Oxalate production by wood-rotting fungi growing in toxic metal-amended medium

In this report, we have identified oxalic acid as an important metabolite elaborated in the response of wood-rotting fungi to toxic metal stress. The formation of oxalate crystals by white rot fungi (Bjerkandera fumosa, Phlebia radiata and Trametes versicolor) and the brown rot fungus Fomitopsis pinicola, grown on media containing high levels of toxic metal ions has been visualized using scanning electron microscopy (SEM) with energy-dispersive X-ray micro-analysis (EDXA) and HPLC. There were no significant differences between the growth of controls (metal-free) and on the 0.5% CaCO(3), Co(3)(PO(4))(2) or Zn(3)(PO(4))(2)-amended plates. ZnO inhibited the growth of all strains. Crystals were not detected in Zn(3)(PO(4))(2)-amended plates. The four examined strains displayed the formation of crystals on ZnO, Co(3)(PO(4))(2) and CaCO(3)-amended plates.     

Modeling of electrodialytic and dialytic removal of Cr, Cu and As from CCA-treated wood chips

A one-dimensional model is developed for simulating the electrodialytic and dialytic treatment of a saturated bed of wood chips containing chromium, copper and arsenic. The movement of Cr, Cu and As is mathematically modeled taking into account the diffusion transport resulting from the concentration gradients of their compounds and the electromigration of their ionic, simple and complex species during the operation. The model also includes the electromigration of the non-contaminant principal ionic species in the system, H(+) and OH(-), proceeding from the electrolysis at the electrodes, Na(+) and NO(3)(-) used as electrolyte solutions in the electrode compartments, and oxalate ions and protons incorporated with the oxalic acid solution during wood chips incubation. The model simulation also takes into account that OH(-) generated on the cathode, during electrodialytic remediation, is periodically neutralized by addition of nitric acid in the cathode compartment. The anion and cation-exchange membranes are simply represented as ionic filters that preclude the transport of co-ions (the cations and anions respectively) with the exception of H(+), which is retarded but considered to pass through the anion-exchange membrane.     

Fungal biodegradation of CCA-treated wood and removal of its metal components

In the present study, 5 isolates of brown-rot fungi were used for fungal bioprocessing (FB) of chromated copper arsenate (CCA)-treated wood wastes: Antrodia vaillantii SEL8501, Fomitopsis palustris TYP0507 and TYP6137, and Crustoderma sp. KUC8065 and KUC8611. The isolates showed notable capacity for the degradation of treated wood and removal of CCA components via the American Wood Protection Association soil block test. Among them, Crustoderma sp. KUC8611 effectively decayed the treated wood, causing a mass loss of up to 60%. F. palustris caused extensive leaching of CrO₃ of up to 79% and As₂O₅ of up to 87%, but only moderate leaching of CuO of up to 50%. This high capacity for removal of CrO₃ and As₂O₅ showed a strong logarithmic relationship with the amount of oxalic acid produced in the decayed wood. The majority of metals removed from treated wood during the decay process were deposited in the soil and feeder strip. Further investigation will be required to establish the capability of selected fungi for FB of full-sized lumber treated with CCA.     

钙对李氏禾富集和耐受铬的调控作用

通过水培实验,研究钙对铬胁迫下李氏禾幼苗生理生化、草酸分泌及铬吸收量的影响,考察钙对李氏禾体内草酸合成的调控,进而促进李氏禾的铬耐性富集能力的作用。结果显示,不同浓度Cr³⁺胁迫下缺钙处理,李氏禾生长受抑制及质膜过氧化作用加剧,体内总草酸含量为对照处理的113%~169%,且主要表现为水溶性草酸含量显著高于对照,水溶性草酸含量为对照处理的135%~197%;高钙处理,李氏禾细胞膜透性、丙二醛（MDA）含量低于对照,李氏禾叶部总草酸含量为对照处理的125%~155%,且主要表现为不溶性草酸含量显著高于对照,其含量为对照处理的181%~270%。低浓度（0.2、0.4 mmol/L）铬胁迫下,高钙处理总铬含量分别为对照处理的175%和215%,高浓度（0.8、1.0 mmol/L）铬胁迫下,总铬含量与对照处理无显著差异（P>0.05）。可见,添加Ca²⁺能在一定Cr³⁺浓度胁迫下,有效缓解铬对李氏禾的毒害,且能通过提高植物体内不溶性草酸含量达到促进植物富集和耐受铬的能力。     

