Removal of an anionic dye (Acid Blue 92) by coagulation–flocculation using chitosan

Chitosan (a biopolymer) is an aminopolysaccharide that can be used for the treatment of colored solutions by coagulation–flocculation (as an alternative to more conventional processes such as sorption). Acid Blue 92 (a sulfonic dye) was selected as a model dye for verifying chitosan's ability to treat textile wastewater. A preliminary experiment demonstrated that chitosan was more efficient at color removal in tap water than in demineralized water, and that a substantially lower concentration of chitosan could be used with tap water. Dye removal reached up to 99% under optimum concentration; i.e., in terms of the acidic solutions and the stoichiometric ratio between the amine groups of the biopolymer and the sulfonic groups in the dye. The flocs were recovered and the dye was efficiently removed using alkaline solutions (0.001–1 M NaOH solutions) and the biopolymer, re-dissolved in acetic acid solution, was reused in a further treatment cycle.     

Pyrolysis of permethrin and formation of precursors of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) under non-oxidative conditions

This article reports the computational and experimental results of the thermal decomposition of permethrin, a potential source of dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF). We have performed a quantum chemical analysis by applying density functional theory to obtain the decomposition pathways of permethrin and the formation mechanism of dibenzofuran. We have conducted the pyrolysis experiments in a tubular reactor and identified the pyrolysis products to demonstrate the agreement between the experimental measurements and quantum chemical calculations. The initiation of the decomposition of permethrin involves principally the aromatisation of permethrin into 3-phenoxyphenylacetic acid, 2-methylphenyl ester (J) and concomitant loss of 2HCl. This rearrangement is followed by the rupture of the O–CH₂ linkage in J, with a rate constant derived from the quantum chemical results of 1 × 10¹⁵ exp(−68 kcal/mol/RT) s⁻¹ for temperatures between 700 and 1300 K. This is confirmed by finding that the rate constant for unimolecular rearrangement of permethrin into J is 1.2 × 10¹² exp(−53 kcal/mol/RT) s⁻¹ over the same range of temperatures and exceeds the direct fission rate constant at all temperatures up to 850 ± 120 °C as well as by the experimental detection of J prior to the detection of the initial products incorporating diphenyl ether, 1-methyl-3-phenoxybenzene, 3-phenoxybenzaldehyde and 1-chloromethyl-3-phenoxybenzene. As the temperature increases, we observe a rise in secondary products formed directly or indirectly (via phenol/phenoxy) including aromatics (naphthalene), biphenyls (biphenyl, 4-methyl-1,1′-biphenyl) and dibenzofuran (DF). In particular, we discover by means of quantum chemistry a direct route from 2-phenoxyphenoxy to naphthalene. We detect no polychlorinated dibenzo-p-dioxins and dibenzofurans. Unlike the case of oxidative pyrolysis [Tame, N.W., Dlugogorski, B.Z., Kennedy, E.M., 2007b. Formation of dioxins in fires of arsenic-free treated wood: Role of organic preservatives. Environ. Sci. Technol. 41, 6425–6432] where significant yields of both PCDD and PCDF were obtained, under non-oxidative conditions the thermal decomposition of permethrin does not form appreciable amounts of PCDD or PCDF and the presence of oxygen (and/or a sizable radical pool) appears necessary for the formation of dibenzo-p-dioxin itself or PCDD/F from phenol/phenoxy.     

Economic potential for conversion to organic farming: a net present value analysis in the East Mau Catchment,Nakuru, Kenya

This paper discusses the economic potential in terms of income changes that may result from conversion to low-external-input agriculture (LEIA) organic farming in a Kenya’s catchment area. A spreadsheet model applying the gross margin and net present value analysis was developed to estimate economic returns to labour and land of alternative smallholder cropping systems in the East Mau Catchment. The income and costs over a 10-year horizon associated with current cropping practices of a typical farm household cultivating 1.12 hectares of maize–bean intercrop, Irish potato, carrots, tomatoes, cabbages and kales mix were characterized based on field work conducted in 2008–2010. An “average” smallholder LEIA organic farm was simulated based on the conventional one, and its income discounted. A comparison was then made of the two farm types. Results indicate annual net present value returns to cropped land average Ksh 21,878/ha ($ 267/ha) and Kshs 22,561/ha (€ 275/ha) in 2010 values for conventional and prototype LEIA organic farming systems, respectively. Net returns are particularly sensitive to crop yields and price and cost of fertilizers and seeds. Further efforts should be made to provide an economic analysis of other LEIA organic farming practices such as composting, double digging and agroforestry in terms of additional labour costs resultant. The model can be extended to build more scenarios on the role of price premiums. Additionally, further research should be done to exploit the socio-demographic factors affecting the adoption of low-external-input systems.     

