Study of the influence of dilute acid pre-treatment conditions on glucose recovery from Moringa oleifera Lam for fuel-ethanol production

The influence of temperature (175 to 195°C), residence time (5 to 15 min), and sulfuric acid concentration in high (2 to 4% w/w) and low (0.5 to 1.5% w/w) levels in dilute acid pretreatment of Moringa oleifera Lam is studied. Glucose recoveries in the liquid fraction and in the hydrolyzed insoluble fraction as well as the presence of inhibitors in the liquid fraction are determined. Best experimental results are achieved at 185°C, 2% w/w acid concentration, and 5 min reaction time obtaining a glucose recovery of 83.68%. An increment in 48.81% in glucose yield compared with the one of not pretreated Moringa is obtained. 0.13 g ethanol/g Moringa from fermentation of pre-hydrolysate and hydrolysate obtained at the optimal pre-treatment conditions are obtained.     

Biodiesel synthesis and characterization using welted thistle plant (Carduus acanthoides) as source of new non-edible seed oil

In this work we applied base catalyzed transesterification to convert non-edible welted thistle oil (Carduus acanthoides) as new non-edible feedstock into biodiesel (Fatty acid methyl esters). The highest biodiesel yield of 88% was obtained using optimized reaction conditions of 70°C and 5:1 molar ratio (methanol:oil). The synthesized esters were characterize and confirmed by the application of NMR and FT-IR techniques. Gas chromatography and mass spectroscopy identified different fatty acids as palmatic acid (C16:0), oleic acid (C18:1), linoleic acid (18:2), arachidic acid (C20:0), eicosanic acid (C20:1), and erucic acid (C22:1) in the oil of welted thistle. Six corresponding methyl esters reported in welted thistle oil biodiesel includes 9-hexadecenoic acid, hexadecanoic acid, 9-octadecadienoic acid, 11-eicosanoic acid, eicosanoic acid and 13-docosenoicacid. Fuel properties, such as density @40°C Kg/L (0.8470), kinematic viscosity @ 40°C c St (4.37), flash point (95°C), cloud point (+4°C), pour point (?5°C), and sulfur contents (0.0112% wt) of the biodiesel produced were compatible with American Society for Testing and Materials D 6751 specifications.     

Enzyme catalyzed biodiesel production from rubber seed oil containing high free fatty acid

Unrefined rubber seed oil contains high levels of free fatty acids and moisture, which make the conventional chemical catalyzed transesterification unsuitable. The method of enzyme catalyzed transesterification is well suited for biodiesel production from rubber seed oil as the enzymes are insensitive to the free fatty acids. In the present work, rubber seed oil was extracted from preserved rubber seed cake by mechanical means. The extraction process was designed and optimized through 2⁴ full factorial design. Extracted oil was subjected to enzymatic transesterification using four different lipases to identify the best one for the purpose. Transesterification process was optimized by considering three influencing variables for biodiesel production viz. methanol/oil molar ratio, catalyst concentration (% w/v) and solvent content (% v/v). A 2³ full factorial design was applied to design the experiments and optimize the biodiesel production. The interactive effects of the independent variables on biodiesel yield were analyzed and regression models were developed for each set of enzyme reactions. Among the four lipases, Thermomysis Lanugonosus Lipase was found to be the most suitable for the transesterification of rubber seed oil with a biodiesel conversion of 92.83% at a molar ratio of 4% and 5% (w/v) enzyme concentration in solvent free reaction medium.     

