Heavy metal resistance and genotypic analysis of metal resistance genes in gram-positive and gram-negative bacteria present in Ni-rich serpentine soil and in the rhizosphere of Alyssum murale

Forty-six bacterial cultures, including one culture collection strain, thirty from the rhizosphere of Alyssum murale and fifteen from Ni-rich soil, were tested for their ability to tolerate arsenate, cadmium, chromium, zinc, mercury, lead, cobalt, copper, and nickel in their growth medium. The resistance patterns, expressed as minimum inhibitory concentrations, for all cultures to the nine different metal ions were surveyed by using the agar dilution method. A large number of the cultures were resistant to Ni (100%), Pb (100%), Zn (100%), Cu (98%), and Co (93%). However, 82, 71, 58 and 47% were sensitive to As, Hg, Cd and Cr(VI), respectively. All cultures had multiple metal-resistant, with heptametal resistance as the major pattern (28.8%). Five of the cultures (about of 11.2% of the total), specifically Arthrobacter rhombi AY509239, Clavibacter xyli AY509235, Microbacterium arabinogalactanolyticum AY509226, Rhizobium mongolense AY509209 and Variovorax paradoxus AY512828 were tolerant to nine different metals. The polymerase chain reaction in combination with DNA sequence analysis was used to investigate the genetic mechanism responsible for the metal resistance in some of these gram-positive and gram-negative bacteria that were, highly resistant to Hg, Zn, Cr and Ni. The czc, chr, ncc and mer genes that are responsible for resistance to Zn, Cr, Ni and Hg, respectively, were shown to be present in these bacteria by using PCR. In the case of, M. arabinogalactanolyticum AY509226 these genes were shown to have high homology to the czcD, chrB, nccA, and mer genes of Ralstonia metallidurans CH34. Therefore, Hg, Zn, Cr and Ni resistance genes are widely distributed in both gram-positive and gram-negative isolates obtained from A. murale rhizosphere and Ni-rich soils.     

Advanced oxidation processes for the treatment of olive-oil mills wastewater

In this work, the treatment of an actual industrial waste with three advanced oxidation processes (AOP) has been studied: conductive-diamond electrooxidation (CDEO), ozonation and Fenton oxidation. The wastewater comes from olive-oil mills (OMW) and contains a COD of nearly 3000 mg dm(-3). CDEO allowed achieving the complete mineralization of the waste with high current efficiencies. Likewise, both ozonation and Fenton oxidation were able to treat the wastes, but they obtained very different results in terms of efficiency and mineralization. The accumulation of oxidation-refractory compounds as final products excludes the use of ozonation and Fenton oxidation as a sole treatment technology. This confirms that besides the hydroxyl-radical mediated oxidation, CDEO combines other important oxidation processes such as the direct electro-oxidation on the diamond surface and the oxidation mediated by other electrochemically formed compounds generated on this electrode.     

Measuring and modelling experimental densities and ultrasonic velocities of aromatic and halogenated environmental pollutants

The potential environmental impact of aromatic and halogenated chemicals from the petrochemical and steel industry is of growning concern. The present paper deals with the modelling and experimental determination of density and speed of sound at the range 278.15-323.15 of six aromatic and halogenated compounds (Benzene, Toluene, Ethylbenzene, Fluorobenzene, 2-Fluorotoluene and Chlorobenzene). Fitting equations were applied to the data in order to correlate for later computer based design. The estimation of the studied properties was made by the application of different theoretical procedures. The Mchaweh-Nasrifar-Moshfeghian model (MNM), an equation of state based on the generalized van der Waals theory which combines the Staverman-Guggenheim combinatorial term of lattice statistics with an attractive lattice gas expression and the Free Length Theory showed a good response at the studied conditions.     

