Elucidation of crude siderophore extracts from supernatants of Pseudomonas sp. ZnCd2003 cultivated in nutrient broth supplemented with Zn, Cd, and Zn plus Cd.

This research aimed to study siderophores secreted from Pseudomonas sp. PDMZnCd2003, a Zn/Cd tolerant bacterium. The effects of Zn and/or Cd stress were examined in nutrient broth to achieve the actual environmental conditions. Acid and alkali supernatants and liquid-liquid extraction with ethyl acetate and butanol were carried out to obtain crude extracts containing different amounts of the metals. The bacterial growth, UV-visible spectra of the supernatants and siderophore production indicated that the production of siderophores tended to be linked to primary metabolites. Pyocyanin was produced in all treatments, while pyoverdine was induced by stress from the metals, especially Cd. FT-IR spectra showed C=O groups and sulfur functional groups that were involved in binding with the metals. LC-MS revealed that pyocyanin, 1-hydroxy phenazine, pyoverdine, and pyochelin were present in the crude extracts. S K-edge XANES spectra showed that the main sulfur species in the extracts were the reduced forms of sulfide, thiol, and disulfide, and their oxidation states were affected by coordination with Zn and/or Cd. In addition, Zn K-edge EXAFS spectra and Cd K-edge EXAFS spectra presented Zn-O and Cd-O as coordination in the first shell, in case the extracts contained less metal. Although the mix O/S ligands had chelation bonding with Zn and Cd in the other extracts. For the role of S groups in pyochelin binding with the metals, this was the first report. The results of these experiments could be extended to Pseudomonas that respond to metal contaminated environments.

Zinc- and cadmium-tolerant endophytic bacteria from Murdannia spectabilis (Kurz) Faden. studied for plant growth-promoting properties, in vitro inoculation, and antagonism.

This research aims to isolate and identify Zn- and Cd-tolerant endophytic bacteria from Murdannia spectabilis, identify their properties with and without Zn and Cd stress, and to investigate the effect of bacterial inoculation in an in vitro system. Twenty-four isolates could survive on trypticase soya agar (TSA) supplemented with Zn (250-500 mg L-1) and/or Cd (20-50 mg L-1) that belonged to the genera Bacillus, Pantoea, Microbacterium, Curtobacterium, Chryseobacterium, Cupriavidus, Siphonobacter, and Pseudomonas. Each strain had different indole-3-acetic acid (IAA), 1-aminocyclopropane-1-carboxylate (ACC) deaminase and siderophore production, nitrogen fixation, phosphate solubilization, and lignocellulosic enzyme characteristics. Cupriavidus plantarum MDR5 and Chryseobacterium sp. MDR7 were selected for inoculation into plantlets that were already occupied by Curtobacterium sp. TMIL due to them have a high tolerance for Zn and Cd while showing no pathogenicity. As determined via an in vitro system, Cupriavidus plantarum MDR5 remained in the plants to a greater extent than Chryseobacterium sp. MDR7, while Curtobacterium sp. TMIL was the dominant species. The Zn plus Cd treatment supported the persistence of Cupriavidus plantarum MDR5. Dual and mixed cultivation showed no antagonistic effects between the endophytes. Although the plant growth and Zn/Cd accumulation were not significantly affected by the Zn-/Cd-tolerant endophytes, the inoculation did not weaken the plants. Therefore, Cupriavidus plantarum MDR5 could be applied in a bioaugmentation process.

Potentially toxic elements to maize in agricultural soils-microbial approach of rhizospheric and bulk soils and phytoaccumulation.

Maize fields near Mae Tao Creek in Pha Te Village, Tak Province, Thailand are contaminated with Zn, Cd, and Pb. This research studied the interaction between levels of the metals contaminating the soil and maize development, heavy metal accumulation in the seeds, and the soil bacterial community structure. Our field experiment was carried out in five plots with metal contents that gradually decreased from a high level near the creek to a lower level further into the land: Zn 380-4883 mg kg-1, Cd 6-85 mg kg-1, and Pb 34-154 mg kg-1. Cultivation and isolation on nutrient agar (NA) was utilized to study the culturable bacterial community, and polymerase chain reaction denaturing gradient gel electrophoresis (PCR-DGGE) was utilized for the unculturable bacterial communities. All statistical analyses clearly indicated that rainfall and irrigation were the main factors affecting total Zn concentration and bioavailable Zn, Cd, and Pb in the field. The variation in the contents of the heavy metals was weakly correlated with the culturable bacterial community indices (Shannon-Wiener, evenness and richness), but the contents resulted in a difference in the overall diversity of the bacteria in the soil. The richness, numbers of culturable rhizobacteria, and maize growth stage significantly affected the amount of Zn and Cd that accumulated in the roots. In addition, maize accumulated a high level of Zn in the seeds, while the low contents of Cd and Pb in the seeds were below our limit of detection. The results obtained could be informative for the management of maize cultivation in the area.

