the statistical difference between trace metals determined seasonally in muscle tissue of H. tubulosa was significant (p?>?0.05). As a result of the study, it was detected that H. tubulosa is a bioindicator species in determining Ni trace metal in sediment. The results were compared to the limit values of National and International Food Safety, and it was detected that Cd and Ni concentrations measured in sediment were above LEL of Ni and Cd concentrations according to Sediment Quality Guidelines.     

Ferrate(VI) enhanced photocatalytic oxidation of pollutants in aqueous TiO<Subscript>2</Subscript> suspensions

Background, aim and scope  

Photocatalytic oxidation using UV irradiation of TiO₂ has been studied extensively and has many potential industrial applications, including the degradation of recalcitrant contaminants in water and wastewater treatment. A limiting factor in the oxidation process is the recombination of conduction band electrons (e ⁻ _cb) with electron holes (h_vb⁺) on the irradiated TiO₂ surface; thus, in aqueous conditions, the presence of an effective electron scavenger will be beneficial to the efficiency of the oxidation process. Ferrate (FeO₄²⁻) has received much recent attention as a water treatment chemical since it behaves simultaneously as an oxidant and coagulant. The combination of ferrate [Fe(VI)] with UV/TiO₂ photocatalysis offers an oxidation synergism arising from the Fe(VI) scavenging of e ⁻ _cb and the corresponding beneficial formation of Fe(V) from the Fe(VI) reduction. This paper reviews recent studies concerning the photocatalytic oxidation of problematic pollutants with and without ferrate.     

Tissue metal levels in Muskrat (Ondatra zibethica) collected near the Sudbury (Ontario) ore-smelters; prospects for biomonitoring marsh pollution

An examination of tissue metal levels in Sudbury-area muskrat (Ondatra zibethica) revealed that animals collected in the vicinity of the local ore-smelters contained elevated burdens of Cd and Ni in their liver and kidneys. Respective tissue concentrations averaged 2-fold and 3- to 6-fold higher than background values and are believed to reflect accumulations resulting from food chain contamination in regional marshes, including that reportedly characterizing Typha latifolia stands-their primary food source-and adherent sediments which may be consumed inadvertently while feeding. No evidence of site-influence or enhanced tissue metal levels was seen for Cu, Pb or Zn. While Cd : Ni accumulations were positively correlated in both the liver (r=0.78) and the kidneys (r=0.65), between-tissue comparisons indicated that hepatic : renal burdens were significantly correlated (r=0.75) only in the case of Ni. With the exception of 30-35% lower hepatic Zn levels in females relative to males within the Sudbury population, tissue metal levels did not vary according to sex or age class at either site. Our findings substantiate the potential of muskrat to serve as useful bioindicators/monitors of metal pollution in semi-aquatic environments.     

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 .     

Simultaneous conversion of CHClF(2) and CH(3)Br to CH(2)CF(2)

Gas phase reaction of CHClF(2) with CH(3)Br in an alumina tube reactor at 773-1123 K as a function of various input ratios of CH(3)Br to CHClF(2) is presented. The major products detected include C(2)F(4), CH(2)CF(2), and CH(4). Minor products include CH(3)Cl, CHF(3), C(2)H(4), C(2)H(2), CH(2)CF-CF(3), and C(2)H(3)F. The reaction produces a high yield of CH(2)CF(2) (53% based on CHClF(2) feed) at 1123 K and an input molar ratio of CH(3)Br to CHClF(2) of 1.8, suggesting that the reaction potentially can be developed as a process to convert two ozone depleting substances (CHClF(2) and CH(3)Br) to a highly valuable chemical, CH(2)CF(2). The reaction of CHClF(2) with CH(3)Cl and CH(3)I was also investigated under similar reaction conditions, to assist in understanding the reaction chemistry involved in the reaction of CHClF(2) with CH(3)Br.