Partial dissolution of ACQ-treated wood in lithium chloride/N-methyl-2-pyrrolidinone: separation of copper from potential lignocellulosic feedstocks

A cellulose solvent system based on lithium chloride (LiCl) in N-methyl-2-pyrrolidinone (NMP) was used to assess the merits of partial dissolutions of coarsely ground wood samples. Alkaline Copper Quaternary (ACQ)-treated pine wood was of particular interest for treatment given the potential to generate a copper-rich stream apart from solid and/or liquid lignocellulosic feedstocks. Treatment with NMP alone gave yields of soluble materials that were higher than typical extractives contents thereby suggesting a limited degree of wood dissolution. Inclusion of LiCl, which disrupts hydrogen bonding, gave lower wood residue recoveries (i.e., higher dissolution) with higher LiCl concentration. Lower wood residue recoveries coincided with lower Klason lignin and hemicellulose-derived sugar contents in the wood residues. After treatment with 8% LiCl in NMP, subsequent filtration afforded 34% of the ACQ-treated sapwood as a wood residue retaining only 2% of the original copper. Pouring the filtrate over an excess of water resulted in the recovery of 30% of the solids and 50% of the copper together as a copper-enriched lignocellulosic precipitate. Results demonstrate a solvent system showing potential as a means to separate heavy metals from preservative-treated wood and to recover lignocellulosic feedstocks that may be suitable for use in a biorefinery.     

Anaerobic biodegradability and methanogenic toxicity of key constituents in copper chemical mechanical planarization effluents of the semiconductor industry

Copper chemical mechanical planarization (CMP) effluents can account for 30-40% of the water discharge in semiconductor manufacturing. CMP effluents contain high concentrations of soluble copper and a complex mixture of organic constituents. The aim of this study is to perform a preliminary assessment of the treatability of CMP effluents in anaerobic sulfidogenic bioreactors inoculated with anaerobic granular sludge by testing individual compounds expected in the CMP effluents. Of all the compounds tested (copper (II), benzotriazoles, polyethylene glycol (M(n) 300), polyethylene glycol (M(n) 860) monooleate, perfluoro-1-octane sulfonate, citric acid, oxalic acid and isopropanol) only copper was found to be inhibitory to methanogenic activity at the concentrations tested. Most of the organic compounds tested were biodegradable with the exception of perfluoro-1-octane sulfonate and benzotriazoles under sulfate reducing conditions and with the exception of the same compounds as well as Triton X-100 under methanogenic conditions. The susceptibility of key components in CMP effluents to anaerobic biodegradation combined with their low microbial inhibition suggest that CMP effluents should be amenable to biological treatment in sulfate reducing bioreactors.     

Field-scale leaching of arsenic, chromium and copper from weathered treated wood

Earlier studies documented the loss of wood preservatives from new wood. The objective of this study was to evaluate losses from weathered treated wood under field conditions by collecting rainfall leachate from 5 different wood types, all with a surface area of 0.21 m². Wood samples included weathered chromate copper arsenate (CCA) treated wood at low (2.7 kg/m³), medium (4.8 kg/m³) and high (35.4 kg/m³) retention levels, new alkaline copper quat (ACQ) treated wood (1.1 kg/m³ as CuO) and new untreated wood. Arsenic was found to leach at a higher rate (100 mg in 1 year for low retention) than chromium and copper (<40 mg) in all CCA-treated wood samples. Copper leached at the highest rate from the ACQ sample (670 mg). Overall results suggest that metals' leaching is a continuous process driven by rainfall, and that the mechanism of release from the wood matrix changes as wood weathers.     

The effect of low molecular weight chelators on iron chelation and free radical generation as studied by ESR measurement

The purpose of this work was to improve our current knowledge of the non-enzymatic mechanisms involved in brown rot fungal decay of wood, but also to improve our understanding of chelator-mediated reactions that may occur in other biological systems where low pH conditions may prevail. Several key steps (iron chelation and reduction) during early non-enzymatic wood decay processes have been studied by using electron spin resonance (ESR). It has been proposed that low molecular weight chelators as well as Fenton reagents are involved in brown rot decay, at least in early non-enzymatic stages. In this work, the binding between a catecholate model chelator and ferric iron was studied by ESR spectroscopy. The effects of the model chelator, Fenton reagents, as well as the reaction conditions on free radical generation were also studied using ESR spin-trapping techniques. The results indicate: (1) The relative quantity of the chelator-iron complex can be determined by measurement of the intensities of the characteristic g = 4.3 ESR signal. (2) The effects of the chelator:iron ratio, the pH, and other reaction parameters on the hydroxyl radical generation in a Fenton type system can be determined using ESR spin-trapping techniques. (3) Data support the hypothesis that superoxide radicals are involved in chelator-mediated Fenton processes.     