Phenolic compounds responding to zinc and/or cadmium treatments in Gynura pseudochina (L.) DC. extracts and biomass.

Gynura pseudochina (L.) DC. is a Zn/Cd hyperaccumulative plant. In an in vivo system under controlled plant age, this research reveals that phenolic compounds and lignification play beneficial roles in protecting G. pseudochina from exposure to an excess of Zn and/or Cd, and Zn reduces Cd toxicity under the dual treatments. The total phenolic content (TPC), total flavonoid content (TFC), and half-maximal inhibitory concentration (IC50) values correspond to the metal dose-response curves. Liquid chromatography-electrospray ionization-quadrupole time of flight-tandem mass spectrometry (LC-ESI-QTOF-MS/MS) is used to characterize phenolic compounds and their glycosides, which could play roles in antioxidant activities and in the esterification of the cell wall, especially derivatives of p-coumaric and caffeic acid. Confocal laser scanning microscopy (CLSM) and micro X-ray fluorescence (µ-XRF) imaging revealed that the accumulation of Zn and Cd in the cell wall involves flavonoid compounds. Low extractable pools of Cd and Zn in the leaf extracts indicate that these elements are tightly bound to the plant biomass structures. The bulk X-ray absorption near edge structure (XANES) spectra indicate that Zn2+ and Cd2+ dominate with O and S ligands, which could be provided by cell walls, phenolic compounds, and sulphur protein. Consequently, the benefit of these results is to support the growth of G. pseudochina for phytoremediation in a Zn- and/or Cd-contaminated site.

Isolation of the Entomopathogenic Fungal Strain Cod-MK1201 from a Cicada Nymph and Assessment of Its Antibacterial Activities.

The entomopathogenic fungus Cod-MK1201 was isolated from a dead cicada nymph. Three regions of ribosomal nuclear DNA, the internal transcribed spacers of nuclear ribosomal DNA repeats (ITS), the partial small subunit of rDNA (nrSSU) , and the partial large subunit of rDNA (nrLSU), and two protein-coding regions, the elongation factor 1α (EF-1α), and the largest subunit of the RNA polymerase II (rpb1) gene, were sequenced and used for fungal identification. The phylogenetic analysis of the ITS and the combined data set of the five genes indicated that the fungal isolate Cod-MK1201 is a new strain of Cordyceps sp. that is closely related to Cordyceps nipponica and C. kanzashiana. Crude extracts of mycelium-cultured Cod-MK1201 were obtained using distilled water and 50% (v/v) ethanol, and the antibacterial activity of each was determined. Both extracts had activity against Gram-positive and Gram-negative bacteria, but the ethanol extract was the more potent of the two. The antibacterial activity of the protein fractions of these extracts was also determined. The protein fraction from the ethanol extract was more antibacterial than the protein fraction from the aqueous extract. Three antibacterial constituents including adenosine, the total phenolic content (TPC), and the total flavonoid content (TFC) was also determined. The results showed that the adenosine content, the TPC, and the TFC of the ethanol extract were more active than those of the aqueous extract. Moreover, synergism was detected between these antibacterial constituents. In conclusion, the entomopathogenic fungal isolate Cod-MK1201 represents a natural source of antibacterial agents.

Application of 'waste' wood-shaving bottom ash for adsorption of azo reactive dye.

The utilization of wood-shaving bottom ash (WBA) for the removal of Red Reactive 141 (RR141), an azo reactive dye, was investigated. WBA/H(2)O and WBA/H(2)SO(4) were made by treating WBA with water and 0.1M H(2)SO(4), respectively, to increase adsorption capacity. Adsorption of RR141 from reactive dye solution (RDS) and reactive dye wastewater (RDW) by WBA/H(2)O and WBA/H(2)SO(4) involved the BET surface area and pore size diameter. Properties of adsorbents, effect of contact time, initial pH of solution, dissolved metals and elution studies indicated that the decolorisation mechanism involved both chemical adsorption and precipitation with calcium ions. In addition, the WBA/H(2)SO(4) surface might contain sulphate-cation complexes that were specific to enhancing dye adsorption from RDW. The adsorption isotherm had a best fit by the Freundlich model. Freundlich parameters showed that WBA/H(2)O used more heterogeneous surface than WBA/H(2)SO(4) and activated carbon for RDW adsorption. A thermodynamic study indicated that RDW adsorption was an endothermic process. The maximum dye adsorption capacities of WBA/H(2)O, WBA/H(2)SO(4) and activated carbon obtained from a Langmuir model at 30 degrees C were 24.3, 29.9, and 41.5mgl(-1), respectively. In addition, WBA/H(2)O and WBA/H(2)SO(4) could reduce colour and high chemical oxygen demand (COD) of real textile wastewater. According to the difficulty in the elution study, it was an environmentally safe disposal of this waste. Therefore, WBA, a waste from combustion of wood shavings, was suitable to be used as an effective adsorbent for azo reactive dye removal.

