Chemical valorization of forest and agricultural by-products. Obtention, chemical characteristics, and mechanical behavior of a novel family of hydrophobic films

Esterification of hemicelluloses of the xylan family was performed in order to produce hydrophobic films. Acylation reactions were carried out with lauroyl chloride in the N,N-dimethylacetamide/lithium chloride homogeneous system using 4-dimethylaminopyridine as activator and were induced by microwave irradiation. In the experimental conditions used, 108 and 172% mass ratios were obtained for the dodecyl-grafted xylan and heteroxylan, respectively. The degrees of substitution (DS) were 1.3 (maximum 2) for xylan and 1.2 (maximum 2.1) for heteroxylan. These products were further characterized by FT-IR spectroscopy. The mechanical and thermomechanical behavior of this new family of hydrophobic films were analyzed and compared to those obtained from cellulose with a similar DS by the means of tensile tests. Our results indicate that the dodecyl-grafted xylan film presents the best rigidity-resistance to traction ratio.     

The alcohol interlock: an underutilized resource for predicting and controlling drunk drivers

This report summarizes evidence presented during the Third Annual Ignition Interlock Symposium at Vero Beach, Florida, 29 October 2002. The ignition interlock prevents a car from starting when blood alcohol concentration (BAC) is elevated. We review some of our prior work as well as introduce previously unpublished results to demonstrate the manner in which the data recorded by the alcohol ignition interlock device can serve as an advance predictor of future driving under the influence (DUI) of alcohol risks. Data used in this current report represent approximately 2,200 ignition interlock users from Alberta, Canada, and about 8,000 interlock users from Quebec, Canada; the Alberta data set contained 5.5 million breath tests and the Quebec data 18.8 million breath tests. All tests are time and date stamped and this information was used to characterize patterns of BAC and vehicle use, and the relationship between BAC elevations and DUI offenses that accumulated after the interlock was removed from the vehicles. Findings from Cox regression show that BAC elevations >.02-.04% are more potent predictors of repeat DUI (p<.0001) than even prior DUI (p<.006), usually found to be the strongest indicator of driver risk. Prior DUI obviously has no use for scaling the risk of first-time offenders. Drivers who are both multiple offenders and who have more than a few elevated interlock BAC tests are much more likely to repeat DUI. The timing and pattern of elevated BAC tests provided during the time drivers were required to use an alcohol ignition interlock device are remarkably similar on both a daily basis and an hourly basis when the interlock programs from the two provinces are compared directly. Both provinces had higher rates of elevated tests on Saturday and Sunday, and the fewest elevated tests on Tuesdays. The absolute rate of elevated tests is similar despite the two provinces adhering to different interlock lockout points (.02% Quebec;.04% Alberta). Charts tracking the Monday-Friday timing of elevated BAC tests by hour are nearly identical for both provinces. The most elevated BAC tests occurred between 7 and 9 A.M. Monday to Friday, even though most vehicle start attempts occurred much later in the day. This higher rate of elevated morning BAC likely represents drinking from the prior evening with alcohol not yet cleared from circulation; those with elevated BAC in the early morning were more likely to have a repeat offense even after accounting for prior DUI and the higher overall rate of elevated BAC tests. This is viewed as evidence of a drinking problem that will lead to impaired driving after the controlling function of the interlock is removed. Policy changes are discussed that might take better advantage of interlock information to improve the public response to drunk driving.     

Improving the extraction of tetrachloroethylene from soil columns using surfactant gradient systems