Synergistic vulnerabilities: climate variability and fire management policy increase farming challenges in southeastern Mexico

Agricultural fire for land preparation is central in the livelihoods of subsistence farmers practicing shifting cultivation. Achieving a good agricultural burn, one in which the biomass is thoroughly consumed within the chosen area, depends on specific weather conditions. Fire use decisions are also shaped by institutions that define the timing and rules for fire use but also constrain the alternatives and shape adaptive capacities. Global and regional climate changes interact with the institutional framing of fire management affecting local fire use and burn outcomes. These effects are documented and analyzed to suggest adaptations to existing governance systems. We examined subsistence farmers’ socio-ecological vulnerability in the Calakmul municipality, located in southeastern Mexico. Using interviews with farmers and government agents, as well as participatory mapping and observation of agricultural burns, we studied fire management knowledge, practices and burn outcomes. Our results describe a continuum of burn outcomes covering good agricultural burns, uncontrolled burns leading to wildfires and “malquemados” literally poorly burned areas. Malquemados represent unsuccessful combustion associated with excess moisture that results in scorched vegetation. We discuss how unexpected early rains trigger effects that cascade through space and the ecological, economic and cultural domains. We argue that fire management has been historically approached from a conservation standpoint yet agricultural fire use and wildfire prevention should also be addressed from a rural development perspective. This shift in fire management would lead to the proper inclusion of the entire array of burn outcomes in studies and policies addressing farmers’ vulnerability amplified by synergistic effects between climate variability and institutional change.     

Biological nitrogen and carbon removal in a gravity flow biomass concentrator reactor for municipal sewage treatment

A novel membrane system, the Biomass Concentrator Reactor (BCR), was evaluated as an alternative technology for the treatment of municipal wastewater. Because the BCR is equipped with a membrane whose average poresize is 20 μm (18–28 μm), the reactor requires low-pressure differential to operate (gravity). The effectiveness of this system was evaluated for the removal of carbon and nitrogen using two identical BCRs, identified as conventional and hybrid, that were operated in parallel. The conventional reactor was operated under full aerobic conditions (i.e., organic carbon and ammonia oxidation), while the hybrid reactor incorporated an anoxic zone for nitrate reduction as well as an aerobic zone for organic carbon and ammonia oxidation. Both reactors were fed synthetic wastewater at a flow rate of 71 L d^?1, which resulted in a hydraulic retention time of 9 h. In the case of the hybrid reactor, the recycle flow from the aerobic zone to the anoxic zone was twice the feed flow rate. Reactor performance was evaluated under two solids retention times (6 and 15 d). Under these conditions, the BCRs achieved nearly 100% mixed liquor solids separation with a hydraulic head differential of less than 2.5 cm. The COD removal efficiency was over 90%. Essentially complete nitrification was achieved in both systems, and nitrogen removal in the hybrid reactor was close to the expected value (67%).     

PM2.5 source apportionment with organic markers in the Southeastern Aerosol Research and Characterization (SEARCH) study

Positive matrix factorization (PMF) and effective variance (EV) solutions to the chemical mass balance (CMB) were applied to PM_2.5 (particulate matter with an aerodynamic diameter <2.5 μm) mass and chemically speciated measurements for samples taken from 2008 to 2010 at the Atlanta, Georgia, and Birmingham, Alabama, sites. Commonly measured PM_2.5 mass, elemental, ionic, and thermal carbon fraction concentrations were supplemented with detailed nonpolar organic speciation by thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS). Source contribution estimates were calculated for motor vehicle exhaust, biomass burning, cooking, coal-fired power plants, road dust, vegetative detritus, and secondary sulfates and nitrates for Atlanta. Similar sources were found for Birmingham, with the addition of an industrial source and the separation of biomass burning into open burning and residential wood combustion. EV-CMB results based on conventional species were qualitatively similar to those estimated by PMF-CMB. Secondary ammonium sulfate was the largest contributor, accounting for 27–38% of PM_2.5, followed by biomass burning (21–24%) and motor vehicle exhaust (9–24%) at both sites, with 4–6% of PM_2.5 attributed to coal-fired power plants by EV-CMB. Including organic compounds in the EV-CMB reduced the motor vehicle exhaust and biomass burning contributions at both sites, with a 13–23% deficit for PM_2.5 mass. The PMF-CMB solution showed mixing of sources within the derived factors, both with and without the addition of speciated organics, as is often the case with complex source mixtures such as those at these urban-scale sites. The nonpolar TD-GC/MS compounds can be obtained from existing filter samples and are a useful complement to the elements, ions, and carbon fractions. However, they should be supplemented with other methods, such as TD-GC/MS on derivitized samples, to obtain a wider range of polar compounds such as sterols, sugars, and organic acids. The PMF and EV solutions to the CMB equations are complementary to, rather than replacements for, each other, as comparisons of their results reveal uncertainties that are not otherwise evident.

