An updated review on advancement in fermentative production strategies for biobutanol using Clostridium spp.

A significant concern of our fuel-dependent era is the unceasing exhaustion of petroleum fuel supplies. In parallel to this, environmental issues such as the greenhouse effect, change in global climate, and increasing global temperature must be addressed on a priority basis. Biobutanol, which has fuel characteristics comparable to gasoline, has attracted global attention as a viable green fuel alternative among the many biofuel alternatives. Renewable biomass could be used for the sustainable production of biobutanol by the acetone-butanol-ethanol (ABE) pathway. Non-extinguishable resources, such as algal and lignocellulosic biomass, and starch are some of the most commonly used feedstock for fermentative production of biobutanol, and each has its particular set of advantages. Clostridium, a gram-positive endospore-forming bacterium that can produce a range of compounds, along with n-butanol is traditionally known for its biobutanol production capabilities. Clostridium fermentation produces biobased n-butanol through ABE fermentation. However, low butanol titer, a lack of suitable feedstock, and product inhibition are the primary difficulties in biobutanol synthesis. Critical issues that are essential for sustainable production of biobutanol include (i) developing high butanol titer producing strains utilizing genetic and metabolic engineering approaches, (ii) renewable biomass that could be used for biobutanol production at a larger scale, and (iii) addressing the limits of traditional batch fermentation by integrated bioprocessing technologies with effective product recovery procedures that have increased the efficiency of biobutanol synthesis. Our paper reviews the current progress in all three aspects of butanol production and presents recent data on current practices in fermentative biobutanol production technology.

     

Degradation of phenolic and chloroaromatic compounds by Coprinus spp

Three species of Coprinus: C. sp, C. cinereus and C. micaceus were compared on solid media for some aspects of their physiological behaviour and cultural requirements (temperature, pH, substrate). Constitutive extracellular enzymatic activities were also determined. The Coprinus spp. exhibited different physiological and cultural features. Cultures of the 3 Coprinus species in synthetic liquid medium showed an efficient degradation of phenolic lignin model compounds (catechol, ferulic acid, guaiacol, phenol, protocatechuic acid syringic acid and vanillic acid) and pentachloronitrobenzene, while pentachlorophenol was not metabolized after 5 days perhaps because of a strong adsorption on mycelial biomass. It was suggested that phenoloxidases were not necessarily required for the metabolization of these compounds. Coprinus species may share a common degrading system for monomeric phenolic and chloroaromatic compounds.     

Formation of toxic species and precursors of PCDD/F in thermal decomposition of alpha-cypermethrin

This article examines the thermal decomposition of alpha-cypermethrin, one of the most common pyrethroid pesticides. The objective was to identify its decomposition pathways and to gain an understanding into the formation of toxic species in the environment, including those that may behave in combustion systems, especially in fires in the environment, as precursors for PCDD/F (polychlorinated dibenzo-p-dioxins and dibenzofurans). The experiments were conducted under non-oxidative conditions using a tubular reactor housed in a three-zone heating furnace and operated with a dilute stream of alpha-cypermethrin in 99.999% nitrogen. The condensable products were identified and quantitated, after being collected in a cold solvent trap and in an activated charcoal cartridge. The study revealed the formation of pollutants including precursors of toxic PCDD/F such as diphenyl ether and phenol. It was also found that the decomposition of alpha-cypermethrin involved parallel pathways of an unusual vinylcyclopropane rearrangement-cum-aromatisation reaction transforming alpha-cypermethrin and a rupture of the C(O)OC(CN) linkage. The former is similar to that occurring in the decomposition of permethrin pesticide, whereas the latter constitutes a newly discovered channel for the formation of pollutants. Density functional theory (DFT) calculations allowed us to attribute the occurrence of the second pathway to the effect of the cyanide group in significantly weakening the OC bond.     

CO2 sequestration by propagation of the fast-growing Azolla spp.

Environmental Science and Pollution Research - Azolla is a group of aquatic floating plants that can achieve very high growth rates compared to other aquatic macrophytes, with a doubling time of...     

Formation of polycyclic aromatic hydrocarbons by ionizing radiations

Gaseous o-terphenyl, 1-phenylnaphthalene, and 9-phenylanthracene were submitted to gamma rays. The yields of cyclization products, polycyclic aromatic hydrocarbons, show that at least one twentieth of the intermediates formed undergo intramolecular reaction.     

