Enzymatic degradation of low-rank coals by a cell-free enzymatic system from Coriolus versicolor

An extracellular fraction from the lignin degrading white-rot fungus, Coriolus versicolor, can biosolubilize leonardite and pretreated lignites in vitro. Leonardite is often found as an overburden to lignite deposits, and is related to humic acid, and is more oxidized than lignites. Extracts from certain fungi such as C. versicolor solubilize leonardite. The biosolubilization activity is at least in part enzymatic in nature. A protein which is at least partly responsible for the solubilization effect has been substantially purified and concentrated by ultrafiltration and ion-exchange chromatography from the broth of an agitated submerged culture of C. versicolor grown in a defined medium. An in vitro coal biosolubilization assay was used to establish the effects of various physical and chemical factors affecting enzyme activity, including temperature and the salt and buffer composition of the reaction mixture. Some initial studies on the mechanism of the enzymatic leonardite biosolubilization reaction are described.     

Chemical composition of organic matter in extremely acid, lignite-containing lake sediments impacted by fly ash contamination

In the Lusatian lignite mining district of eastern Germany, extremely acid lakes developed during ground water rising after exploitation of lignite in open-cast mines. The reasons of plant colonization (Juncus bulbosus L.) of some lakes exhibiting moderate pH values while others remain extremely acid and unvegetated are unknown. Alkalinity gain may be achieved by addition of alkaline materials and/or decomposition of organic matter. Our objective was to examine fly ash deposition and the resulting changes in organic matter composition in the uppermost 0 to 5 cm of the sediment sampled from vegetated and unvegetated lakes. Bulk soil and particle size fractions were analyzed for elemental composition, magnetic susceptibility, and chemical structure of the organic matter by 13C solid-state nuclear magnetic resonance (NMR) spectroscopy. The lignite content of the samples was estimated by 14C activity measurements. The pH values decreased with increasing depth and the changes in pH were found to be correlated with changes in magnetic susceptibility. Carbon and nitrogen contents were found to decrease with increasing depth. The C to N ratios are consistent with the (i) the presence of decomposing plant residues and/or microbial material such as algae in the upper 0 to 5 cm of the sediment and (ii) the dominance of lignite in the layers below this depth as confirmed by 14C activity measurements. The structural analyses of the particle size separates from the 0- to 5-cm depth were consistent with the presence of organic matter derived from plant material. This study confirms that fly ash is an important source of alkalinity in the upper 0 to 5 cm of the sediment that enhanced plant growth and led to enrichment of the sediment with organic matter derived from plant material.     

催化氧化法处理含硫废碱液新技术的开发与应用

在炼油生产中,合理处理产生的大量废碱液,使其不污染环境,一直是我们努力研究的课题。辽河石化分公司所采用的处理方法是:将含硫化物废碱液催化氧化,使其中有毒的硫化物快速氧化成亚硫酸盐、硫代硫酸盐及硫酸盐等物质。经过处理的含硫化物废碱液已进行了脱臭,并且回收了有利用价值的碱液。碱液吸收SO2后生产出合格的亚硫酸钠产品,达到了废液综合利用的目的。     

PHOSPHATE IN WATERS: I. REDUCTION USING NORTHERN LIGNITE FLY ASH1

Fly ashes fiom lignite coal fixed steam electric plants contain appreciable amounts of materials that can, in principle, decrease the phosphorus concentration in surface waters. Typical samples of un-weathered fly ash were used to test efficacies of removal of phosphorus from standard phosphate solutions and actual lake water samples. The effects of changing parameters such as contact time, pH, fly ash/water ratios, and solution temperature are presented. Water soluble and insoluble factors in the ash both appear to be reactive constituents. Trials with municipal waste waters showed near quantitative removal of ortho-phosphate.     