Degradation of 14C-atrazine bound residues in brown soil and rendzina fractions

The remobilization and the fate of 14C-ring labeled atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine) bound residues was examined in relation with the turnover of natural soil organic matter. Soil fractions of a brown soil and a rendzina were incubated under controled laboratory conditions. The mineralization of natural organic matter and atrazine-bound residues was respectively estimated by the amounts of CO2 and 14CO2 evolved during the incubation. The remobilization and distribution of 14C residues among the soil organic fractions were achieved after physical-chemical extractions of the samples. Comparisons of samples in abiotic and biotic conditions allowed us to assess the influence of microbial activity on the fate of atrazine-bound residues. The mineralization curves showed that natural organic matter and atrazine-bound residues had similar decomposition patterns. After 100 d of incubation, 0.8 to 3.6% of total organic C was evolved as CO2, while only 0.1% of the initial radioactivity was mineralized as CO2, and 7 to 15% was becoming extractable with water and methanol. Few differences were observed in the distribution of residues within organic compounds for both fractions of the rendzina, except a decrease of the 14C radioactivity of the 50- to 5000-microm fraction and a slight increase of that of humin. For the 0- to 5000-microm brown soil fraction, increased radioactivity in humin at the expense of humic (HA) and fulvic (FA) acids was detected after incubation, while for the 0- to 50-microm fraction more radioactivity was recovered with FA.     

The treatment of textile wastewater including chromium(VI) and reactive dye by sulfate-reducing bacterial enrichment

Sulfate-reducing bacteria (SRB) that could grow on modified Postgate C medium (PC) containing chromium(VI) were isolated from industrial wastewaters and their chromium(VI) reduction capacities were investigated as a function of changes in the initial pH values, chromium, sulfate, NaCl and reactive dye concentrations. The optimum pH value at 50 mg l(-1) initial chromium(VI) concentration was determined to be 8. Chromium(VI) reduction by SRB was investigated at 22.7-98.4 mg l(-1) initial chromium(VI) concentrations. At the end of the experiments, the mixed cultures of SRB were found to reduce within 2-6 days more than 99% of the initial chromium(VI) levels, which ranged from 22.7 to 74.9 mg l(-1). The effects of the initial 0-9.0 g l(-1) concentrations of disodium sulfate and 0-6% (w/v) concentrations of NaCI to chromium reduction showed that the lowest concentrations of sulfate and NaCI were the best for chromium reduction in the PC medium including 50 mg l(-1) chromium(VI). Chromium(VI) reduction in 50 mg l(-1) and 25-100 mg l(-1) Remazol Blue, Reactive Black B or Reactive Red RB containing media were also investigated. In the experiments, 25-30% of the initial dye concentrations and 95% of the chromium(VI) was removed from the medium at the end of 72-h and 24-h incubation periods, respectively.     

Ethanol production from alkali-pretreated oil palm empty fruit bunch by simultaneous saccharification and fermentation with mucor indicus

Oil palm empty fruit bunch (OPEFB) is a potential raw material for production of lignocellulosic bioethanol. The OPEFB was pretreated with 8% sodium hydroxide (NaOH) solution at 100°C for 10 to 90 min. Enzymatic digestion was carried out using cellulase and β-glucosidase at 45°C for 24 h. It was then inoculated with Mucor indicus spores suspension and fermented under anaerobic conditions at 37°C for 96 h. Sodium hydroxide pretreatment effectively removed 51–57% of lignin in the OPEFB and also its hemicellulose (40–84%). The highest glucan digestibility (0.75 g/g theoretical glucose) was achieved in 40-min NaOH pretreatment. Fermentation by M. indicus resulted in 68.4% of the theoretical ethanol yield, while glycerol (16.2–83.2 mg/g), succinic acid (0–0.4 mg/g), and acetic acid (0–0.9 mg/g) were its by-products. According to these results, 11.75 million tons of dry OPEFB in Indonesia can be converted into 1.5 billion liters of ethanol per year.     

Production of chicken fat ethyl esters via optomized protocols with dry washing by silica gel

The chicken fat ethyl ester (CFEE) was developed through alkali-catalyzed transesterification with ethanol using potassium hydroxide (KOH) as a catalyst. Parameters affecting the process of transesterification such as the catalyst concentration, ethanol to oil molar ratio, reaction temperature, and reaction duration are investigated. As a result, maximum CFEEs of 90% (~96.21 ester content% w/w) was obtained under optimal conditions of 1.0 wt.% KOH, 8:1 ethanol to fat molar ratio, a reaction temperature of 70°C, and a duration of 90 min. Dry washing method using (3.0% w/w) of silica gel was used to purify the crude ethyl ester from the residual catalyst, glycerol, and other impurities. Properties of the produced ethyl esters were determined and found in accordance with specifications prescribed by the ASTM standards. Moreover, blends of CFEEs and petrodiesel were prepared and evaluated according to ASTM test methods.     

