Application of 1D and 2D MFR reactor technology for the isolation of insecticidal and anti-microbial properties from pyrolysis bio-oils

Valuable chemicals can be separated from agricultural residues by chemical or thermochemical processes. The application of pyrolysis has already been demonstrated as an efficient means to produce a liquid with a high concentration of desired product. The objective of this study was to apply an insect and microorganism bioassay-guided approach to separate and isolate pesticidal compounds from bio-oil produced through biomass pyrolysis. Tobacco leaf (Nicotianata bacum), tomato plant (Solanum lycopersicum), and spent coffee (Coffea arabica) grounds were pyrolyzed at 10°C/min from ambient to 565°C using the mechanically fluidized reactor (MFR). With one-dimensional (1D) MFR pyrolysis, the composition of the product vapors varied as the reactor temperature was raised allowing for the selection of the temperature range that corresponds to vapors with a high concentration of pesticidal properties. Further product separation was performed in a fractional condensation train, or 2D MFR pyrolysis, thus allowing for the separation of vapor components according to their condensation temperature. The 300–400°C tobacco and tomato bio-oil cuts from the 1D MFR showed the highest insecticidal and anti-microbial activity compared to the other bio-oil cuts. The 300–350 and 350–400°C bio-oil cuts produced by 2D MFR had the highest insecticidal activity when the bio-oil was collected from the 210°C condenser. The tobacco and tomato bio-oil had similar insecticidal activity (LC₅₀ of 2.1 and 2.2 mg/mL) when the bio-oil was collected in the 210°C condenser from the 300–350°C reactor temperature gases. The 2D MFR does concentrate the pesticidal products compared to the 1D MFR and thus can reduce the need for further separation steps such as solvent extraction.     

Recycling plant wax constituents for chemical defense: hemi-biosynthesis of triterpene saponins from β-amyrin in a leaf beetle

Several species of Doryphorina leaf beetles from Central- and South America produce oleanane triterpene glycosides in their defensive glands. The presence of pentacyclic triterpenes in insects is intriguing since they lack the key enzymes necessary to synthesize these compounds. Since -amyrin is a common constituent of leaf waxes, we hypothesized that these leaf beetles use this compound as a precursor to their oleanane glycosides. To test this hypothesis we first confirmed the presence of -amyrin in Ipomoea batatas, the food plant of Platyphora kollari. Next, adults of P. kollari were fed for 10 days with I. batatas leaf disks painted with a solution of [2,2,3-²H₃]-amyrin ([2,2,3-²H₃]-1). The secretion from their defensive glands was collected and analyzed by HPLC-ESIMS. The results demonstrated that the secretion of beetles fed with an amount of [2,2,3-²H₃]-amyrin corresponding to the quantity of unlabeled (natural) -amyrin present in the leaf disks contained on average 5.1% of [2,2,3-²H₃]-3-O--d-glucopyranosyl-(1-->4)--d-glucuronopyranosyl-hederagenin ([2,2,3-²H₃]-2), whereas the secretions of beetles fed with 10 times this amount of [2,2,3-²H₃]-amyrin contained on average 23.9% of [2,2,3-²H₃]-2. In both series of experiments, the percentage of labeled versus unlabeled triterpene glycoside in the secretion was positively correlated with the amount of deuterated -amyrin ingested. These results demonstrate for the first time that some leaf beetles are able to metabolize a widespread triterpenic constituent of leaf wax into more complex glycosides that are stored in their defensive glands.     

Does the queen win it all? Queen–worker conflict over male production in the bumblebee,<Emphasis Type="Italic"> Bombus terrestris</Emphasis>

Social insects provide a useful model for studying the evolutionary balance between cooperation and conflict linked to genetic structure. We investigated the outcome of this conflict in the bumblebee, Bombus terrestris, whose annual colony life cycle is characterized by overt competition over male production. We established artificial colonies composed of a queen and unrelated workers by daily exchange of callow workers between colony pairs of distinct genetic make-up. Using microsatellite analysis, this procedure allowed an exact calculation of the proportion of worker-derived males. The development and social behavior of these artificial colonies were similar to those of normal colonies. Despite a high worker reproduction attempt (63.8% of workers had developed ovaries and 38.4% were egg-layers), we found that on average 95% of the males produced during the competition phase (CPh) were queen-derived. However, in four colonies, queen death resulted in a considerable amount of worker-derived male production. The different putative ultimate causes of this efficient control by the queen are discussed, and we suggest a possible scenario of an evolutionary arms race that may occur between these two female castes.     

Field Evidence of Dissolution and Degradation Rates Enhancement During ISCR and ENA Treatments of Chlorinated Solvents

This article presents field tests comparing two methods of treatment of chlorinated solvents undertaken at the same site. The site is an automobile factory where two chlorinated solvents (CS) plumes were identified. At the first source, in situ chemical reduction (ISCR) was applied, while at the second one, enhanced natural attenuation (ENA) was used. A set of specific multilevel sampling wells were installed approximately 20 m downgradient of the sources to estimate the efficiency of the treatments. The presence of a low‐permeability layer (source 1) or a thick oil lens (source 2) in the top part of the aquifer prevented the CS from reaching the bottom of the aquifer. These layers led to difficulties treating the contamination. At the ISCR and ENA treatment zones, the concentrations of tetrachloroethene (PCE) and trichloroethene (TCE) did not change significantly, while the concentration of metabolites (cis‐1,2‐DCE, vinyl chloride, and ethene) significantly increased 50 to 150 days after treatment. Due to high concentration of CS in the source zone, a mass balance calculation, including chlorine, was possible. It showed that around 1 to 2 percent of the injected products were used to reduce the CS. A detailed analysis and 1D analytical modeling of CS concentrations showed that the treatment led to a large (two to three times) increase in dissolution of the organic phase. This explains why, despite an efficient treatment, the PCE and TCE concentrations remained virtually unchanged. Degradation rates also increased due to the treatment. Due to some differences in the source‐zone chemistry, it was not possible to differentiate between the ISCR and ENA efficiencies. © 2013 Wiley Periodicals, Inc.     