Nitrogen fertilization effects on stream water cadmium concentration

High transition metal concentrations were previously unexpectedly observed in soil water extracted by suction lysimeters following forest N fertilization. This observation called for additional measurements to investigate if the finding is a general phenomenon and, if so, whether stream water concentrations of transition metals could increase as a result of N fertilization. The measured levels of Cd in the preliminary findings were well above health limits for drinking water. Hence, the problem could be of major concern. Here we report on soil water and stream water concentrations at two partly fertilized watersheds. All sites were situated in the central part of Sweden. The N application (150 kg N ha(-1) in the form of calcium ammonium nitrate) resulted in increased concentrations of nitrate, and a pulse of acidity through the soil profile, which increased the solubility of transition metals (mainly Cd and Zn) and Al. Stream water concentrations of transition metals, on the other hand, were not affected during the studied period by the increased solubility of transition metals in the soil. The data imply that the solubilized transition metals probably insolubilize further down the soil profile, and that there is no risk from forest N fertilization (at normal soil pH levels) of transition metal levels increasing in nearby surface waters. To our knowledge, this is the first time this side effect of N fertilization has been considered.     

Rhamnolipid morphology and phenanthrene solubility at different pH values

The effect of pH and rhamnolipids on the solubility of phenanthrene was investigated in a sand-water system. Batch phenanthrene solubilization experiments in this system showed that the highest phenanthrene solubility occurred at pH 5 in the presence of 240 and 150 mg L(-1) rhamnolipids. As the pH was increased from 5 to 7, the apparent solubility of phenanthrene decreased and then stabilized from pH 7 to 8. At pH 4, a dramatic decrease in phenanthrene solubility was observed. This result is in contrast to previous findings obtained in an aqueous system without soil particles. To investigate the reason for this decrease, the critical micelle concentrations (CMCs) were measured in the presence or absence of sand particles, and the maximum amount of sorbed biosurfactant at each pH was calculated based on the differences of the two CMC values. More rhamnolipid molecules were lost by the sorption into sand particles at pH 4 than at other pH values; this explains the dramatic decrease of solubility at pH 4 in the sand-water system. To confirm the explanation for the different solubilizing capacity that results from the structural change of biosurfactant aggregate, cryo-transmission electron microscopy was used. Micrographs showed that the rhamnolipid morphology changed from large lamellar sheets, to vesicle, and then to micelle as the pH increased. The large and multilamellar vesicles at pH 5 were considered to be the most effective structure for the solubilization of phenanthrene.     

Bioproduction of ferric sulfate used during heavy metals removal from sewage sludge

Toxic metals removal from wastewater sewage sludge can be achieved through microbial processes involving Acidithiobacillus ferrooxidans. The oxidation of ferrous ions by A. ferrooxidans, cultured in sewage sludge filtrate, was studied in both batch and continuous flow stirred tank reactors. Sewage sludge filtrate containing natural nutrients (phosphorus and nitrogen) was recovered as effluent following the dehydration of a primary and secondary sludge mixture. Batch and continuous flow stirred tank reactor tests demonstrated that A. ferrooxidans were able to grow and completely oxidize ferrous iron in a culture medium containing more than 80% (v v(-1)) sewage sludge filtrate with 10 g Fe(II) L(-1) added. Toxic levels were reached when total organic carbon in the sewage sludge filtrate exceeded 250 mg L(-1). The ferric iron solution produced in the sludge filtrate by A. ferrooxidans was used to solubilize heavy metals in primary and secondary sludge. The solubilization of Cu, Cr, and Zn yielded 71, 49, and 80%, respectively. This is comparable with the yield percentages obtained using a FeCl(3) solution. The cost of treating wastewater sewage sludge by bioproducing a ferric ion solution from sewage sludge is three times less expensive than the conventional method requiring a commercial ferric chloride solution.     