In this work, we extend the recently developed gradient approach for surfactant-enhanced remediation of dense non-aqueous phase liquid (DNAPL)-impacted sites. The goal of the gradient approach is to maximize the DNAPL solubilization capacity in swollen micelles (Type I aqueous microemulsions) while at the same time minimizing the potential for DNAPL mobilization. In this work, we introduce a modified version of the capillary/trapping curve that we refer to as the gradient curve to help interpret and/or design the gradient approach. The gradient curve presents the residual DNAPL saturation as a function of interfacial tension and microemulsion viscosity. This approach demonstrates that keeping a low viscosity of the microemulsion phase is not only important for keeping a low head loss during surfactant flooding but also to prevent oil mobilization. Eight microemulsion systems were evaluated in this research; these systems were evaluated based on their tetrachloroethylene (PCE) solubilization capacity, interfacial tension (IFT), viscosity, density, and coalescence kinetics. Two of these systems were chosen for evaluation in site-specific column tests using an increasing electrolyte gradient to produce a decreasing IFT/increasing solubilization gradient system. The column studies were conducted with media from Dover Air Force Base in Dover, DE. Both solubilized and mobilized DNAPL were quantified. During the column studies, we observed that substantial PCE was mobilized when the residual level of PCE in the column was significantly higher than the steady-state residual saturation level being approach (as predicted from the gradient curve). Four column studies were performed, three of which were used to asses the validity of the gradient curve in predicting the residual saturation after each gradient step. From these tests we observed that starting IFTs of less than 1 mN/m all produced the same mobilization potential. In the last column, we used an additional gradient step with an initial IFT above 1 mN/m to dramatically reduce the amount of PCE mobilize. Based on the good agreement between column results and projections based on the gradient curve, we propose this as a preferred method for designing gradient surfactant flushing systems.     

Quantitative tolerance values for common stream benthic macroinvertebrates in the Yangtze River Delta,Eastern China

Aquatic organisms’ tolerance to water pollution is widely used to monitor and assess freshwater ecosystem health. Tolerance values (TVs) estimated based on statistical analyses of species-environment relationships are more objective than those assigned by expert opinion. Region-specific TVs are the basis for developing accurate bioassessment metrics particularly in developing countries, where both aquatic biota and their responses to human disturbances have been poorly documented. We used principal component analysis to derive a synthetic gradient for four stressor variables (total nitrogen, total phosphorus, dissolved oxygen, and % silt) based on 286 sampling sites in the Taihu Lake and Qiantang River basins (Yangtze River Delta), China. We used the scores of taxa on the first principal component (PC1), which explained 49.8 % of the variance, to estimate the tolerance values (TV_r) of 163 macroinvertebrates taxa that were collected from at least 20 sites, 81 of which were not included in the Hilsenhoff TV lists (TV_h) of 1987. All estimates were scaled into the range of 1–10 as in TV_h. Of all the taxa with different TVs, 46.3 % of TV_r were lower and 52.4 % were higher than TV_h. TV_r were significantly (p?<?0.01, Fig. 2), but weakly (r ²?=?0.34), correlated with TV_h. Seven biotic metrics based on TV_r were more strongly correlated with the main stressors and were more effective at discriminating references sites from impacted sites than those based on TV_h. Our results highlight the importance of developing region-specific TVs for macroinvertebrate-based bioassessment and to facilitate assessment of streams in China, particularly in the Yangtze River Delta.     

Benthic Impacts of Intertidal Oyster Culture, with Consideration of Taxonomic Sufficiency

An investigation of the impacts from elevated intertidal Pacific oyster culture in a New Zealand estuary showed enhanced sedimentation beneath culture racks compared with other sites. Seabed elevation beneath racks was generally lower than between them, suggesting that topographic patterns more likely result from a local effect of rack structures on hydrodynamic processes than from enhanced deposition. Compared with control sites, seabed sediments within the farm had a greater silt/clay and organic content, and a lower redox potential and shear strength. While a marked trend in macrofaunal species richness was not evident, species composition and dominance patterns were consistent with a disturbance gradient, with farm effects not evident 35 m from the perimeter of the racks. Of the environmental variables measured, sediment shear strength was most closely associated with the distribution and density of macrofauna, suggesting that human-induced disturbance from farming operations may have contributed to the biological patterns. To evaluate the taxonomic sufficiency needed to document impacts, aggregation to the family level based on Linnean classification was compared with an aggregation scheme based on `general groups' identifiable with limited taxonomic expertise. Compared with species-level analyses, spatial patterns of impact were equally discernible at both aggregation levels used, provided density rather than presence/absence data were used. Once baseline conditions are established and the efficacy of taxonomic aggregation demonstrated, a `general group' scheme provides an appropriate and increasingly relevant tool for routine monitoring.     