Desorption of copper and cadmium from soils enhanced by organic acids

The adsorption/desorption behavior of copper and cadmium on soils was investigated in this study. The adsorption isotherm of copper and cadmium conformed to Langmuir equation better than Freundlich equation. The effect of ionic strength, pH, and organic acid, including ethylenediamine tetraacetic disodium acid salt (EDTA), citric acid, oxalic acid and tartaric acid, on the desorption of copper and cadmium was studied. The desorption of copper and cadmium increased with the increase of ionic strength, while the desorption decreased with the rise of pH. The desorption of copper and cadmium enhanced by organic acids was influenced by pH. EDTA showed excellent enhancement on the desorption of both copper and cadmium; citric acid demonstrated great enhancement on the desorption of copper but negligible enhancement on the desorption of cadmium; oxalic acid enhanced the desorption of copper only at pH around 6.4 and enhanced the desorption of cadmium in the pH range from 6.4 to 10.7; tartaric acid slightly enhanced the desorption of copper but negligibly enhanced the desorption of cadmium. The desorption mechanism in the presence of organic acids were explained as the competition of complexation, adsorption and precipitation. The net effect determined the desorption efficiency. This study provided guidance for the selection of organic acids to enhance the electrokinetic (EK) remediation of copper and cadmium from contaminated soils.     

Acid and aluminum effects on freshwater zooplankton: an in situ Mesocosm study

An in situ mesocosm experiment was performed to evaluate the role of aluminum toxicity in determining zooplankton community responses to take acidification. Large plastic enclosures were suspended in East Twin Lake, Ohio, USA, and duplicates were either untreated controls (pH 8.8), acidified to pH 4.5 over a 23 day period, or acidified and also spiked with incremental additions of Al, to produce a final inorganic monomeric Al level of 180 microg/liter at pH 4.5. Zooplankton abundance and species richness declined in both acid treatments, relative to the control, as numerous acid-sensitive species were eliminated. All of the acid-sensitive species were also Al-sensitive, declining in abundance more rapidly in the acid plus Al treatment than in the acid-alone treatment. Only two small cladocerans (Bosmina longirostris and Chydorus sphaericus) were acid tolerant. Both were also tolerant of elevated Al levels.     

Mycelium growth and degradation of creosote-treated wood by basydiomycetes

Tolerance of wood decay fungi of the genera Agrocybe, Armillaria, Auricularia, Daedalea, Pleurotus, Trametes to the presence of various amounts of creosote-treated wood (CTW) in the growth medium was compared. In the case of the most tolerant strain, Pleurotus ostreatus SMR 684, extracellular laccase and peroxidase specific activities were monitored during growth in the presence of CTW. Degradation of various creosote-constituting polycyclic aromatic hydrocarbons by this strain was evaluated by GC-MS and the ecotoxicity of treated and untreated CTW was compared by Microtox test.     

Atmospheric production of oxalic acid/oxalate and nitric acid/nitrate in the Tampa Bay airshed: Parallel pathways

Oxalic acid is the dominant dicarboxylic acid (DCA), and it constitutes up to 50% of total atmospheric DCAs, especially in non-urban and marine atmospheres. A significant amount of particulate H₂Ox/oxalate (Ox) occurred in the coarse particle fraction of a dichotomous sampler, the ratio of oxalate concentrations in the PM₁₀ to PM_2.5 fractions ranged from 1 to 2, with mean±sd being 1.4±0.2. These results suggest that oxalate does not solely originate in the gas phase and condense into particles. Gaseous H₂Ox concentrations are much lower than particulate Ox concentrations and are well correlated with HNO₃, HCHO, and O₃, supporting a photochemical origin. Of special relevance to the Bay Region Atmospheric Chemistry Experiment (BRACE) is the extent of nitrogen deposition in the Tampa Bay estuary. Hydroxyl radical is primarily responsible for the conversion of NO₂ to HNO₃, the latter being much more easily deposited. Hydroxyl radical is also responsible for the aqueous phase formation of oxalic acid from alkenes. Hence, we propose that an estimate of OH can be obtained from H₂Ox/Ox production rate and we accordingly show that the product of total oxalate concentration and NO₂ concentration approximately predicts the total nitrate concentration during the same period.     