混凝强化形成好氧颗粒污泥

为了缩短好氧颗粒污泥形成的时间,通过在颗粒污泥形成初期投加混凝剂的方式,研究强化造粒条件下颗粒污泥的形成过程及其特性。结果发现,投加混凝剂后,反应器在第8天出现了颗粒污泥,并在第25天时实现完全颗粒化,比未加混凝剂反应器颗粒形成的时间缩短了2 d,完全颗粒化时间缩短了10 d。强化造粒条件下形成的颗粒污泥,颗粒强度、比重分别为99.03%和1.1892,分别比对照高出3.28%和0.1539。可以看出,在混凝强化造粒条件下培养出的颗粒污泥,与常规方法相比具有颗粒化进程快,颗粒强度大,比重大等优点。     

Formation of cyanoarenes by combustion of nitrogen containing polymers

The formation of cyano group-containing polycyclic aromatic compounds (cyanoarenes) and nitrogen-containing aromatic compounds (azaarenes) during combustion processes is described. The experiments were carried out by combustion of nitrogen containing polymers (nylon 6, polyacrylonitrile and polyamide) in a combustion chamber ,to simulate combustion processes of waste incineration plants. The result from experiments, in which only one nitrogen containing polymer was burnt, showed the formation of several cyanoarenes. We conclude that during combustion processes in which hydrogen cyanide is formed, air pollution by cyanoarenes and azaarenes (in ppb or ppm concentrations) may occur.     

Biodegradation capacity of tributyltin by two Chlorella species

Two microalgal species, Chlorella vulgaris and Chlorella sp., which showed high tributyltin (TBT) tolerant ability were investigated for their capabilities in degrading TBT at sublethal concentration. The distribution of TBT and its degraded products dibutyltin (DBT) and monobutyltin (MBT) in the incubation medium, extracellular surface and intracellular fraction were monitored during an exposure period of 14 days. Results showed that biosorption of TBT by the algal cell wall was the major mechanism in reducing 40% of the initial TBT from the medium in the first 2 days. The half-life of TBT incubated with C. vulgaris was 60 h while that of Chlorella sp. was 80 h. The occurrence of DBT at Day 1 in the culture medium provided direct evidence to the biodegradation of TBT by both Chlorella species. At the end of the experimental period, 27 and 41% of the original TBT were recovered as DBT and MBT in cultures of C. vulgaris, respectively. In contrast, DBT appeared to be the only degradation product of Chlorella sp. and only 26% of the original TBT was transformed to DBT. Despite the same genus, TBT was debutylated to a greater extent to MBT by C. vulgaris, while DBT was the end degradation product by Chlorella sp. The capability of such debutylating process therefore accounted for the higher tolerant ability of C. vulgaris than Chlorella sp.     

Population dynamics of Digitaria spp submitted to selection pressure by herbicides in sugarcane crop

The objective of this research was to study population dynamics of the weed crabgrass, genus Digitaria, submitted to selection pressure by herbicides currently applied in sugarcane crops in Brazil. In the first experiment two crabgrass species (Digitaria nuda and Digitaria ciliaris) and eight herbicide treatments applied in preemergence were used, and control percentage was evaluated at 7, 14, and 21 days after herbicide application (DAA). In the second experiment the level of tolerance through dose-response curve was determined for the species D. nuda and D. ciliaris, to the herbicides imazapyr, tebuthiuron, ametryne, and metribuzin. All the herbicides studied were efficient in controlling D. ciliaris, however, for D. nuda the best results were obtained only with ametryne, metribuzin, and isoxaflutole. The relation (T/S) between the rate required to reduce plant dry biomass (GR50) at 21 DAA of D. nuda and D. ciliaris was 16 for imazapyr and 6.3 for tebuthiuron, showing differential susceptibility of species; however for ametryne the rate T/S of 1.1 showed that D. nuda was not tolerant to this herbicide. For metribuzin, at 1.92 kg a.i. ha(-1), reduction of dry biomass was 80 and 90% to D. nuda and D. ciliaris, respectively. Even being controlled by metribuzin, D. nuda presented a higher level of tolerance to this herbicide, what was confirmed by the relationship T/S 14.4. As general conclusion of the research, it can be stated that the species D. nuda is more tolerant to ALS inhibiting herbicides and substituted urea, when compared with D. ciliaris; probably, D. nuda was selected by repetitive use of these herbicides.     