Paternity alone does not predict long-term investment in juveniles by male baboons

Adult male chacma baboons (Papio hamadryas ursinus) form preferential associations, or friendships, with particular lactating females. Males exhibit high levels of affiliative contact with their friends’ infants and defend them from potentially infanticidal attacks (Palombit et al. 1997). Little is known about males’ associations with juveniles once they have passed the period of infanticidal risk. We conducted an observational, experimental, and genetic study of adult male and juvenile chacma baboons in the Moremi Reserve, Botswana. We identified preferential associations between males and juveniles and used behavioral data and a playback experiment to explore whether those associations have potential fitness benefits for juveniles. We determined whether males preferentially invest in care of their own offspring. We also determined how often males invest in care of their former friends’ offspring. The majority of juveniles exhibited preferential associations with one or two males, who had almost always been their mother’s friend during infancy. However, in only a subset of these relationships was the male the actual father, in part because many fathers died or disappeared before their offspring were weaned. Male caretakers intervened on behalf of their juvenile associates in social conflicts more often than they intervened on behalf of unconnected juveniles, and they did not appear to differentiate between genetic offspring and unrelated associates. Playbacks of juveniles’ distress calls elicited a stronger response from their caretakers than from control males. Chacma males may provide care to unrelated offspring of former friends because the costs associated with such care are low compared with the potentially high fitness costs of refusing aid to a juvenile who is a possible offspring.     

Peacocks orient their courtship displays towards the sun

We studied two courtship displays of male peafowl (Pavo cristatus), focusing particularly on male orientation relative to the position of the sun. During the “wing-shaking” display, females were generally behind the displaying male, and male orientation with respect to the position of the sun was not significantly different from random. However, during the pre-copulatory “train-rattling” display, males were on average directed at about 45° to the right of the sun azimuth with the female positioned directly in front, suggesting that this behaviour is involved in the communication of a visual signal. A model presentation experiment confirmed that courting peacocks were more likely to perform the train-rattling display when the female was on the sunny side of their erect train, but more likely to perform wing-shaking behaviour when the female was on the shaded side of the male. This study underscores the importance of visual signalling in peafowl courtship, and we suggest that an angle of about 45° relative to the sun may allow males to enhance the appearance of their iridescent eyespot feathers. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

The feasibility of processing lead-based paint abatement wastes through primary and secondary lead smelters

This study was undertaken to determine the feasibility of processing soil and lead-based paint (LBP) abatement waste through primary and secondary lead smelting facilities. The main objectives were to determine the compatibility of soil and LBP abatement waste with lead smelting circuits; the costs associated with transporting and processing the abatement waste through a smelter; and a review of major environmental laws or regulations which may impact the lead smelting industry's ability to carry out this process. While not all categories of LBP wastes are suited for reclamation through lead smelters, sufficient classes are to make the effort worthwhile. Specifically, lead paint chips, dusts, heatgun sludge, soils and certain blasting abrasives appear metallurgically compatible with the lead smelting circuits. Additionally, there do not appear to be any current regulatory statutes that forbid the process from being carried out, so long as certain permit modifications are obtained. Finally, the estimated smelting costs seem to compare favourably with current treatment and disposal fees at approved landfills. However, despite the promise of these initial findings, a great deal of work remains to be done if the concept of processing lead paint wastes through lead smelters for reclamation is to become a reality.     

Interphase mass transfer during chemical oxidation of TCE DNAPL in an aqueous system

The chemical oxidation of trichloroethene dense non-aqueous phase liquid by permanganate was studied in an aqueous system using micro-reaction/extraction vessels in a novel approach. Experiments were conducted at ambient temperature ( approximately 20 degrees C) under static and mixed conditions to evaluate the rate of TCE(DNAPL) dissolution as a function of permanganate concentration. Chemical oxidation by permanganate was shown to increase the rate of TCE(DNAPL) dissolution under static conditions and decrease the rate of dissolution under mixed conditions. The apparent inconsistency in results appears to result from the local deposition of a film at the DNAPL interface composed of manganese oxide solids as discovered through visual observation with the aid of a Goniometer. Data from interfacial deposition experiments suggest that the film formed rapidly and reached maturation within approximately 2 h with little or no growth occurring thereafter. A conceptual model of the reaction and mass transfer processes occurring at the DNAPL interface was proposed based on the experimental results.