Kinetics of carbon mineralization of biochars compared with wheat straw in three soils

Application of biochars to soils may stabilize soil organic matter and sequester carbon (C). The objectives of our research were to study in vitro C mineralization kinetics of various biochars in comparison with wheat straw in three soils and to study their contribution to C stabilization. Three soils (Oxisol, Alfisol topsoil, and Alfisol subsoil) were incubated at 25°C with wheat straw, charcoal, hydrothermal carbonization coal (HTC), low-temperature conversion coal (LTC), and a control (natural organic matter). Carbon mineralization was analyzed by alkali absorption of CO released at regular intervals over 365 d. Soil samples taken after 5 and 365 d of incubation were analyzed for soluble organic C and inorganic N. Chemical characterization of biochars and straw for C and N bonds was performed with Fourier transformation spectroscopy and with the N fractionation method, respectively. The LTC treatment contained more N in the heterocyclic-bound N fraction as compared with the biochars and straw. Charcoal was highly carbonized when compared with the HTC and LTC. The results show higher C mineralization and a lower half-life of straw-C compared with biochars. Among biochars, HTC showed some C mineralization when compared with charcoal and LTC over 365 d. Carbon mineralization rates were different in the three soils. The half-life of charcoal-C was higher in the Oxisol than in the Alfisol topsoil and subsoil, possibly due to high Fe-oxides in the Oxisol. The LTC-C had a higher half-life, possibly due to N unavailability. We conclude that biochar stabilization can be influenced by soil type.     

Effect of cobalt sorption on metal fractionation in anaerobic granular sludge

A sequential extraction procedure was applied to two anaerobic methanogenic sludges (Eerbeek and Nedalco) to examine the speciation of micro- and macronutrients in the sludges after cobalt sorption by exposing the sludge to a 1 mM Co solution for 4 d at pH 7 and 30 degrees C. The effect of different physicochemical conditions on cobalt sorption was studied as well: effect of pH (6-8), effect of competition by a second trace element (Ni or Fe), modification of the granular matrix by glutaraldehyde or heat treatment, and EDTA (ethylenediaminetetraacetic acid) addition. Sorbed Co was found to distribute between the carbonates, organic matter + sulfides, and residual fractions. Cobalt adsorption resulted in an antagonistic interaction with other metals present in the granular matrix, evidenced by the solubilization of other trace elements (e.g., Ni, Cu, and Zn) as well as macronutrients (especially Ca and Fe). Modification of the sludge matrix by glutaraldehyde or heat treatment, or exposure to EDTA, led to serious modifications of the Co sorption capacity and strong interactions with multivalent cations (i.e., Ca(2+) and Fe(2+)).     

Leaching characteristics of solid wastes from thermal power plants of western Turkey and comparison of toxicity methodologies

Use of lignite in power generation has led to increasing environmental problems associated not only with gaseous emissions, but also with the disposal of ash residues. In particular, use of low quality coals with high ash content results in huge quantities of both fly and bottom ashes to be disposed of. A main problem related to coal ash disposal is the heavy metal content of the residue. In this regard, experimental results of numerous studies indicate that toxic trace metals may leach when fly and bottom ashes are in contact with water. In this study, fly and bottom ash samples obtained from thermal power plants, namely Yenikoy, Kemerkoy and Yatagan, located at the southwestern coast of Turkey, were subjected to toxicity tests such as the extraction (EP) and toxicity characteristic leaching (TCLP) procedures of the US Environmental Protection Agency (USEPA) and the so-called 'Method A' extraction procedure of the American Society of Testing and Material (ASTM). The geochemical composition of ash samples showed variations depending on the coal burned in the plants. Furthermore, the EP, TCLP and ASTM toxicity tests showed variations such that the ash samples were classified as 'toxic waste' based on EP and TCLP results whereas they were classified as 'non-toxic' based on ASTM results, indicating test results are pH dependent. When the extraction results were compared with the chemical composition of water samples obtained in the vicinity of the thermal power plants, it was found that the results obtained using the ASTM procedure cannot be used to predict subsurface contamination whereas the EP and TCLP procedures can be used.     

Developing of a pricing model for Turkish lignite used in thermal plants

The objective of this paper is to develop a general pricing model for Turkish Lignite, which is mainly sold to thermal plants. This model will contribute to the development of coal mining within the scope of privatization efforts of the Turkish energy market. The paper consists of two stages. First, data of 10 thermal plants have been evaluated by using hedonic pricing analysis to determine influential price parameters. The results of hedonic regression analysis indicate the effect and importance of calorific value and electricity price on lignite prices. Second, a general coal-pricing model has been developed by taking into account the results of hedonic analysis. Comparison of the coal prices estimated by the developed pricing model and the coal prices obtained from thermal plants indicates an acceptable relation.     