A process model to estimate the cost of industrial scale biodiesel production from waste cooking oil by supercritical transesterification

This paper describes the conceptual design of a production process in which waste cooking oil is converted via supercritical transesterification with methanol to methyl esters (biodiesel).Since waste cooking oil contains water and free fatty acids, supercritical transesterification offers great advantage to eliminate the pre-treatment capital and operating cost.A supercritical transesterification process for biodiesel continuous production from waste cooking oil has been studied for three plant capacities (125,000; 80,000 and 8000 tonnes biodiesel/year). It can be concluded that biodiesel by supercritical transesterification can be scaled up resulting high purity of methyl esters (99.8%) and almost pure glycerol (96.4%) attained as by-product.The economic assessment of the biodiesel plant shows that biodiesel can be sold at US$ 0.17/l (125,000 tonnes/year), US$ 0.24/l (80,000 tonnes/year) and US$ 0.52/l for the smallest capacity (8000 tonnes/year).The sensitive key factors for the economic feasibility of the plant are: raw material price, plant capacity, glycerol price and capital cost.Overall conclusion is that the process can compete with the existing alkali and acid catalyzed processes.Especially for the conversion of waste cooking oil to biodiesel, the supercritical process is an interesting technical and economical alternative.     

Hydrothermal liquefaction phase behavior of microalgae & model compounds in fused silica capillary reactor

A fused silica capillary reactor combined with a heating/cooling stage, a microscope and a digital camera were used to investigate phase behavior during the hydrothermal liquefaction of microalgae (Dunaliella tertiolecta) and model compounds, including soya protein and glycine, starch, glucose and xylose, stearic acid and palmitic acid. Bubbles were generated at 246°C and disappeared at 360°C upon heating when Dunaliella tertiolecta used as feedstocks. Moreover, liquid products were generated at 300°C upon heating and oily liquid products began to separate out at 250°C upon cooling. The phase behavior of soya protein was similar to that of the Dunaliella tertiolecta. Meanwhile, there only observed the bubbles generation during hydrothermal liquefaction of glycine. Heating the starch, glucose and xylose above 350°C generated black solids from carbonization. Stearic acid and palmitic acid only had the process of melting, dissolution, dispersion and precipitation.     

Transesterification of Caesalpinia eriostachys seed oil using heterogeneous and homogeneous basic catalysts

Caesalpinea eriostachys seed oil, as a source of triglycerides with potential application for biodiesel production in Mexico is introduced. Its lipid profile obtained by Gas Chromatography-Mass Spectrometry (GC-MS) revealed saturated and unsaturated glycerol esters as the constituents. Therefore, heterogeneous and homogeneous catalyzed transesterification reactions were assayed employing ZnAl hydrotalcites and KOH, as the catalysts, respectively. The transesterification reactions yielded 59% for Zn/Al(2), 79% for Zn/Al(4), and 90% for KOH, depicting typical behavior, as in biodiesel production data from literature, where Zn-Al hydrotalcites or KOH were assayed. The caloric, density, viscosity values, and fatty acid methyl esters profile from reaction products were concordant to EN 14214, suggesting C. eriostachys as a promising feedstock for biodiesel production.     

Adsorption of arsenate and arsenite on ferrihydrite in the presence and absence of dissolved organic carbon

The adsorption of As(V) and As(III) on synthetic two-line ferrihydrite in the presence and absence of a peat humic acid (HAp), Suwannee River fulvic acid (FA), or citric acid (CA) was investigated. Previous work with goethite has demonstrated the ability of dissolved organic carbon (DOC) to decrease As(V) and As(III) adsorption. The results obtained demonstrate that As(V) adsorption on ferrihydrite was decreased only in the presence of CA. Arsenate decreased the adsorption of all organic acids except HAp. Both FA and CA reduced As(III) adsorption on ferrihydrite, while HAp had no effect. Fulvic and citric acid adsorption on ferrihydrite was decreased in the presence of As(III); however, FA and CA adsorption increased at lower pH, which was consistent with decreased As(III) adsorption. Peat humic acid did not decrease As(III) adsorption, and we believe that the adsorption process of HAp and As(III) and As(V) on ferrihydrite are independent of each other. Previously, we observed that As(V) adsorption on goethite decreased in the presence of HAp > FA > CA, while As(III) adsorption on goethite was decreased similarly to that on ferrihydrite in the presence of CA > FA approximately HAp, yet As(III) adsorption on ferrihydrite was greater than on goethite. The observed differences between this study and the earlier study on goethite are believed to be an intricate function of ferrihydrite's surface characteristics, which affect the mechanisms of adsorption and hence the affinity of organic acids such as HAp, FA, and CA for the ferrihydrite surface. As such, the adsorption of DOCs to ferrihydrite are assumed to be less favorable and to occur with a fewer number of ligands, resulting in lower surface coverage of weaker bond strength.     