Formation of 9,10-phenanthrenequinone by atmospheric gas-phase reactions of phenanthrene

Phenanthrene is a 3-ring polycyclic aromatic hydrocarbon which exists mainly in the gas-phase in the atmosphere. Recent concern over the presence of 9,10-phenanthrenequinone in ambient particles led us to study the products of the gas-phase reactions of phenanthrene with hydroxyl radicals, nitrate radicals and ozone. The formation yields of 9,10-phenanthrenequinone were measured to be ∼3%, 33±9%, and ∼2% from the OH radical, NO₃ radical and O₃ reactions, respectively. Calculations suggest that daytime OH radical-initiated and nighttime NO₃ radical-initiated reactions of gas-phase phenanthrene may be significant sources of 9,10-phenanthrenequinone in ambient atmospheres. In contrast, the ozone reaction with phenanthrene is unlikely to contribute significantly to ambient 9,10-phenanthrenequinone.     

Formation of chloroform by aqueous chlorination of organic compounds.

Thirty organic compounds were selected to investigate their chloroform formation characteristics during chlorination with sodium hypochlorite at pH-values 7.0 and 8.0. These experiments were conducted under conditions similar to those applied on the chlorination of raw water. The results indicated that the chloroform concentrations occurred by the all tested compounds was in the ppm range. The maximum levels of chloroform (11-13 mg/l) were determined during the reaction of resorcinol and phloroglucinol at pH-value 8.0.     

Formation of chlorodibenzofurans by thermal decomposition of vinylidene chloride polymer

This is the first reported measurement of four kinds of chlorodibenzofurans formed in the pyrolytic decomposition of vinylidene chloride, a polymer used as wrapping film. 3-Chloro isomer was the most abundant among four monochlorodibenzofurans.     

Formation of PCDDs and PCDFs by the chlorination of water

Two samples of tab water and double distilled water were chlorinated using chlorine gas. A series of PCDFs could be identified from these experiments, however no PCDDs could be found. The two water samples gave very similar isomeric patterns ( . . tetra-CDFs), however the congener profile (Cl₄ --- Cl₈) was different. These experiments indicate that all products formed by chlorination reactions are potentially contaminated by PCDFs by a specific “chlorine pattern”.     

Kinetics of phenol and chlorophenol utilization by Acinetobacter species

Although microbial transformations via cometabolism have been widely observed, the few available kinetic models of cometabolism have not adequately addressed the case of inhibition from both the growth and nongrowth substrates. The present study investigated the degradation kinetics of self-inhibitory growth (phenol) and nongrowth (4-chlorophenol, 4-CP) substrates, present individually and in combination. Specifically, batch experiments were performed using an Acinetobacter isolate growing on phenol alone and with 4-CP present. In addition, batch experiments were also performed to evaluate the transformation of 4-CP by resting, phenol-induced Acinetobacter cultures. The Haldane kinetic model adequately predicted the biodegradation of phenol alone, although a slight discrepancy was noted in cases of higher initial phenol concentrations. Similarly, a Haldane model for substrate utilization was also able to describe the trends in 4-CP transformation by the resting cell cultures. The 4-CP transformation by the Acinetobacter species growing on phenol was modeled using a competitive kinetic model of cometabolism, which included growth and nongrowth substrate inhibition and cross-inhibition terms. Excellent agreement was obtained between the model predictions using experimentally estimated parameter values and the experimental data for the synchronous disappearance of phenol and 4-CP.     