Mechanism of Cr(VI) adsorption by coir pith studied by ESR and adsorption kinetic.

The oxidation state of chromium in coir pith after Cr(VI) adsorption from aqueous solution was investigated using electron spin resonance (ESR). To elucidate the mechanism of chromium adsorption on coir pith, the adsorption studies of Cr(VI) onto lignin, alpha-cellulose and holocellulose extracted from coir pith were also studied. ESR signals of Cr(V) and Cr(III) were observed in coir pith adsorbed Cr(VI) at solution pH 2, while ESR spectra of lignin extracted from coir pith revealed only the Cr(III) signal. In addition, ESR signal of Cr(V) was observed in alpha-cellulose and holocellulose extracted from coir pith adsorbed Cr(VI). These results confirmed that lignin in coir pith reduced Cr(VI) to Cr(III) while alpha-cellulose and holocellulose extracted from coir pith reduced Cr(VI) to Cr(V). The Cr(V) signal exhibited in ESR of alpha-cellulose and holocellulose might be bound with glucose in cellulose part of coir pith. In addition, xylose which is main in pentosan part of coir pith, indicated that it is involved in form complex with Cr(V) on coir pith. The adsorption kinetic of Cr(VI) from aqueous solution on coir pith was also investigated and described well with pseudo second order model. ESR and desorption experiments confirmed that Cr(VI), Cr(V) and Cr(III), exist in coir pith after Cr(VI) adsorption. The desorption data indicated that the percentage of Cr(VI), Cr(V) and Cr(III) in coir pith were 15.63%, 12.89% and 71.48%, respectively.

Column study of chromium(VI) adsorption from electroplating industry by coconut coir pith.

The removal of Cr(VI) from electroplating wastewater by coir pith was investigated in a fixed-bed column. The experiments were conducted to study the effect of important parameters such as bed depth (40-60cm) and flow rate (10-30ml min(-1)). At 0.05 C(t)/C(0), the breakthrough volume increased as flow rate decreased or a bed depth increased due to an increase in empty bed contact time (EBCT). The bed depth service time model (BDST) fit well with the experimental data in the initial region of the breakthrough curve, while the simulation of the whole curve using non-linear regression analysis was effective using the Thomas model. The adsorption capacity estimated from the BDST model was reduced with increasing flow rate, which was 16.40mg cm(-3) or 137.91mg Cr(VI)g(-1) coir pith for the flow rates of 10ml min(-1) and 14.05mg cm(-3) or 118.20mg Cr(VI)g(-1) coir pith for the flow rates of 30ml min(-1). At the highest bed depth (60cm) and the lowest flow rate (10mlmin(-1)), the maximum adsorption reached 201.47mg Cr(VI)g(-1) adsorbent according to the Thomas model. The column was regenerated by eluting chromium using 2M HNO(3) after adsorption studies. The desorption of Cr(III) in each of three cycles was about 67-70%. The desorption of Cr(III) in each cycle did not reach 100% due to the fact that Cr(V) was present through the reduction of Cr(VI), and was still in coir pith, possibly bound to glucose in the cellulose part of coir pith. Therefore, the Cr(V) complex cannot be desorbed in solution. The evidence of Cr(V) signal was observed in coir pith, alpha-cellulose and holocellulose extracted from coir pith using electron spin resonance (ESR).

Chromium removal from electroplating wastewater by coir pith.