Cadmium binding by fractions of dissolved organic matter and humic substances from municipal solid waste compost

The agricultural practice of amending soils with composted municipal solid waste (MSW) adds significant amounts of organic matter and trace metals, including Cd. Under these conditions, soluble organic complexes of Cd formed in the compost may be more significant than previously thought, due to Cd bioavailability and mobility in the soil environment. To study the relative importance of different types of organic ligands in MSW compost for the binding of Cd, six fractions of the dissolved organic matter (DOM) in addition to humic acid (HA) and fulvic acid (FA) were extracted and their complexation of Cd quantified at pH 7 using an ion-selective electrode (ISE). The highest complexing capacities (CC) for Cd were found for the most humified ligands: HA (2386 micromol Cd g(-1) C of ligand), predialyzed FA (2468 micromol Cd g(-1) C), and HoA, a fulvic-type, easily soluble fraction (1042 micromol Cd g(-1) C). The differences in CC for Cd of the various organic ligands were not directly related to total acid-titratable or carboxylic groups, indicating the importance of sterical issues and other functional groups. The strength of association between Cd and the organic ligands was characterized by calculating stability constants for binding at the strongest sites (pK(int)) and modeling the distribution of binding site strengths. The pK(int) values of the DOM fractions ranged between 6.93 (HiN: polysaccharides) and 8.11 (HiB: proteins and aminosugars), compared with 10.05 for HA and 7.98 for FA. Hence, the highly complex and only partially soluble organic molecules from compost such as HA and FA demonstrated the highest capacity to sequester Cd. However, strong Cd binding of organic ligands containing N-functional groups (HiB) in addition to a high CC of soluble, humified ligands like HoA indicated the relevance of these fractions for the organic complexation of Cd in solution.     

Optimization of esterification of fatty acid rubber seed oil for methyl ester synthesis in a plug flow reactor

To date, non-food vegetable oil has been considered as the primary source for biodiesel production. Rubber seed oil has high acid value (34 mgKOH/g) and can be used for biodiesel synthesis. The purpose of this study was to investigate esterification of fatty acid, which derived from rubber seed oil, in a plug flow reactor system at high temperature and low methanol consumption. Response surface methodology was applied for design experiment and optimization of esterification reaction. Temperature, methanol consumption, and sulfuric acid were chosen as variables to examine their influence in a conversion to methyl ester. At 140°C, at 5:1 methanol to fatty acid ratio (by mole), H₂SO₄ 1.5 (%v/w), and space time 20 min, the conversion to methyl ester attained 98.2%. Fourier transform infrared spectroscopy (FTIR) and gas chromatography-Mass spectrometry (GC-MS) were used for analysis and to confirm the formation of methyl ester. Methyl ester was characterized for biodiesel fuel properties in accordance to ASTM standard.     

Potential biodiesel-producing microalgae: two new strains of Amphikrikos sp.

BH32 and BH43 were isolated and identified as Amphikrikos sp. based on morphological characteristics and phylogenetic trees. They shared the same 18S rRNA sequences, but possessed different amounts of introns in their 18S rDNAs. The specific growth rate, cellular component and fatty acid profile under different growth stages have been surveyed. Their main fatty acids were found to be C16 and C18 groups. Our results indicated that both of them could be taken as excellent candidates of biodiesel. Moreover, the intra-genus polymorphism of 18S rDNA caused by intron presence/absence can provide valuable information for the study of intron evolution.     