Biodegradation of aromatic compounds by white rot and ectomycorrhizal fungal species and the accumulation of chlorinated benzoic acid in ectomycorrhizal pine seedlings

The capability of different white rot (WR, Heterobasidion annosum, Phanerochaete chrysosporium, Trametes versicolor) and ectomycorrhizal (ECM, Paxillus involutus, Suillus bovinus) fungal species to degrade different aromatic compounds and the absorption of 3-chlorobenzoic acid (3-CBA) by ECM pine seedlings was examined. The effect of aromatic compounds on the fungal biomass development varied considerably and depended on (a) the compound, (b) the external concentration, and (c) the fungal species. The highest effect on the fungal biomass development was observed for 3-CBA. Generally the tolerance of WR fungi against aromatic compounds was higher than that of the biotrophic fungal species. The capability of different fungi to degrade aromatic substances varied between the species but not generally between biotrophic and saprotrophic fungi. The highest degradation capability for aromatic compounds was detected for T. versicolor and H. annosum, whereas for Phanerochaete chrysosporium and the ECM fungi lower degradation rates were found. However, Paxillus involutus and S. bovinus showed comparable degradation rates at low concentrations of benzoic acid and 4-hydroxybenzoic acid. In contrast to liquid cultures, where no biodegradation of 3-CBA by S. bovinus was observed, mycorrhizal pines inoculated with S. bovinus showed a low capability to remove 3-CBA from soil substrates. Additional X-ray microanalytical investigations showed, that 3-CBA supplied to mycorrhizal plants was accumulated in the root cell cytoplasm and is translocated across the endodermis to the shoot of mycorrhizal pine seedlings.     

Gas chromatography/mass spectrometry of paraquat UV-ozonation products

The chromatographic and mass spectral properties of 13 compounds isolated from the reaction of UV and ozone on paraquat are described. The products were extracted from the acidified reaction mixture and converted to TMS derivatives. The identified products were the diTMS ester of oxalic acid (m/z 234), the TMS ester of 4-picolinic acid (m/z 195), the diTMS ester of succinic acid (m/z 262), the diTMS derivative of N-formylglycine, 4,4'-bipyridyl (m/z 156), the triTMS derivative of malic acid (m/z 350), and the diTMS derivative of a hydroxy-4-picolinic acid. Structural features and tentative identification of some of the remaining compounds are discussed. The most prominent peak on the chromatogram has a probable molecular ion at m/z 219, isomeric to the diTMS derivative of glycine. The structures presented suggest that demethylation, ring oxidation and fragmentation of one or both rings of the bipyridinium di-cation occur during UV-ozonation of paraquat.     

碱法麦草浆漂白废水脱色白腐菌的筛选及脱色研究

从腐木上采集,经多次分离纯化筛选出2株具有较高漂白废水脱色能力的菌株F7、F9,与Phanerochaete Chrysosporium在相同的条件下处理碱法麦草浆CE段混合漂白废水,培养4d脱色率分别为74．44％,46．67％和62．22％。延长培养时间至第8d,F7菌脱色效果不明显,而F9菌脱色可增至67．58％。     

Effects of acidifying reagents on microwave treatment of dairy manure

Dairy manure, acidified using organic acids (acetic, oxalic, and citric acid) were treated with microwave enhanced advanced oxidation process (MW/H₂O₂-AOP). The effect of a mixture of oxalic acid and commonly used mineral acids (sulfuric and hydrochloric acid) on MW/H₂O₂-AOP was also examined. Substantial amounts of phosphorus were released under MW/H₂O₂-AOP, regardless of organic acid or mineral acid used. All three organic acids were good acidifying reagents; however, only oxalic acid could remove free calcium ion in the solution, and improve settleability of dairy manure. The MW/H₂O₂-AOP and calcium removal process could be combined into a single-stage process, which could release phosphate, solubilize solids and remove calcium from dairy manure at the same time. A mixture of oxalic acid and mineral acid produced the maximum volume of clear supernatant and had an ideal molar ratio of calcium to magnesium for effective struvite (magnesium ammonium phosphate) crystallization process. A single-stage MW/H₂O₂-AOP would simplify the process and reduce mineral acid consumption compared to a two-stage operation. The results of a pilot scale study demonstrate that MW/H₂O₂-AOP is effective in treating manure and recovering resource from dairy farms.     

