X-42钢在碳酸钠-碳酸氢钠溶液中慢拉伸时电化学噪音信号的小波分析

本文应用小波分析理论研究了X42管线钢在0.5 mol/l Na2CO3 1 mol/l NaHCO3溶液中,在-950mVSCE、-1100mVSCE阴极极化条件下,慢应变速率实验过程中的极化电流信号.结果表明,极化电流信号的低频部分代表着其发展趋势.在阴极极化时,由于阴极析氢造成的体系pH值升高,因而电流信号有逐渐增大的趋势.而且,在对SSRT过程中阴极极化电流信号进行分析时,并未发现第二类间断点.因此,对于工业腐蚀监控,是否可用出现第二类间断点来预测X-42钢在土壤中的应力腐蚀失效,还有待于进一步的研究与探讨.     

PAFS-PDM混凝剂处理油田钻井废水实验

文章以硫酸铝、硫酸铁与聚二甲基二烯丙基氯化铵(PDM)为原料,制备PAFS-PDM复合混凝剂并表征其结构形态,同时考察了pH值、混凝剂投加量对油田钻井废水中COD的去除率以及溶液中Zeta电位的影响,为复合混凝剂的开发及使用提供一定的参考。研究结果表明:当PAFS-PDM复合混凝剂的投加量为8 000 mg/L、pH值为5时对塔里木油田钻井废水中COD的去除率达93.05%,此时溶液中Zeta电位较低。XRD衍射及SEM表征结果显示,制备的PAFS-PDM复合混凝剂中存在铝铁—羟基聚合物,微观形态下复合混凝剂将聚合形成的扇形片状结构再相互连接成发散立体结构,从而增大了比表面积,提高了混凝剂的吸附架桥能力,结合Zeta电位分析得出PAFS-PDM复合混凝剂为阳离子型混凝剂,而且具有较强的电中和能力。     

电位滴定法测定水中高锰酸盐指数

提出实验室用电位滴定测定水中高锰酸盐指数的方法。在国标法的基础上研究及优化了标定方法和实验方法,用电位滴定仪测定水中高锰酸盐指数,方法的检出限约为0.15mg/L,测定下限为0.60mg/L。实验证明,标准样品测量值均在推荐值范围内,对0.6mg/L,5.0mg/L,8.0mg/L浓度的NaC2O4标准溶液进行5次测定,得到的相对标准偏差分别为1.59%,0.97%,0.73%。在做低浓度的水样时,高锰酸钾溶液的浓度可以选择0.005mol/L。     

隧道内不同行驶工况下CO浓度分布及预测模式研究

本文通过现场实测,获取了在不同行驶工况下深圳市横龙山隧道内CO浓度分布情况.结果表明,在堵车、缓行及正常行驶3种情况下,隧道入口、隧道中及隧道出口的CO浓度均逐渐升高,堵车时隧道内CO浓度最高,正常行驶时的浓度最低.采用环保部机动车排污监控中心关于在用车综合排放因子的研究成果中第3阶段汽车尾气排放标准计算隧道内CO浓度,结果与实测数据相符,CO在纵向全射流通风隧道内扩散规律符合一维纵向空气质量扩散方程.     

铀在土壤中的吸附动力学

以四川盆地红层丘陵区涪江河谷两岸广泛分布的第四系中更新统亚粘土为对象,用动态法测定了铀在该土壤中的平衡吸附量,为极低放废物的处置提供一些理论依据。研究了流速、土壤粒度及铀溶液初始浓度对土壤吸附铀的影响,并用常用的吸附动力学方程对实验数据进行了拟合。结果表明：土壤粒度小的平衡吸附量较大;流速越小、平衡吸附量越大;铀溶液的初始浓度越大,平衡吸附量越大;在用动力学方程拟合时,E lovich方程的拟合度最好;该土壤对铀的最大吸附率为61.1%,吸附性能较差。     

草木灰对亚甲基蓝的吸附研究

本实验目的是研究草木灰对吸附亚甲基蓝的去除效果,探讨了亚甲基蓝初始量、吸附时间、pH值等对吸附效果的影响,并运用伪一级、伪二级反应动力学模型和Laugmuir、Freundlich等温线模型进行拟合。结果表明,草木灰对亚甲基蓝溶液的吸附在5 min~30 min速率比较快,约在65 min内达到吸附平衡,pH越大越有利于吸附,浓度在5mg/L时草木灰对亚甲基蓝的吸附最佳。与伪二级动力学曲线模型拟合效果较好,由Laugmuir等温线模型计算得出理论最大吸附容量Qm为2.275 mg/g,吸附性能优异。     