Dual-function growth medium and structural soil for use as porous pavement

Permeable grass-covered surfaces can reduce the quantity of storm water runoff and filter out potentially harmful chemicals. The objective of this study was to develop permeable structural soils that sustained healthy turf growth and filtered heavy metals from contaminated pavement runoff. The basic soil medium was a 50:50 mixture (v/v) of expanded shale (ExSh) and quartz sand (QS). The ExSh component consisted of (i) large-diameter particles (3-6 mm), (ii) small-diameter particles (1-3 mm), or (iii) a 50:50 mixture (v/v) of the two. The basic blends were mixed with 0, 10, and 20% sphagnum peat moss (v/v) and 0, 10, and 20% natural zeolites (v/v) and placed in 15-cm-diameter pots in a greenhouse. Bermudagrass plugs were planted in each pot. The addition of sphagnum peat moss to the basic ExSh/QS blend increased bermudagrass growth and improved plant response to added fertilizer. Zeolites had no significant effect on plant growth in the absence of sphagnum peat moss. Growing mediums that contained 10 to 20% sphagnum peat moss and 10 to 20% zeolites consistently produced more bermudagrass biomass than the unamended ExSh/QS mixture. Changing the ratio of small- to large-diameter ExSh in the basic medium did not affect bermudagrass yield. Very low amounts of Cd, Cu, Pb, and Zn were recovered in leachate after the addition of 10 mg metal per pot, suggesting that most heavy metals (>99%) were retained in the growing mediums. Zeolites reduced the amount of Cd and Pb in leachate water, but not Cu or Zn.     

Microbial response to heavy metal-polluted soils: community analysis from phospholipid-linked fatty acids and ester-linked fatty acids extracts

Heavy metal pollution of soil is of concern for human health and ecosystem function. The soil microbial community should be a sensitive indicator of metal contamination effects on bioavailability and biogeochemical processes. Simple methods are needed to determine the degree of in situ pollution and effectiveness of remediating metal-contaminated soils. Currently, phospholipid-linked fatty acids (PLFAs) are preferred for microbial profiling but this method is time consuming, whereas direct soil extraction and transesterification of total ester-linked fatty acids (ELFAs) is attractive because of its simplicity. The 1998 mining acid-metal spill of >4000 ha in the Guadiamar watershed (southwestern Spain) provided a unique opportunity to study these two microbial lipid profiling methods. Replicated treatments were set up as nonpolluted, heavy metal polluted and reclaimed, and polluted soils. Inferences from whole community-diversity analysis and correlations of individual fatty acids with metals suggested Cu, Cd, and Zn were the most important in affecting microbial community structure, along with pH. The microbial stress marker, monounsaturated fatty acids, was significantly lower for reclaimed and polluted soil over nonpolluted soils for both PLFA and ELFA extraction. Another stress marker, the monounsaturated to saturated fatty acids ratio, only showed this for the PLFA. The general fungal marker (18:2omega6c), the arbuscule mycorrhizae marker (16:1omega5c), and iso- and anteiso-branched PLFAs (gram positive bacteria) were suppressed with increasing pollution whereas 17:0cy (gram negative bacteria) increased with metal pollution. For both extraction methods, richness and diversity were greater in nonpolluted soils and lowest in polluted soils. The ELFA method was sensitive for reflecting metal pollution on microbial communities and could be suitable for routine use in ecological monitoring and risk assessment programs because of its simplicity and reproducibility.     

Assessment of biomass and lipid productivity and biodiesel quality of an indigenous microalga Chlorella sorokiniana MIC-G5