The leaching characteristics of selenium from coal fly ashes

The leaching characteristics of selenium from several bituminous and subbituminous coal fly ashes under different pH conditions were investigated using batch methods. Results indicated that pH had a significant effect on selenium leaching from bituminous coal ash. The minimum selenium leaching occurred in the pH range between 3 and 4, while the maximum selenium leaching occurred at pH 12. The release of selenium from subbituminous coal ashes was very low for the entire experimental pH range, possibly due to the high content of calcium which can form hydration or precipitation products as a sink for selenium. The adsorption results for different selenium species indicated that Se(VI) was hardly adsorbable on either bituminous coal ashes or subbituminous coal ashes at any pH. However, Se(IV) was highly adsorbed by bituminous coal ashes under acidic pH conditions and was mostly removed by subbituminous coal ashes across the entire pH range. This result suggests that the majority of selenium released from the tested fly ashes was Se(IV). A speciation-based model was developed to simulate the adsorption of Se(IV) on bituminous coal fly ash, and the pH-independent adsorption constants of HSeO3* and SeO3 2* were determined. The modeling approach is useful for understanding and predicting the release process of selenium from fly ash.     

Biodegradation of nitrogen-enriched lignite

Biodegradation of nitrogen-enriched lignite by soil bacteria previously acclimated in hydrogen peroxide-acetic acid lignitic substrate was carried out to assess the effects of nitrogen functional groups on the biodegradation of lignite. Chlorination, oxidation plus nitration, and ammoniation were applied in an attempt to modify the chemical structure of lignite so as to obtain a lignitic substrate that is more compatible to the enzymatical system of ordinary soil bacteria than that of unmodified lignite. Incorporation of nitrogen containing functional groups into lignite structure achieved 4.71 wt%, a value five times higher than that usually found in unmodified (raw) lignite. Data collected through a 16 day incubation time, monitoring production as well as depletion of both nitrate and organic acids, concluded that biodegradation was expedited by the incorporation of nitrogen into the structure of lignite. Twenty-eight compounds were identified based on the results from GC/MS analysis of the products.     

Cyclodextrin-enhanced solubilization of pentachlorophenol in water

The solubilization of pentachlorophenol (PCP) by beta-cyclodextrin (beta-CD) and three of its most used derivatives, methyl-beta-cyclodextrin (MCD), hydroxypropyl-beta-cyclodextrin (HPCD) and carboxymethyl-beta-cyclodextrin (CMCD), has been investigated. The formation of soluble inclusion complexes between PCP and cyclodextrin (CDs) increases the aqueous solubility of PCP. Due to the ionizable nature of PCP, the effects of pH and ionic strength on the equilibrium complexation were evaluated. All CDs were found to form 1:1 inclusion complexes. Equilibrium constants calculated from solubility enhancement experiments revealed that the stability of the complexes was dependent on the polarity of the compound, on the ionic strength and on the cyclodextrin type. In general, weaker equilibrium constants were observed for PCP with beta-CD than with MCD or CMCD. For all CDs, the complexation or the solubilization efficiency of PCP (weak acid) depended on pH and ionic strength. Moreover, we observed that the solubility of the beta-CD/PCP complex was lower than that of the beta-CD molecule and dependent on the ionic strength of the solution. Although the equilibrium constant of PCP/CD complex was found to be higher at pH 3 than at pH 7 in water, extraction of PCP from porous media by a CD solution at neutral pH would be achievable due to the higher PCP aqueous solubility in neutral/basic media.     

HOW MUCH UNDERGROUND WATER STORAGE CAPACITY DOES TEXAS HAVE?1

Water imported into Texas under the Texas Water Plan must be stored in surface or underground reservoirs. Ground-water levels are being drawn down heavily in many parts of Texas. This is causing a shift of much water from a surface- to a groundwater environment. The lowering water tables have resulted in a great reduction in wastage of water through evapotranspiration and spring and well flow. The methods used in estimating the quantities of underground storage capacity available in Texas are discussed. Some problems will be encountered in the use of dewatered underground storage capacity by artificial recharge. In spite of these problems, probably 60 to 70 percent of the dewatered storage capacity of Texas aquifers can be reused for groundwater storage. Most of this capacity is located where it can be used in conjunction with the Texas Water Plan.     