Distribution and transport of coal tar-derived PAHs in fine-grained residuum

We investigated the distribution and transport of coal tar-derived polycyclic aromatic hydrocarbons (PAHs) in fine-grained residuum and alluvial floodplain deposits that underlie a former manufactured gas plant. All 16 USEPA priority pollutant PAHs are present at this site and have penetrated the entire 4-5m thickness of clayey sediments, which unconformably overly limestone bedrock. Concentrations of less hydrophobic PAHs (e.g., naphthalene, 0.011-384mg kg(-1)) were about 10 times higher than those of highly hydrophobic PAHs (e.g., benzo[g,h,i]perylene -0.002 to 56.03mgkg(-1)). Microscopic examination of thin-sections of the clay-rich sediments showed that fractures and rootholes, which can act as pathways for flow, occur throughout the profiles. Tarry residue was found coating some fractures and rootholes, indicating that coal tar was, in some cases, able to penetrate as an immiscible phase. However, in the vast majority of samples in which PAHs were detected, there was no detectable tar residue, suggesting that much of the transport occurred in the dissolved phase. Examination of thin-sections with an epifluorescent microscope indicated that PAHs, which fluoresce brightly when exposed to UV light, are distributed throughout the soil matrix, rather than being confined to fractures and rootholes. The widespread distribution of PAHs is most likely due to diffusion-controlled exchange between the fast-flow pathways in the fractures and rootholes and the relatively immobile water in the fine-grained matrix. This implies that fractures and rootholes can play a major role in controlling transport of highly hydrophobic compounds in fine-grained sediments, which would otherwise act as barriers to contaminant migration.     

Biosurfactant technology for remediation of cadmium and lead contaminated soils

This research focuses on column experiments conducted to evaluate the potential of environmentally compatible rhamnolipid biosurfactant produced by Pseudomonas aeruginosa strain BS2 to remove heavy metals (Cd and Pb) from artificially contaminated soil. Results have shown that di-rhamnolipid removes not only the leachable or available fraction of Cd and Pb but also the bound metals as compared to tap water which removed the mobile fraction only. Washing of contaminated soil with tap water revealed that approximately 2.7% of Cd and 9.8% of Pb in contaminated soil was in freely available or weakly bound forms whereas washing with rhamnolipid removed 92% of Cd and 88% of Pb after 36 h of leaching. This indicated that di-rhamnolipid selectively favours mobilization of metals in the order of Cd>Pb. Biosurfactant specificity observed towards specific metal will help in preferential elution of specific contaminant using di-rhamnolipid. It was further observed that pH of the leachates collected from heavy metal contaminated soil column treated with di-rhamnolipid solution was low (6.60-6.78) as compared to that of leachates from heavy metal contaminated soil column treated with tap water (pH 6.90-7.25), which showed high dissolution of metal species from the contaminated soil and effective leaching of metals with treatment with biosurfactant. The microbial population of the contaminated soil was increased after removal of metals by biosurfactant indicating the decrease of toxicity of metals to soil microflora. This study shows that biosurfactant technology can be an effective and nondestructive method for bioremediation of cadmium and lead contaminated soil.     

Heavy metal-rich wastes sequester in mineral phases through a glass-ceramic process

Certain sludges generated by industry are rich in contaminating elements and are a major environmental problem. In this study, we determine the ability of these contaminating elements to be incorporated into a glass-matrix and in various mineral phases after a crystallization process. The contaminating elements studied were obtained from sewage sludges (SS) and galvanic sludges (GS), our raw materials. The sludge samples were taken from urban wastewater treatment plant in Catalonia (NE Spain) with high levels of phosphorus oxide (P(2)O(5)). In silica glasses, P(2)O(5) acts as a network former. We determined the chemical composition of both the SS and GS, as well as their thermal behaviour by differential thermal analysis and thermal gravimetric analysis (DTA-TG) to obtain their melting curves. The vitreous transition temperature of the obtained glass was established by dilatometer technique at 725 degrees C. The DTA-TG curve of the glass obtained has an exothermal wide peak at 860 degrees C corresponding to crystallization of the two phases: a spinel phase and a phosphate phase. A second exothermal wide peak at 960 degrees C was attributed to the crystallization of aluminium pyroxene, anorthite and fluor-apatite, with two exothermal phenomena attributed to the evolution of these phases. An exothermal peak at 1100 degrees C was attributed to gehlenite crystallization. Scanning electron microscope observations and energy-dispersed X-ray spectroscopy microanalyses of glass-ceramic showed that the contaminating elements were concentrated in the spinel phases, which are the first phases to crystallize during the cooling of glass. Finally, the spinel structure permits the incorporation of all the contaminating elements into it.     

