Acetone-induced photodechlorination of Aroclor 1254 in alkaline 2-propanol: Probing the mechanism by thermolysis in the presence of di-t- butyl peroxide

Aroclor 1254 (1860 mg/l) in alkaline 2-propanol and in the presence of acetone (4% v/v) was photodechlorinated to biphenyl at λ >300 nm with exceptionally high quantum yield (Φ= 18). Under similar conditions photodechlorination of extracts of Aroclor 1254 contaminated soil (730 mg/kg) proceeded with lower quantum yield Φ= 0.4. While oxygen severely quenched photolysis, dechlorination was accomplished under thermal conditions using di-t-butyl peroxide, t-BuOOBu-t, as free radical initiator. A free radical chain reaction is suggested in which acetone triplet, T₁(n,π*), or t-BuO^· radical abstracts H-atom from 2-propanol to give the ketyl radical, (CH₃)₂ OH, which after losing a proton to the alkaline medium gives the ketyl radical anion, (CH₃)₂CHO^·−. The Aroclor in turn reacts with the latter species through an electron-transfer process giving unstable aryl radical anion, , which cleaves releasing the chloride anion, Cl⁻ and the aryl radical, A^·     

Sperm traits of the quacking frog, Crinia georgiana: intra- and interpopulation variation in a species with a high risk of sperm competition

Sperm traits often show extreme variation both between and within species. Between-species variation may often be interpreted in the context of a sperm competition theory, but within-species variation has remained unexplained. Previous studies on intraspecific variation in sperm traits have focused on a limited set of variables and may have failed to explain observed variation because of potential trade-offs between different sperm traits. We report on variation in number, size, motility and longevity of sperm in the frog Crinia georgiana, a species where sperm competition is common. We found intrapopulation variation in sperm size and motility and interpopulation variation in relative sperm number and size. When we combined relative sperm number and size into one variable, and motility and longevity into another, we found significant interpopulation variation in these variables as well. We also detected considerable intra- and significant interpopulation variation in cumulative sperm quality, a combination of all four sperm traits. Furthermore, a significant effect of the interaction between population origin and male size on sperm characteristics indicated interpopulation variation in the strength of selection acting on sperm traits of males adopting different mating strategies. We discuss heterogeneity in the reproductive environment, a complex genetic background in the determination of sperm characteristics and varying levels of developmental noise as potential contributors to the observed variation in sperm traits.     

Selenium and nano-selenium in plant nutrition

Selenium (Se) is a naturally occurring metalloid element which occurs nearly in all environments. Se is considered as a finite and non-renewable resource on the Earth. The common sources of Se in earth’s crust occur in association with sulfide minerals such as metal selenide, whereas it is rarely found in elemental form (Se⁰). While there is no evidence of Se need for higher plants, several reports show that when Se added at low concentrations, Se exerts beneficial effects on plant growth. Se may act as quasi-essential micronutrient through altering different physiological and biochemical traits. Thus, plants vary considerably in their physiological and biochemical response to Se. This review focusses on the physiological importance of Se forms as well as different Se fertilizers for higher plants, especially plant growth, uptake, transport, and metabolism.     

Size-dependent characterisation of historical gold mine wastes to examine human pathways of exposure to arsenic and other potentially toxic elements

Abandoned historical gold mining wastes often exist as geographically extensive, unremediated, and poorly contained deposits that contain elevated levels of As and other potentially toxic elements (PTEs). One of the key variables governing human exposure to PTEs in mine waste is particle size. By applying a size-resolved approach to mine waste characterisation, this study reports on the proportions of mine waste relevant to human exposure and mobility, as well as their corresponding PTE concentrations, in four distinct historical mine wastes from the gold province in Central Victoria, Australia. To the best of our knowledge, such a detailed investigation and comparison of historical mining wastes has not been conducted in this mining-affected region. Mass distribution analysis revealed notable proportions of waste material in the readily ingestible size fraction (≤250 µm; 36.1–75.6 %) and the dust size fraction (≤100 µm; 5.9–45.6 %), suggesting a high potential for human exposure and dust mobilisation. Common to all mine waste types were statistically significant inverse trends between particle size and levels of As and Zn. Enrichment of As in the finest investigated size fraction (≤53 µm) is of particular concern as these particles are highly susceptible to long-distance atmospheric transport. Human populations that reside in the prevailing wind direction from a mine waste deposit may be at risk of As exposure via inhalation and/or ingestion pathways. Enrichment of PTEs in the finer size fractions indicates that human health risk assessments based on bulk contaminant concentrations may underestimate potential exposure intensities.     

Variation in fertilisation abilities between hemiclonal hybrid and sexual parental males of sympatric water frogs (<Emphasis Type="Italic">Rana lessonae</Emphasis>,<Emphasis Type="Italic"> R. esculenta</Emphasis>,<Emphasis Type="Italic"> R. ridibunda</Emphasis>)

In many species, males and females mate with multiple partners, which gives rise to sperm competition and multiple paternity. The experiments on water frogs presented here demonstrate that such sperm competition can affect the structure and dynamics of mixed-species communities. The hybrid frog Rana esculenta (LR) mates with one of its parental species, usually R. lessonae (LL), although in some areas R. ridibunda (RR), to regain the premeiotically eliminated parental genome ("hybridogenesis"). Mixed LL/LR-populations are stable although hybrid numbers should continuously increase at the expense of parental animals, because of differences in female fecundity and other factors. This would finally lead to the extinction of the sexual host, followed by that of the sexual parasite, unless the reproductive superiority of R. esculenta is reduced by other factors, such as lower hybrid male fertility. Eggs from LL- and LR-females were fertilised in vitro by single- and multi-male sperm suspensions of LL-, LR- and RR-males. In all experiments, the proportion of offspring sired by R. esculenta sperm was significantly lower than that sired by R. lessonae or R. ridibunda sperm. Gonad mass, sperm morphology, sperm swimming velocity, and sperm survival did not explain these differences in fertilisation success; nor did gamete recognition and compatibility. Sperm density was the only trait that paralleled fertilisation success, but it offers no explanation either, because densities were equalised for the in-vitro fertilisations. In natural LL/LR populations, the significantly smaller amount, poorer competitive ability and lower long-term survival of R. esculenta compared to R. lessonae sperm will reduce the initial reproductive superiority of hybrids and contribute to the stabilisation of mixed water-frog populations. Differences in fertilisation ability are also likely to be relevant for the structure and dynamics of several other systems with encounters between eggs and sperm from different genotypes, ecotypes, ploidy levels and/or species.