Degradation and leaching potential of pesticides in biobed systems

Biobeds provide a potential solution to pesticide contamination of surface waters arising from the farmyard. Previous work has shown that biobeds can effectively treat spills and splashes of pesticide. This study investigated the potential for biobeds to treat much larger volumes and amounts of pesticide waste not only arising from spills but also from washing processes. Two systems were assessed using a range of pesticides at the semi-field scale, ie a lined biobed system and an unlined system. Studies using the lined biobeds demonstrated that water management was crucial, with biobeds needing to be covered to exclude rain-water. Once covered, the top of the biobed became hydrophobic, restricting moisture loss and resulting in saturated conditions at depth. The drying out of the top layer coincided with a measured decrease in microbial biomass in the treated biobeds. Applied pesticides were effectively retained within the 0-5 cm layer. Whilst all pesticides tested degraded, low moisture content and microbial activity meant degradation rates were low. Studies using unlined biobeds showed that only the most mobile pesticides leached, and for these > 99% was removed by the system, with a significant proportion degraded within 9 months. Peak concentrations of the two most mobile pesticides did however exceeded the limits that are likely to be required by regulatory bodies. However, it is thought that these limits could be reached by optimisation of the system.     

Degradation of pesticides in biobeds: the effect of concentration and pesticide mixtures

Biobeds aim to create an environment whereby any pesticide spills are retained and then degraded, thus reducing the potential for surface or groundwater contamination. Biobeds may receive high concentrations of relatively complex mixtures of pesticides. The effects of concentration and pesticide interaction on degradation rate were therefore investigated. At concentrations up to 20 times the maximum recommended application rate for isoproturon and chlorothalonil, the rate of degradation in topsoil and biomix decreased with increasing concentration. With the exception of isoproturon at concentrations above 11 mg kg(-1), degradation was quicker in biomix (a composted mixture of topsoil, compost, and wheat straw) than in topsoil. One possible explanation for faster isoproturon degradation in topsoil as compared to biomix may be that previous treatments of isoproturon applied to the field soil as part of normal agricultural practices had resulted in proliferation of microbial communities specifically adapted to use isoproturon as an energy source. Such microbial adaptation could enhance the performance of a biobed. Studies with a mixture of isoproturon and chlorothalonil showed that interactions between pesticides are possible. In biomix, the degradation of either isoproturon or chlorothalonil was unaffected by the presence of the other pesticide, whereas in topsoil, isoproturon DT(50) values increased from 18.5 to 71.5 days in the presence of chlorothalonil. These studies suggest that biobeds appear capable of treating high concentrations of more than one pesticide.     

Leaching of pesticides from biobeds: effect of biobed depth and water loading

Pesticides may be released to farmyard surfaces as a result of spillages, leakages, and the decontamination of tractors and sprayers. Biobeds can be used to intercept and treat contaminated runoff, thus minimizing losses to the environment. Previous studies using lined and unlined biobeds showed that water management was the limiting factor for both systems. While lined biobeds effectively retained pesticides, the system rapidly became water logged and degradation was slow. Studies using unlined biobeds showed that >99% of the applied pesticides were removed by the system, with a significant proportion degraded within 9 months. However, peak concentrations of certain pesticides (Koc < 125) were unacceptable to the regulatory authorities. These experiments were designed to optimize the design and management of unlined biobeds. Experiments performed to investigate the relationship between biobed depth and water loading showed that biobeds need to have a minimum depth of 1-1.5 m. The surface area dimension of the biobed depends on the water loading, which is controlled by the nature and frequency of pesticide handling activities on the farm. Leaching losses of all but the most mobile (Koc < 15) pesticides were <0.32% of the applied dose from 1.5 m deep biobeds subject to a water loading of 1175 L m(-2). These were reduced to <0.06% when a water loading of 688 L m(-2) was applied and down to <0.0001% for a water loading of 202 L m(-2). On the basis of these data, a 1.5 m deep biobed, subject to a maximum water loading of 1121 L m(-2) and with a surface area of 40 m(2) should be able to treat < or =44000 L of pesticide waste and washings such that the average concentration of all pesticides, other than those classified as very mobile, does not exceed 5 microg L(-1). This level of treatment can be improved by further reduction in the hydraulic loading.     

Lithospheric Contributions to Arc Magmatism: Isotope Variations Along Strike in Volcanoes of Honshu, Japan

Major chemical exchange between the crust and mantle occurs in subduction zone environments, profoundly affecting the chemical evolution of Earth. The relative contributions of the subducting slab, mantle wedge, and arc lithosphere to the generation of island arc magmas, and ultimately new continental crust, are controversial. Isotopic data for lavas from a transect of volcanoes in a single arc segment of northern Honshu, Japan, have distinct variations coincident with changes in crustal lithology. These data imply that the relatively thin crustal lithosphere is an active geochemical filter for all traversing magmas and is responsible for significant modification of primary mantle melts.     

Size Dependence of Structural Metastability in Semiconductor Nanocrystals

The kinetics of a first-order, solid-solid phase transition were investigated in the prototypical nanocrystal system CdSe as a function of crystallite size. In contrast to extended solids, nanocrystals convert from one structure to another by single nucleation events, and the transformations obey simple unimolecular kinetics. Barrier heights were observed to increase with increasing nanocrystal size, although they also depend on the nature of the nanocrystal surface. These results are analogous to magnetic phase transitions in nanocrystals and suggest general rules that may be of use in the discovery of new metastable phases.     