Factors affecting the ratio of cation exchange capacity to clay content in lignite overburden

Unusually high cation exchange capacity (CEC) values relative to clay content are frequently reported for lignite overburden and minesoils. The CEC to percent clay ratio is commonly greater than one and would require that the average charge of the clay fraction be greater than 100 cmol(c) kg(-1). A comparison of methods for particle-size distribution suggests that the major reason lignite overburden samples have CEC to percent clay ratios greater than one is incomplete dispersion of aggregates of clay minerals or shale fragments. Preliminary investigations revealed the presence of shale fragments, smectite, and partially weathered mica in the silt fraction. Methods commonly used in soil textural analysis underestimated clay content by approximately 24%. The silt fraction may, therefore, provide a "hidden" source of CEC. Another important factor influencing the CEC to percent clay ratio was the presence of organic materials (lignite) in the samples. Lignite may make a significant contribution to CEC in overburden materials. In a study designed to estimate the pH-dependent charge of both the mineral and organic fractions, the CEC of overburden organic constituents was determined to be approximately 158 cmol(c) kg(-1) at pH 8.2. The high CEC to percent clay ratio in lignite overburden and minesoils may be resolved by adjusting methods for clay determination to optimize dispersion and by accounting for CEC due to organic materials. An alternative approach is to use existing methodology and use correction factors to account for incomplete dispersion of clay minerals and the charge contributions of organic materials.     

微山湖养殖湖区水体中多环芳烃的分布及来源

采用HPLC定量分析微山湖养殖湖区水体中16种优先控制PAHs的总量浓度范围在5348.8～12970.8ng/L之间,平均值为8671.5ng/L,处于中等偏高污染水平;养殖湖区水体中的多环芳烃主要来源于养殖船只的石油泄露及煤炭、木材与石油的不完全燃烧,PAHs的组成以2～3环为主。     

PHOSPHATE IN WATERS: II. PLANT AVAILABILITY OF LIGNITE FLY ASH EXTRACTED FORMS IN GREENHOUSE TRIALS1

ABSTRACT: Orthophosphate P was removed from municipal waste water, lake waters, and P-spiked solutions by contact with fly ash from lignite burning electric power generating plants. The recovered ash was increased in total P content 3-fold, and Bray No. 1 soluble P, 9-fold. Phosphorus enriched ash so prepared was used in greenhouse trials with sand or soil as the major substrate material. Recovery of added P by barley plants ranged from 3 to 26 percent in the sand cultures and from 2 to 17 percent for soil cultures. Phosphorus contained in normal ash was partially available to barley under the conditions of these experiments. High B and the pozzolanic effect induced by ash reduced plant growth significantly.     

水煤浆在节能减排中的应用及发展前景

水煤浆是由60%~68%的煤和32%~40%的水或废水经研磨混合,在0.5%添加剂作用下形成的一种均匀稳定的流体洁净燃料,以流态雾化喷燃方式燃烧。水煤浆技术基本成熟,已被广泛应用于工业锅炉和窑炉。在同等条件下,水煤浆与燃煤相比可节煤32%,减排SO2和烟尘分别达到77%和82%以上;燃自制水煤浆时可节省燃料费20%以上。将水煤浆技术应用于治理棉浆粕黑液时,不仅投资比碱回收工程少1/2,而且实现了零排放。自"十五"以来,国家一直十分重视水煤浆产业,其发展前景十分广阔。     

盐碱地养鱼的水质改良

报道了盐碱地池塘、水库、湖泊养鱼中的水质改良技术。池塘水质改良措施主要为加注淡水、施用有机肥、注水与施肥相结合、改造盐碱土质、控制生石灰用量及合理注排水 ;水库、湖泊等大水面水质改良的主要措施是引淡水和增施肥料 (有机肥和化肥 )。