Coir pith is a by-product from padding used in mattress factories. It contains a high amount of lignin. Therefore, this study investigated the use of coir pith in the removal of hexavalent chromium from electroplating wastewater by varying the parameters, such as the system pH, contact time, adsorbent dosage, and temperature. The maximum removal (99.99%) was obtained at 2% (w/v) dosage, particle size <75microm, at initial Cr(VI) 1647mgl(-1), system pH 2, and an equilibrium time of 18h. The adsorption isotherm of coir pith fitted reasonably well with the Langmuir model. The maximum Cr(VI) adsorption capacity of coir pith at 15, 30, 45 and 60 degrees C was 138.04, 197.23, 262.89 and 317.65mgCr(VI)g(-1) coir pith, respectively. Thermodynamic parameters indicated an endothermic process and the adsorption process was favored at high temperature. Desorption studies of Cr(VI) on coir pith and X-ray absorption near edge structure (XANES) suggested that most of the chromium bound on the coir pith was in Cr(III) form due to the fact that the toxic Cr(VI) adsorbed on the coir pith by electrostatic attraction was easily reduced to less toxic Cr(III). Fourier transform infrared (FT-IR) spectrometry analysis indicated that the carbonyl (CO) groups and methoxy (O-CH(3)) groups from the lignin structure in coir pith may be involved in the mechanism of chromium adsorption. The reduced Cr(III) on the coir pith surface may be bound with CO groups and O-CH(3) groups through coordinate covalent bonding in which a lone pair of electrons in the oxygen atoms of the methoxy and carbonyl groups can be donated to form a shared bond with Cr(III).

Adsorption of Reactive Red 141 from wastewater onto modified chitin.

This research involved the adsorption of synthetic reactive dye wastewater (SRDW) by chitin modified by sodium hypochlorite and original chitin in batch experiments. The comparison of maximum adsorption capacity used the Langmuir model to describe SRDW adsorption onto chitin and modified chitin under a system pH of 11.0. Maximum dye adsorption by chitin increased from 133mgg(-1) to 167mgg(-1) at temperatures of 30-60 degrees C, respectively. For modified chitin, the capacity decreased from 124mgg(-1) to 59mgg(-1) when the temperature increased from 30 degrees C to 60 degrees C, respectively. Both Na(2)SO(4) and Na(2)CO(3) increased in dye adsorption. The spectra of attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectrometry confirmed the hydroxyl groups as functional groups of modified chitin, which affected the modification and the SRDW adsorption. The adsorbed dyes were eluted by distilled water and 1M NaOH to confirm the dye adsorption mechanism. Total elution of modified chitin and chitin were 92.76% and 55.29%, respectively. Although modified chitin had a maximum adsorption capacity less than chitin, elution of the dye from modified chitin was easier than chitin. Therefore, modified chitin could be suitable in a column system for dye pre-concentration as well as wastewater minimisation. In addition, the column study showed that modified chitin could be used for more than four cycles of adsorption and elution by distilled water.

Recovery of gold from gold slag by wood shaving fly ash.

Wood shaving fly ash was used as an alternative adsorbent for gold preconcentration from gold slag. The maximum gold adsorption capacity of wood shaving fly ash washed with tap water (WSFW) at 20, 30, 40, and 60 degrees C was 8.68, 7.79, 7.44, and 7.25 mg(Au)/g(adsorbent), respectively, while of activated carbon it was 76.78, 60.95, 56.13, and 51.90 mg(Au)/g(adsorbent), respectively. Deionized water at 100 degrees C could elute gold adsorbed onto WSFW to 71%. The effect of the increasing temperature of water, 30, 60, and 100 degrees C, implied that the adsorption mechanism was mainly physical adsorption. The negative values of enthalpy change (DeltaH) and free energy change (DeltaG) indicated an exothermic and spontaneous process, respectively. The positive values of entropy change (DeltaS) indicated increasing disorder of the system. The advantages of wood shaving fly ash are the purification of gold and the easier recycling of gold from the gold-adsorbed adsorbent.

Adsorption mechanism of synthetic reactive dye wastewater by chitosan.

Chitosan was able to remove the color from synthetic reactive dye wastewater (SRDW) under acidic and caustic conditions. The effect of the initial pH on SRDW indicated that electrostatic interaction occurred between the effective functional groups (amino groups) and the dye under acidic conditions. Moreover, SRDW adsorption under caustic conditions was also affected by the covalent bonding of dye and hydroxyl groups of chitosan. In addition, elution tests confirmed that chemical adsorption occurred under acidic conditions, while both physical and chemical adsorption appeared under caustic conditions. The spectra of attenuated total reflectance Fourier transform infrared spectrometry confirmed the functional groups of chitosan that affected the SRDW adsorption. However, the maximum adsorption capacities of chitosan increased when the temperature increased. The maximum adsorption capacity of chitosan obtained from the Langmuir model was 68, 110, and 156 mg g(-1) under a system pH of 11.0 at 20, 40, and 60 degrees C, respectively. The negative values of enthalpy change (DeltaH), free energy change (DeltaG), and entropy change (DeltaS) indicated an exothermic, spontaneous process and decreasing disorder of the system, respectively. Therefore, the mechanism of SRDW adsorption by chitosan was probably by chemical adsorption for a wide range of pH's and at high temperatures.