Green chemistry with process intensification for sustainable biodiesel production

Biodiesel as a renewable fuel has the potential to replace non-renewable fossil fuels and associated environmental pollution. The most commonly used method in biodiesel production is transesterification of virgin and used oil feedstock. However, the chemical reaction (transesterification) does not proceed spontaneously, which means excess reactants are required to move the reaction to completion. The biodiesel reaction efficiency can be improved by incorporating green chemistry principles and process intensification effects. Green chemistry principles can be used to design chemical products and processes that reduce or eliminate the use and generation of hazardous substances. Microwave- and ultrasound-enhanced biodiesel synthesis can improve the reaction efficiency due to higher product recovery, low by-product formation, and reduced energy consumption. In addition, utilization of green metrics such as E-factor, atom economy (utilization), mass intensity or mass productivity, and reaction mass efficiency can help design safer and highly efficient biodiesel synthesis. Green chemistry principles have been analyzed for other processes in greater details, but they are rarely discussed in the context of biodiesel production. Process intensification by microwave- and ultrasound-mediated biodiesel production was never discussed from the perspective of green chemistry and sustainable process development. This research review article discusses the role of green chemistry and process intensification in biodiesel production followed by specific examples and illustrations on green metrics of microwave- and ultrasound-enhanced biodiesel synthesis and the effect of catalysts and solvents including discussions on reaction kinetics and activation energy in detail for the first time in the literature.     

Unusual polar metabolites in the groundwater of a contaminated waste site indicate a new pathway of mononitrotoluene transformation

At a mononitrotoluene-contaminated waste disposal site, the groundwater was screened for polar transformation products of mononitrotoluenes, by means of HPLC-MS, HPLC-NMR and further off-line NMR and MS techniques. Besides expected metabolites such as aminotoluenes (ATs) and nitrobenzoic acids (NBAs), three unknowns (di- and tetrahydro-derivatives of (2-oxo-quinolin-3-yl) acetic acid) could be identified which, in the context of explosives and related compounds, are new metabolites. Evidence could be provided by microcosm experiments with 2-nitrotoluene (2-NT) that these metabolites are microbial transformation products of 2-NT under anaerobic conditions. The NMR and MS data are presented and the possible pathway for the formation of these metabolites after addition of 2-NT to fumarate is discussed.     

Transesterification of waste vegetable oil under pulse sonication using ethanol,methanol and ethanol–methanol mixtures

This study reports on the effects of direct pulse sonication and the type of alcohol (methanol and ethanol) on the transesterification reaction of waste vegetable oil without any external heating or mechanical mixing. Biodiesel yields and optimum process conditions for the transesterification reaction involving ethanol, methanol, and ethanol–methanol mixtures were evaluated. The effects of ultrasonic power densities (by varying sample volumes), power output rates (in W), and ultrasonic intensities (by varying the reactor size) were studied for transesterification reaction with ethanol, methanol and ethanol–methanol (50%-50%) mixtures. The optimum process conditions for ethanol or methanol based transesterification reaction of waste vegetable oil were determined as: 9:1 alcohol to oil ratio, 1% wt. catalyst amount, 1–2 min reaction time at a power output rate between 75 and 150 W. It was shown that the transesterification reactions using ethanol–methanol mixtures resulted in biodiesel yields as high as >99% at lower power density and ultrasound intensity when compared to ethanol or methanol based transesterification reactions.     

Evaluating the sampling pattern when detecting Zones of Abrupt Change

We present a method for detecting the zones where an irregularly sampled variable changes abruptly in the plane. Such zones are called Zones of Abrupt Change (ZACs). This method not only allows estimation of ZACs, but also testing of their statistical significance against the null hypothesis of a stationary correlated random field. The sampling pattern, in particular its local density, is crucial in the detection of potential ZACs. In this paper, we address the problem of evaluating the sampling pattern by assessing the power of the local test used for detecting ZACs. It is shown that mapping the power allows us to identify zones where ZACs may or may not be detected. The methodology is applied to a soil data set sampled at eight different dates in an agricultural field. Detecting ZACs for the soil water content allowed us to identify permanent structures in the agricultural field related to the boundaries between different soil types. Mapping the power for various sampling densities proved to be useful to determine the minimal sampling density necessary for detecting ZACs.