Implications:?Organic markers can be measured on currently acquired PM_2.5 filter samples by thermal methods. These markers can complement element, ion, and carbon fraction measurements from long-term speciation networks. Applying the positive matrix factorization and effective variance solutions for the chemical mass balance equations provides useful information on the accuracy of the source contribution estimates. Nonpolar compounds need to be complemented with polar compounds to better apportion cooking and secondary organic aerosol contributors.     

IAPCS: A Computer Model that Evaluates Pollution Control Systems for Utility Boilers

The IAPCS model, developed by U.S. EPA’s Air and Energy Engineering Research Laboratory and made available to the public through the National Technical Information Service, can be used by utility companies, architectural and engineering companies, and regulatory agencies at all levels of government to evaluate commercially available technologies for control of SO₂, NO_x, and particulate matter emissions from coal-fired utility boilers with respect to performance and cost. The model is considered to be a useful tool to compare alternative control strategies to be used by utilities to comply with the requirements of the CAA, and to evaluate the sensitivity of control costs with respect to many of the significant variables affecting costs.

To illustrate the use of the model for site-specific studies, the authors used the model to estimate control costs for SO₂ and NO_x control at Detroit Edison’s Monroe plant and two hypothetical plants under consideration and at three plants operated by New York State Electric and Gas Corporation. The economic and technical assumptions used to drive the model were those proposed by the utilities if cited, and if not cited, the model default values were used. The economic format and methodologies for costs cited in the Electric Power Research Institute’s Technical Assessment Guide are used in the IAPCS model. Depending on the specific conditions and assumptions for the cases evaluated, SO₂ control costs ranged from $417 to $3,159 per ton of SO₂ removed, and NO_x control costs ranged from $461 to $3,537 per ton of NO_x removed or reduced.     

Biofiltration Control of Hydrogen Sulfide 1. Design and Operational Parameters

Laboratory scale biological filter systems for control of hydrogen sulfide (H₂S) in waste gas have been studied and the optimum design and operating parameters determined. Extensive tests have been conducted to evaluate the effect of various filter bed operating parameters such as temperature, retention time, H₂S concentration, and H₂S loading rate. Variable properties of new and used composts such as sulfate content, acidity, and water content have been studied for their influence on H₂S removal efficiency. The effects of compost particle size distribution on system pressure drop and the maximum H₂S elimination capacity were examined. Biofiltration systems containing various types of yard waste compost as the filter material have been observed to remove hydrogen sulfide with efficiencies greater than 99.9 percent for H₂S inlet concentrations in the range from 5 to 2650 ppmv.     

Experimental exposure of juvenile savannah monitors (Varanus exanthematicus) to an environmentally relevant mixture of three contaminants: effects and accumulation in tissues

Using varanids as indicators of pollution in African continental wetlands was previously proposed. The present study aimed at understanding experimentally how monitors absorb and accumulate pollutants and how they are affected. The relevance of non-destructive sampling was also evaluated. Savannah monitors (Varanus exanthematicus) were orally exposed during 6 months to a mixture of lead, 4,4′-dichlorodiphenyltrichloroethane (4,4′-DDT) and chlorpyrifos-ethyl (CPF) or to the vehicle only. Proportionally to their mass, exposed monitors received the same dose: 20 then 10 mg lead?kg^?1, 2 then 0.5 mg CPF?kg^?1 and 4 mg 4,4′-DDT?kg^?1. Individuals surviving contamination were euthanized after 4 or 6 months of experiment. Tissues were analysed for lead by atomic absorption spectrophotometry and for DDT and CPF by gas chromatography. Exposed monitors absorbed all three pollutants but only lead (essentially in bone, tail tips and phalanxes) and 4,4′-DDT plus its main metabolites (essentially in fat and liver) accumulated. CPF killed ten individuals. Clear correlations occurred between the total quantity of lead or 4,4′-DDT administered and concentrations in tissues. Tail tips and skin samples are recommended non-destructive indicators for lead and organochlorine pesticides contamination, respectively. This work confirms that monitors can be used as relevant indicators of environmental pollution by lead and organochlorine pesticides. Although varanids withstand heavy lead and DDT contamination, our results suggest that CPF can be lethal at very low doses to the herpetofauna and emphasize the importance of considering all taxa in impact assessment studies, including reptiles.