Environmental effects of one thousand years of copper production at Falun, central Sweden

Copper production in Falun, central Sweden, has emitted sulfur dioxide (SO2) and metals to the air during at least 1000 years. Emissions peaked in the 17th century when Falun produced 2/3 of the world's copper supply. This area offers unique opportunities to study long-term effects of acid deposition and metal pollution, including recovery following the three centuries of decreasing SO2 and metal deposition. Here we present a 1000-yr perspective on local emissions of SO2, estimated air concentrations and dry deposition of SO2, as well as results on acidification and metal pollution of soils and lakes. Despite a long period when deposition of SO2 exceeded the critical load, soil acidification is limited to the most heavily polluted area 12 km NW and SE from the mine. According to diatom analyses of take sediments, only 8 of 14 lakes have become acidified (0.4-0.8 pH units). None of these lakes show recovery from acidification, probably due to large amounts of sulfate still accumulated in the soils and changes in land use.     

Speciation and leachability of copper in mine tailings from porphyry copper mining: influence of particle size

Mine tailing from the El Teniente-Codelco copper mine situated in VI Region of Chile was analysed in order to evaluate the mobility and speciation of copper in the solid material. Mine tailing was sampled after the rougher flotation circuits, and the copper content was measured to 1150 mg kg (-1) dry matter. This tailing was segmented into fractions of different size intervals: 0-38, 38-45, 45-53, 53-75, 75-106, 106-150, 150-212, and >212 microm, respectively. Copper content determination, sequential chemical extraction, and desorption experiments were carried out for each size interval in order to evaluate the speciation of copper. It was found that the particles of smallest size contained 50-60% weak acid leachable copper, whereas only 32% of the copper found in largest particles could be leached in weak acid. Copper oxides and carbonates were the dominating species in the smaller particles, and the larger particles contained considerable amounts of sulphides.     

Effects of Cutrine-Plus® algaecide and predators on wood frog (Lithobates sylvaticus) tadpole survival and growth

Copper contamination is increasing in many aquatic ecosystems. One mode by which copper can be introduced into aquatic ecosystems is as an algaecide, such as Cutrine-Plus®. Using a mesocosm experiment, we examined the effects of Cutrine-Plus® on wood frog (Lithobates sylvaticus) tadpoles. In addition, we examined how the presence of a nonnative predator the Western mosquitofish (Gambusia affinis) may interact with exposure to Cutrine-Plus®. Exposure to our low and high Cutrine-Plus® treatments had a strong negative effect on the wood frog tadpoles, and survivorship was greatly decreased in the low treatment, and no tadpoles survived in the high treatment. Additionally, the tadpoles that survived the low treatment were significantly smaller than those in the control treatment. Mosquitofish had no effect on the survivorship or growth of wood frog tadpoles, and mosquitofish presence did not have a significant interaction with the Cutrine-Plus® treatments. Cutrine-Plus® clearly had a negative effect on wood frog tadpoles at the concentrations used in our experiment, which were at and below the label-recommended dosages, suggesting that the use of Cutrine-Plus® in natural ponds may have negative consequences for wood frog populations and possibly other amphibians.     

Intercomparison of the measurements of oxalic acid in aerosols by gas chromatography and ion chromatography

Oxalate, the anion of oxalic acid, is one of the most abundant measurable organic species in atmospheric aerosols. Traditionally, this bifunctional species has been measured by gas chromatography (GC) after derivatization to butyl ester and by ion chromatography (IC) without derivatization. However, there are few published comparisons of the two techniques. Here, we report the results of an intercomparison study for the measurement of oxalic acid in Arctic aerosols (<2.5 μm, n = 82) collected in 1992 using GC and IC. The concentrations of oxalic acid by GC ranged from 6.5–59.1 ng m^?3 (av. 26.0 ng m^?3, median 26.2 ng m^?3) whereas those by IC ranged from 6.6–52.1 ng m^?3 (av. 26.6 ng m^?3, median 25.4 ng m^?3). They showed a good correlation (r = 0.84) with a slope of 0.96. Thus, observations of oxalate obtained by GC employing dibutyl esters are almost equal to those by IC. Because the accuracy of oxalic acid by GC method largely depends on the method used, it is important to strictly examine the recovery in each study.