Modeling analyses of the effects of changes in nitrogen oxides emissions from the electric power sector on ozone levels in the eastern United States

In this paper, we examine the changes in ambient ozone concentrations simulated by the Community Multiscale Air Quality (CMAQ) model for summer 2002 under three different nitrogen oxides (NOx) emission scenarios. Two emission scenarios represent best estimates of 2002 and 2004 emissions; they allow assessment of the impact of the NOx emissions reductions imposed on the utility sector by the NOx State Implementation Plan (SIP) Call. The third scenario represents a hypothetical rendering of what NOx emissions would have been in 2002 if no emission controls had been imposed on the utility sector. Examination of the modeled median and 95th percentile daily maximum 8-hr average ozone concentrations reveals that median ozone levels estimated for the 2004 emission scenario were less than those modeled for 2002 in the region most affected by the NOx SIP Call. Comparison of the "no-control" with the "2002" scenario revealed that ozone concentrations would have been much higher in much of the eastern United States if the utility sector had not implemented NOx emission controls; exceptions occurred in the immediate vicinity of major point sources where increased NO titration tends to lower ozone levels.     

An ecological approach to environmental impact assessment

Carbon cycling analysis is presented as a means for assessing anthropogenic perturbations in an ecosystem. Data from oligotrophic, eutrophic, and dystrophic (bog) lakes are used to show general trends in the lacustrine carbon cycle. The oligotrophic lake is an unstressed system and the eutrophic lake is under nutrient enrichment with high algal standing crops and productivity. The bog lake is a pH-stressed environment that is primarily a grazing ecosystem. It is hoped that a more effective environmental impact assessment will result from the use of carbon cycling as a unifying concept in ecosystem analysis.     

Ecological restoration as a strategy for conserving biological diversity

Though the restoration of disturbed ecosystems has so far played a relatively modest role in the effort to conserve biological diversity, there are reasons to suspect that its role will increase and that its contribution to the maintenance of diversity will ultimately prove crucial as techniques are further refined and as pristine areas for preservation become scarcer and more expensive.It is now possible to restore a number of North American communities with some confidence. However, it should be noted that many current efforts to return degraded lands to productive use, like attempts to reclaim land disturbed by mining, try only for rehabilitation to a socially acceptable condition and fall considerably short of actually restoring a native ecological community.Possible uses for restoration in the conservation of biodiversity include not only the creation of habitat on derelict sites, but also techniques for enlarging and redesigning existing reserves. Restoration may even make it possible to move reserves entirely in response to long-term events, such as changes in climate. Restoration in the form of reintroduction of single species to preexisting or restored habitat is also a critical link in programs to conserve species ex situ in the expectation of eventually returning them to the wild. And restoration provides opportunities to increase diversity through activities as diverse as management of utility corridors, transportation rights-of-way, and parks.     

Human exposure to PCBs, PBDEs and HBCDs in Ghana: Temporal variation, sources of exposure and estimation of daily intakes by infants

Human exposure to polychlorinated biphenyls (PCBs) and brominated flame retardants (BFRs) such as polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs) was evaluated in Ghana using breast milk samples collected in 2004 and 2009. Mean levels and ranges of PBDEs (4.5; 0.86-18 ng/g lw) and PCBs (62; 15-160 ng/g lw) observed in the present study were unexpectedly high, in spite of the fact that Ghana is a non-industrialized country when compared with many of the Asian and European countries. Significant increases were found in the concentrations of PCBs and PBDEs over the years, while no significant increase was observed for HBCDs. Estimated hazard quotient (HQ) showed that all the mothers had HQ values exceeding the threshold of 1 for PCBs, indicating potential health risk for their children. PCBs in dirty oils and obsolete equipment should be of concern as potential sources in Ghana, and e-waste recycling with little or no experience in safe handling could be a threat to this sub-region noted for unregulated disposal of e-waste. The results may point towards an increase in trends in human milk in Ghana, especially in the larger cities but further analysis would be required to confirm this upward trend in levels. This is the first study to report BFRs in human breast milk from Africa, and undoubtedly from Ghana.