Influence of mature compost amendment on total and bioavailable polycyclic aromatic hydrocarbons in contaminated soils

A laboratory microcosm study was carried out to assess the influence of compost amendment on the degradation and bioavailability of PAHs in contaminated soils. Three soils, contaminated with diesel, coal ash and coal tar, respectively, were amended with two composts made from contrasting feedstock (green waste and predominantly meat waste) at two different rates (250 and 750 t ha^?1) and incubated for 8 months. During this period the treatments were sampled for PAH analysis after 0, 3, 6 and 8 months. Total and bioavailable fractions were obtained by sequential ultrasonic solvent extraction and hydroxypropyl-β-cyclodextrin extraction, respectively, and PAHs were identified and quantified by GC–MS. Bioavailability decrease due to sorption was only observed at the first 3 months in the diesel spiked soil. After 8 months, compost addition resulted in over 90% loss of total PAHs irrespective of soil types. Desorption and degradation contributed to 30% and 70%, respectively, of the PAH loss in the spiked soil, while PAH loss in the other two soils resulted from 40% enhanced desorption and 60% enhanced degradation. Compost type and application rates had little influence on PAH bioavailability, but higher PAH removal was observed at higher initial concentration during the early stage of incubation. The bioavailable fraction of PAH was inversely correlated to the number of benzene rings and the octanol–water partition coefficient. Further degradation was not likely after 8-month although over 30% of the residual PAHs were bioavailable, which highlighted the application of bioavailability concept during remediation activities.     

Green sand reclamation using a fluidized bed with an attrition nozzle

The objective of this study was to determine the technical feasibility of green sand reclamation using attrition in a gas–solid fluidized bed. Reclamation of foundry sand is becoming important as it may help solve concerns related to transportation and dumping of the used sand, and reduce production costs by recycling sand. The crucial step in green sand reclamation is the removal of small clay particles that are bound to the sand particles.For this study two different types of green sand were used and supplied by two different foundries. Tests were performed in a fluidized bed equipped with an attrition nozzle operating at pressures of either 350 or 550 kPa (50 or 80 psig). Attrition experiments for one green sand were performed on either unburned or burned (calcined) green sand, to determine the effect of prior calcination of the green sand on its reclamation potential by attrition. Calcination temperatures of over 700 °C were employed, and the results suggest that calcination facilitates the removal of clay from the green sand.Green sand was analyzed for clay and organic content, acid request, and particle size before and after attrition. Attriting calcined green sand produces the best results. Also experiments conducted at the highest attrition pressure of 550 kPa gave good results. According to the mass balance, the mass lost during the attrition process may be limited to less than 14%, and this could be considered acceptable. The volume of air required for the attrition nozzle is rather high and this may adversely affect the economics of the process.     

Predator guild does not influence orangutan alarm call rates and combinations

Monkey alarm calls have shown that in the primate clade, combinatorial rules in acoustic communication are not exclusive to humans. A recent hypothesis suggests that the number of different call combinations in monkeys increases with increased number of predator species. However, the existence of combinatorial rules in great ape alarm calls remains largely unstudied, despite its obvious relevance to ideas about the evolution of human speech. In this paper, we examine the potential use of combinatorial rules in the alarm calls of the only Asian great ape: the orangutan. Alarm calls in orangutans are composed of syllables (with either one or two distinct elements), which in turn are organized into sequences. Tigers and clouded leopards are predators for Sumatran orangutans, but in Borneo, tigers are extinct. Thus, orangutans make a suitable great ape model to assess alarm call composition in relation to the size of the predator guild. We exposed orangutans on both islands to a tiger and control model. Response compositionality was analyzed at two levels (i.e., syllable and syllable sequences) between models and populations. Results were corroborated using information theory algorithms. We made specific, directed predictions for the variation expected if orangutans used combinatorial rules. None of these predictions were met, indicating that monkey alarm call combinatorial rules do not have direct homologues in orangutans. If these results are replicated in other great apes, this indicates that predation did not drive selection towards ever more combinatorial rules in the human lineage.     

BIOLOGICAL AND ECONOMIC IMPLICATIONS OF SACRAMENTO WATERSHED MANAGEMENT OPTIONS1

ABSTRACT: This paper brings together spatially and temporally explicit mechanistic models of hydrodynamic, water quality, and ecological processes with an economic model to examine water management alternatives for California's Sacramento River and Delta ecosystem, a large‐scale watershed. Overallocated water supplies in most years, combined with increasing demand for water for environmental purposes, have created a politically charged atmosphere and a need for quantitative assessment of the implications of policy alternatives. By developing and analyzing a common set of policy scenarios, this integrated framework allows us to consider tradeoffs between agricultural economic factors, water quality, and population dynamics for two at‐risk fish species. We analyze two rather extreme types of policy options; one involves structural modifications to change the flow of water within the watershed but no change in water diversions, while the other reallocates water from agricultural users to fish and wildlife. Results suggest that substantial environmental improvements could be made at a relatively modest cost to farmers (1 to 4 percent reductions in revenues) but that those costs could be significant locally. In addition to tradeoffs between farmers and environmental interests, results suggest that policy makers may need to balance competing environmental objectives.