Biodegradation pathways of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) by Clostridium acetobutylicum cell-free extract

Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), a military high explosive, is becoming an increasingly important pollutant in the US. The cleanup of RDX-contaminated soil and groundwater has been a serious challenge due to its recalcitrance in the environment. This study was conducted to determine the biodegradation kinetics of RDX by crude cell extract of Clostridium acetobutylicum (ATCC 824), and to examine whether this bacterium will carry out reductive transformation pathways similar to the transformation of 2,4,6-trinitrotoluene (TNT), 2,4- and 2,6-dinitrotoluenes (DNTs) we have reported previously. Batch studies on the anaerobic transformation of RDX were conducted in serum bottles with U-ring-14C-RDX. RDX and its transformation products were quantified by HPLC and qualified by LC/ MS interfaced to two soft ionization techniques--an atmospheric pressure ionization and an electron spray ionization (API-ES). Results demonstrated that C. acetobutylicum is capable of transforming RDX with H2 as the electron donor. The transformation followed a zero-order kinetics and the rates increased with increasing H2. RDX was transformed into several polar intermediates that could not be separated by reverse-phase HPLC and its molecular ions were unstable under the condition of commonly used electron impact detector. Using a polar and water immiscible solvent (ethyl acetate) and the softer MS ionization techniques, mass spectroscopy detected the presence of several RDX derivatives including mononitroso-, monohydroxylamino-, mononitrosomonohydroxylamino-, monoamino-, diamino-, and triamino-compounds. The presence of hydroxylamino compounds is analogous to the transformation of TNT and DNTs we elucidated previously.     

Formation of aromatic chlorinated compounds catalyzed by copper and iron

This study shows the catalyzing effects of iron and copper on the formation of chlorinated compounds such as chlorobenzenes (ClBzs), chlorophenols (CIPhs), polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). Both total concentrations and congener distributions have been studied. The parameters and conditions varied during the combustion tests were the complete and incomplete combustion and the metal and chlorine addition. The incomplete combustion promoted the formation of organic chlorinated compounds in flue gas particles. Highly chlorinated congeners of PCDD/F were dominant in the flue gas particles, whereas the importance of lower chlorinated congener were increased in the gas phase. In the complete combustion conditions the concentrations of PCDD/Fs increased when the degree of chlorination were high, nevertheless the concentrations of tetra and penta PCDD/Fs were higher in the gas phase than the concentrations in the fly ash particles. Organic chlorine promoted the formation of chlorinated compounds more effectively than inorganic chlorine, which instead promoted the formation of PCDD/Fs in the gas phase, especially with copper catalyst. Different concentration levels of chlorinated compounds were observed in the gas phase and in particles when the chlorine source and combustion conditions were varied from incomplete to optimum conditions. Both copper and iron seem to have a catalytic effect on PCDD/F formation.     

Formation of bound residues by naphthalene and cis-naphthalene-1,2-dihydrodiol

The formation of bound residues by naphthalene and its metabolite, cis-naphthalene-1,2-dihydrodiol, in a sediment (1% OC), a silty loam soil (2.9% OC) and a peat (26% OC) was examined. The experiments were carried out under both sterile and nonsterile conditions for up to 35 days. The samples containing bound contaminant were hydrolyzed at an alkaline pH and fractionated using 3,000 and 500 Da molecular weight cutoff ultrafiltration membranes in series. The results for all the geosorbents examined showed that bound residue formation is low for naphthalene and between 5 and 20 times higher for the metabolite. The amount of bound residues released by hydrolysis was higher for the metabolite than for the parent compound for all the samples. The molecular weight distribution of bound radioactivity after hydrolysis showed binding to the high molecular weight components of the sediment organic matter and to the low molecular weight components for soil and peat organic matter when incubated with cis-naphthalene-1,2-dihydrodiol. Experiments performed with naphthalene-UL-(14)C showed larger amounts of bound residue found than in experiments with naphthalene-1-(14)C.     

The definition of species richness used by species sensitivity distributions approximates observed effects of salinity on stream macroinvertebrates

The risk of chemicals for ecological communities is often forecast with species sensitivity distributions (SSDs) which are used to predict the concentration which will protect p% of species (PC_p value). However, at the PC_p value, species richness in nature would not necessary be p% less than at uncontaminated sites. The definition of species richness inherent to SSDs (contaminant category richness) contrasts with species richness typically measured in most field studies (point richness). We determine, for salinity in eastern Australia, whether these definitions of stream macroinvertebrate species richness are commensurable. There were strong relationships (r² ≥ 0.87) between mean point species, family and Ephemeroptera, Trichoptera and Plecoptera species richness and their respective contamination category richness. Despite differences in the definition of richness used by SSDs and field biomonitoring, their results in terms of relative species loss from salinity in south-east Australia are similar. We conclude that in our system both definitions are commensurable.