Reductive dechlorination of tetrachloroethene in a sand reactor using a potentiostat

In this study, an electrochemical system was investigated to enhance abiotic dechlorination of chlorinated solvents in contaminated soil in situ. A potentiostatic electrolysis sand reactor was developed and tested to evaluate tetrachloroethene (PCE) dechlorination in saturated sand. When operated with recirculating nutrient-supplemented water the reactor sustained a low oxidation reduction potential (ORP) at the cathode (<-400 mV standard hydrogen electrode [SHE]), a pH less than 9.4, and electric current >5 mA at room temperature with the cathodic potential controlled at -950 mV SHE. Tetrachloroethene in the electrolysis reactor had a half-life of 6.8 d compared with the control bioreactor without electrolysis, which had a PCE half-life of 16.4 d. Ethane and ethene were the main dechlorination products in the test reactor, while trichloroethene (TCE) accumulated in the nutrient-amended control reactor without electrolysis. An electrolysis reactor operated with water not amended with nutrients showed a PCE half-life of 7.6 d, suggesting that most of dechlorination activity in the reactor was abiotic. Since complete dechlorination can be achieved under moderate pH and temperature, this type of electrolysis technology is attractive as a remedial method for subsurface chloroethene contamination.     

Effect of chloride ions on the oxidation of aniline by Fenton's reagent

The objective of this study was to experimentally probe the mechanism of chloride ions specifically affecting aniline oxidation by Fenton's reagent. Batch experiments were carried out to investigate the effects of pH, Fe2+, H2O2 and chloride concentration on the oxidation reaction. Results show that the inhibition caused by chloride ions can be overcome by extending the reaction time if the concentration of chloride ions is low. At a high concentration of chloride ions, however, the oxidation of aniline was inhibited, and actually ceased due to the complexation of Fe-Cl. In this study, the chloride ion concentration was kept at 0.2 M in the experiments when studying the effect of ferrous ion concentration on the Fenton reaction. If the ratio of [Cl-]/[Fe2+] was < or = 200, the inhibition effect was very significant. In other words, adding more ferrous ions rather than hydrogen peroxide can break the inhibition originating from the chloride ions at an initial stage of pH 3. The inhibition effect of chloride ions on the aniline reaction depended on the reaction pH; the extent of inhibition decreased with increasing the initial pH as long as the pH was less than 5. Consequently, the inhibition effect by chloride ions was primarily due to the complexation of iron species and chloride ions. The influence of chloride ions on aniline oxidation due to the competition of hydroxyl radicals was not significant.     

Reduction of copper(II) by iron(II)

Laboratory and field investigations have clearly demonstrated the important role of reduced iron (Fe(II)) in reductive transformations of first-row transition metal species. However, interactions of Fe(II) and copper (Cu) are not clearly understood. This study examined the reduction of Cu(II) by Fe(II) in stirred-batch experiments at pH 5.2 and 5.5 as influenced by chloride (Cl-) concentration (0.002-0.1 M), initial metal concentration (0.1-9.1 mM), and reaction time (1-60 min) under anoxic conditions. Reduction of Cu(II) to Cu(I) by dissolved Fe(II) was rapid under all experimental conditions and the stability of the products explains the driving force for the redox reaction. Under conditions of low [Cl-] and high initial metal concentration, >40% of total Cu and Fe were removed from solution after 1 min, which accompanied formation of a brownish-red precipitate. X-ray diffraction (XRD) patterns of the precipitates revealed the presence of cuprite (Cu2O), a Cu(I) mineral, based on d-spacings located at 0.248, 0.215, 0.151, and 0.129 nm. Fourier transform infrared (FTIR) spectroscopy corroborated XRD data for the presence of Cu2O, with features located at 518, 625, and 698 cm(-1). Increasing [Cl-] stabilized the dissolved Cu(I) product against Cu2O precipitation and resulted in more Fe precipitated from solution (relative to Cu) that appears to be present as poorly crystalline lepidocrocite (gamma-FeOOH). This process may be important in anoxic soil environments, where dissolved Fe(II) levels can accumulate.     