Generation of biodiesel from microalgae has been extensively investigated; however, its quality is often not suitable for use as fuel. Our investigation involved the evaluation of biodiesel quality using a native isolate Chlorella sorokiniana MIC-G5, as specified by American Society for Testing and Materials (ASTM), after transesterification of lipids with methanol, in the presence of sodium methoxide. Total quantity of lipids extracted from dry biomass, of approximately 410–450 mg g^?1 was characterized using FTIR and ¹H NMR. After transesterification, the total saturated and unsaturated fatty acid methyl esters (FAMEs) were 43% and 57%, respectively. The major FAMEs present in the biodiesel were methyl palmitate (C16:0), methyl oleate (C18:1), and methyl linoleate (C18:2), and the ¹H NMR spectra matched with criteria prescribed for high-quality biodiesel. The biodiesel exhibited a density of 0.873 g cm^–3, viscosity of 3.418 mm² s^?1, cetane number (CN) of 57.85, high heating value (HHV) of 40.25, iodine value of 71.823 g I₂ 100 g^?1, degree of unsaturation (DU) of 58%, and a cold filter plugging point (CFPP) of –5.22°C. Critical fuel parameters, including oxidation stability, CN, HHV, iodine value, flash point, cloud point, pour point, density, and viscosity were in accordance with the methyl ester composition and structural configuration. Hence, C. sorokiniana can be a promising feedstock for biodiesel generation.     

The use of tailor-made acidic deep eutectic solvents for preparation of quercetin-enriched extracts from onion solid wastes

The current examination dealt with the development of a methodology to produce quercetin, a multifunctional bio-flavonoid, by designing task-specific, highly acidic deep eutectic solvents, based on glycerol and natural organic acids. The purpose was to achieve a simultaneous hydrolysis of spiraeoside, the major quercetin glycoconjugate occurring in onion solid wastes, and quercetin extraction. After an initial performance screening, the combination of glycerol/oxalic acid was identified as the highest-performing system, and further investigation showed that the most efficacious molar ratio was glycerol/oxalic acid 3:1. Further study of hydrolysis/extractions conditions suggested 30 min, at 130°C, to be the best operating conditions, giving the highest yield of 19.65 mg quercetin per grams of dry mass. The extract obtained under these conditions displayed significantly enhanced antiradical activity, compared to control extracts prepared with water or aqueous ethanol. On the other hand, results on the ferric-reducing power were rather contradictory. It is proposed that such a methodology may be implemented to valorize onion solid wastes, for the production of extracts significantly enriched in quercetin, with increased antiradical properties.     

Field-scale remediation of a metolachlor-contaminated spill site using zerovalent iron

Pesticide spills are common occurrences at agricultural cooperatives and farmsteads. When inadvertent spills occur, chemicals normally beneficial can become point sources of ground and surface water contamination. We report results from a field trial where approximately 765 m3 of soil from a metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl) acetamide] spill site was treated with zerovalent iron (Fe0). Preliminary laboratory experiments confirmed metolachlor dechlorination by Fe0 in aqueous solution and that this process could be accelerated by adding appropriate proportions of Al2(SO4)3 or acetic acid (CH3COOH). The field project was initiated by moving the stockpiled, contaminated soil into windrows using common earth-moving equipment. The soil was then mixed with water (0.35-0.40 kg H2O kg(-1)) and various combinations of 5% Fe0 (w/w),2% Al2(SO4)3 (w/w), and 0.5% acetic acid (v/w). Windrows were covered with clear plastic and incubated without additional mixing for 90 d. Approximately every 14 d, the plastic sheeting was removed for soil sampling and the surface of the windrows rewetted. Metolachlor concentrations were significantly reduced and varied among treatments. The addition of Fe0 alone decreased metolachlor concentration from 1789 to 504 mg kg(-1) within 90 d, whereas adding Fe0 with Al2(SO4)3 and CH3COOH decreased the concentration from 1402 to 13 mg kg(-1). These results provide evidence that zerovalent iron can be used for on-site, field-scale treatment of pesticide-contaminated soil.     

Recovery of phosphate from calcinated bone by dissolution in hydrochloric acid solutions

In this study, the optimum conditions of dissolution of calcinated bone in HCl solutions with different concentrations are investigated. Recovery of phosphate from calcinated bone by dissolution with hydrochloric acid solutions was investigated in a batch reactor, it was observed that a 32% hydrochloric acid solution can dissolve the calcinated bone effectively. Using the Taguchi fractional design method, it was found that the optimum process conditions, at which 67.2% P₂O₅ dissolution was reached, were as follows: Reaction temperature: 318 K, solid-to-liquid ratio: 1/5 (g ml⁻¹), acid concentrations:32 (% w/v), stirring speed:400 min⁻¹ and reaction time: 60 min.