Sulfidation treatment of molten incineration fly ashes with Na2S for zinc, lead and copper resource recovery

The present study focuses on the conversion of heavy metals involved in molten incineration fly ashes to metal sulfides which could be thereafter separated by flotation. The sulfidation treatment was carried out for five molten incineration fly ashes (Fly ash-A to Fly ash-E) by contacting each fly ash with Na(2)S solution for a period of 10 min to 6h. The initial molar ratio of S(2-) to Me(2+) was adjusted to 1.20. The conversion of heavy metals to metal sulfides was evaluated by measuring the S(2-) residual concentrations using an ion selective electrode. The formation of metal sulfides was studied by XRD and SEM-EDS analyses. In the case of Fly ash-A to Fly ash-D, more than 79% of heavy metals of zinc, lead and copper was converted to metal sulfides within the contacting period of 0.5h owing to a fast conversion of metal chlorides to metal sulfides. By contrast, the conversion of about 35% was achieved for Fly ash-E within the same contacting period, which was attributed to a high content of metal oxides. Further, the S(2-) to Me(2+) molar ratio was reduced to 1.00 to minimize Na(2)S consumption and the conversions obtained within the contacting period of 0.5h varied from 76% for Fly ash-D to 91% for Fly ash-C. Finally, soluble salts such as NaCl and KCl were removed during the sulfidation treatment, which brought about a significant enrichment in metals content by a factor varying from 1.5 for Fly ash-D to 4.9 for Fly ash-A.     

Binding affinity of proanthocyanidin from waste Pinus radiata bark onto proline-rich bovine achilles tendon collagen type I

Binding affinity of proanthocyanidin (PA) purified from Pinus radiata bark waste onto bovine Achilles tendon collagen (type I) was studied. Adsorption of PA onto the collagen was optimized by examining pH, contact time and temperature. The adsorption was pH-dependent. The maximum adsorption capacity (Q(0)) of PA on collagen was found to be 211 mg g(-1) using the Langmuir isotherm. Comparison between two adsorbents also showed that collagen had higher adsorptivity of approximately 20% more than PVPP (polyvinyl polypyrrolidone). The high affinity between PA and collagen was further confirmed in solvent solubility experiments. The observed solvent resistance was thought to be mainly due to a hydrophobic stacking mechanism reinforced by hydrogen bonding. FT-IR spectra clearly indicated the presence of PA adsorbed on collagen. The results have interesting implications that PA can be a good protective agent for collagen against collagenase and other enzymes.     

Temporal variability in particle-associated pesticide exposure in a temporarily open estuary, Western Cape, South Africa

This study assesses the risk of current-use pesticides in a temporarily open estuary in South Africa by developing probabilistic risk estimates. Particle-associated pesticides (chlorpyrifos, prothiofos, cypermethrin, fenvalerate, endosulfan and p,p-DDE) and physicochemical parameters (salinity, temperature, flow, and total organic content (TOC)) were measured in the Lourens River estuary (Western Cape) twice a month over a period of two years and equilibrium partitioning theory was applied to calculate concentrations of pesticides in the water. The 90th percentile concentrations of pesticides associated to suspended particles and the calculated concentrations in water were 34.0microg kg(-1) and 0.15microg l(-1) for prothiofos, 19.6microg kg(-1) and 0.45microg l(-1) for chlorpyrifos and 18.6microg kg(-1) and 0.16microg l(-1) for endosulfan. Highest average concentrations were found around the summer season due to higher application rates and as a result of the low flow during this season. Species sensitivity distribution indicated a 1.5-2.8 times higher toxicity (hazardous concentration HC5) for marine organisms compared to freshwater organisms. The calculated concentrations in the water exceeded all threshold values suggested by international water guidelines. Chlorpyrifos and endosulfan posed the highest acute risk to the Lourens River estuary. No sufficient toxicity data and threshold values were found for prothiofos.     

Effect of pre-treatment and supporting media on Ni(II), Cu(II), Al(III) and Fe(III) sorption by plant root material

In this work Paspalum notatum root material was used to elucidate the influence of acid leaching pre-treatment and of sorption medium on metal adsorption. Ground P. notatum root was leached with 0.14M HNO(3). Leached root material (LRM) and non-leached root material (NLRM) were employed to flow sorption of Ni(II), Cu(II), Al(III) and Fe(III) in 0.5M CH(3)COONH(4) medium at pH 6.5. For LRM the sorption was also studied in 0.5M KNO(3) medium. The acid pre-treatment increased the sorption capacity (SC) for all ions studied. For the KNO(3) medium, Cu(II) and Fe(III) sorption was higher than in CH(3)COONH(4) and the type of the Ni(II) isotherm's model changed. The Freundlich model was the most representative isotherm model to describe metallic ions sorption. The (1)H NMR spectra showed differences between LRM and NLRM and the acid-basic potentiometric titration elucidated that acid-leaching procedure affected the root material sorption sites once only two predominant sorption sites were found for LRM (phenolic and amine, both able cations sorption) and five sorption sites (two carboxylic, amine and two phenolic) were founded for NLRM.