Synergistic Effect of Porcine Follicular Fluid and Dibutyryl Cyclic Adenosine Monophosphate on Development of Parthenogenetically Activated Oocytes from Pre‐Pubertal Gilts

This study investigated the effect of porcine follicular fluid (PFF) and dibutyryl cyclic adenosine monophosphate (dbcAMP) during in vitro maturation (IVM) of porcine oocytes on meiotic maturation, fertilization and embryo development, and compared the effect of supplementing the embryo culture media with PFF or foetal bovine serum (FBS) on embryo development. Oocytes from pre‐pubertal gilts were IVM for 44 h, and parthenogenetically activated or in vitro‐fertilized. Embryos were cultured in porcine zygote medium (PZM3) for 7 days. Cleavage and blastocyst rates were evaluated at 48 h and 7 days of culture. The supplementation of the IVM medium with 25% PFF and 1 mm dbcAMP for the first 22 h resulted in more (p < 0.05) embryos developing to the blastocyst stage as compared with the inclusion of dbcAMP alone. The dbcAMP + PFF combination increased (p < 0.05) the average number of nuclei per blastocyst as compared with either of these components alone or in its absence. A synergistic effect of dbcAMP + PFF during IVM was also reflected in the capacity of oocytes to regulate sperm penetration and prevent polyspermy, as twice as many oocytes from the control group were penetrated by more than one sperm as compared with those matured in the presence of both dbcAMP and PFF. The supplementation of PZM3 with 10% FBS from days 5 to 7 of culture significantly improved the total cell quantity in embryos derived either from control or dbcAMP + PFF matured oocytes. There was no effect on the total cell quantity when FBS was replaced by the same concentration of PFF. These studies showed that dbcAMP, PFF and FBS can improve both the quantity (57.3% vs 41.5%) and quality (74.8 vs 33.3 nuclei) of porcine blastocysts derived from oocytes recovered of pre‐pubertal gilts.     

Evaluation of a lower tier exposure assessment model for veterinary medicines

Veterinary antibiotics are used in large quantities in the European Union, and one of the key environmental exposure routes is via the application of manure containing excreted antibiotics to arable land as fertilizer. It is a legal requirement to assess the environmental risk of veterinary medicines, and this is done in two stages. A key decision parameter in phase I of these assessments is the predicted environmental concentration (PEC) in soil, and if a trigger value of 100 microg/kg is exceeded, then further phase II studies on the fate, behavior, and effects are carried out. A widely used model to calculate manure and soil PECs is the Uniform Approach. This study evaluated the Uniform Approach in two ways: first, by reviewing existing data, addressing data gaps by performing degradation studies, and then calculating soil and manure PECs for the veterinary antibiotics sulfachloropyridazine, oxytetracycline, and tylosin applied to arable land via liquid pig manure and comparing these data with the results from two field-scale fate studies; second, by collating monitoring data and making a comparison with modeled data. The data comparisons indicated that the Uniform Approach model performed conservatively, with initial PECs being up to 2 orders of magnitude greater than measured environmental concentrations, providing confidence in the use of the model in the risk assessment process, although the assumption of first-order degradation kinetics in the model may underestimate the environmental persistence of veterinary antibiotics.     

Fertility Results after Vaginal Deposition of Frozen‐Thawed Buck Semen Diluted with Two Different Extenders Using One‐ or Two‐Step Procedures

In two field trials (T1 and T2), the effect of two different extenders for buck semen was tested. Semen from six (T1) and seven (T2) bucks of the Norwegian Dairy Goat breed was diluted either in a milk‐based extender containing egg yolk (M) or in a commercially available extender without egg yolk [Andromed^® (A)]. Dilution in M was performed in a two‐step procedure including centrifugation of the ejaculates and removal of the supernatant, while dilution in A was performed in one step. During the two trials (T1 and T2) 514 and 714, does, respectively, were artificially inseminated during natural oestrus, and the farmers performed the inseminations themselves after attending an artificial insemination (AI) training course. Vaginal insemination with 200 × 10⁶ spermatozoa diluted in M resulted in a 25‐day non‐return rate (NRR) and kidding rate of 37.3% and 24.5%, respectively, while semen diluted in A resulted in 31.7% NRR and a kidding rate of 19.8% (T1). In T2, NRR and kidding rate for AI performed with semen diluted with M were 42.7% and 28.5%, respectively, while dilution in A gave 37.2% NRR and a kidding rate of 26.8%. There was no significant effect of extender in the two trials [T1:p = 0.068 (NRR), p = 0.148 (kidding rate), T2:p = 0.096 (NRR), p = 0.38 (kidding rate)], but farmer had a significant effect on the fertility parameters in both trials. In conclusion, the present studies may indicate that Andromed^® is suitable for buck semen. However, more research is necessary to confirm the results and to improve the fertility of does after vaginal AI with frozen‐thawed semen.     

Transient phase-induced nucleation

A transient metastable rotator phase occurring on crystallization of hexadecane into its triclinic phase from the supercooled melt was directly observed with time-resolved synchrotron x-ray scattering. In this system, the limit of supercooling (the crystallization temperature) is determined by the thermodynamic stability of the transient phase with respect to the liquid. The crystallization kinetics of the homologous series of n-alkanes was measured and explained in terms of a crossover from stability to "long-lived" metastability to transient metastability. This crossover allowed further confirmation of the nature of the transient phase.