The effects of throughfall manipulation on soil leaching in a deciduous forest

The effects of changing precipitation on soil leaching in a deciduous forest were examined by experimentally manipulating throughfall fluxes in the field. In addition to an ambient treatment (AMB), throughfall fluxes were reduced by 33% (DRY treatment) and increased by 33% (WET treatment) using a system of rain gutters and sprinklers on Walker Branch Watershed, Tennessee. Soil leaching was measured with resin lysimeters in the O horizons and with ceramic cup lysimeters in the E (25 cm) and Bt (70 cm) horizons. Large and statistically significant treatment effects on N fluxes were found in the O horizons (lower N fluxes in the DRY and higher N fluxes in the WET treatment). Together with the greater O horizon N content observed in the DRY treatment, this suggested that N was being immobilized at a greater rate in the DRY treatment than in the AMB or WET treatments. No statistically significant treatment effects on soil solution were found in the E horizons with the exception of (Ca2+ + Mg2+) to K+ ratio. Statistically significant treatment effects on electrical conductivity (EC), pH, Ca2+, Mg2+, K+, Na+, SO4(2-), and Cl- were found in the Bt horizons due to differences between the DRY and other treatments. Despite this, calculated fluxes of Ca2+, Mg2+, K+, Na+, SO4(2-), and Cl- were lowest in the DRY treatment. These results suggest that lower precipitation will cause temporary N immobilization in litter and long-term enrichment in soil base cations whereas increased precipitation will cause long-term depletion of soil base cations.     

Evaluation of water treatment sludge for ameliorating acid mine waste

This study investigated the liming effect of water treatment sludge on acid mine spoils. The study was conducted with sludge from a water purification plant along the Vaal River catchments in South Africa. The optimum application rate for liming acid spoils and the speed and depth with which the sludge reacted with the mine waste were investigated. Chemical analysis indicated that the sludge is suitable as a liming agent because of its alkaline pH (8.08), high bicarbonate concentration (183.03 mg L(-1)), and low salinity (electrical conductivity = 76 mS m(-1)). The high cation exchange capacity of 15.47 cmol(c) kg(-1) and elevated nitrate concentration (73.16 mg L(-1)) also increase its value as an ameliorative material. The soluble concentrations for manganese, aluminum, lead, and selenium were high at a pH of 5 although only selenium (0.83 mg L(-1)) warranted some concern. According to experimental results, the application of 10 Mg ha(-1) of sludge to acid gold tailings increased the leach water pH from 4.5 to more than 7.5 and also increased the medium pH from 2.4 to 7.5. The addition of sludge further reduced the solubility of iron, manganese, copper, and zinc in the ameliorated gold tailings, but increased the electrical conductivity. The liming tempo was highest in the coal discard profile that had a coarse particle size distribution and took the longest to move through the gold tailings that had a fine particle size distribution. Results from this study indicate that the water treatment sludge investigated is suitable as a liming agent for rehabilitation of acid mine waste.     

Leachate chemistry of field-weathered spent mushroom substrate

Passive leaching by rainfall and snowmelt is a popular method to treat piles of spent mushroom substrate (SMS) before its reuse. During this field weathering process, leachate percolates into the underlying soils. A field study was conducted to examine the chemistry of SMS leachate and effects of infiltration. Two SMS piles were deposited (90 and 150 cm in height) over a Typic Hapludult and weathered for 24 mo. Leachate was collected biweekly using passive capillary samplers. The SMS leachate contained high concentrations of dissolved organic carbon (DOC; 0.8-11.0 g L(-1)), dissolved organic nitrogen (DON; 0.1-2 g L(-1)), and inorganic salts. The pH, electrical conductivity, and acid neutralizing capacity were 6.6 to 9.0, 21 to 66 ds m(-1), and 10 to 75 mmolc L(-1), respectively. Inorganic chemistry of the leachate was dominated by K+, Cl-, and SO24-. Leachate DOC was predominantly low molecular weight (<1000 Da) organic acids. During 2 yr of weathering, the 90-cm SMS pile released (per cubic meter of SMS) 3.0 kg of DOC, 1.6 kg of dissolved N, and 26.6 kg of inorganic salts. The 150-cm pile released (per cubic meter of SMS) 2.8 kg of DOC, 0.7 kg of dissolved N, and 13.6 kg of inorganic salts. The 150 cm pile retained more water and exhibited lower net nitrification compared with the 90-cm pile. The top 90 cm of soil retained 20 to 89% of the leachate solutes. Weathering of SMS in piles of 90 cm depth or greater may adversely affect ground water quality.     

Effects of environmental factors on 1,3-dichloropropene hydrolysis in water and soil

Hydrolysis is the major pathway for fumigant 1,3-dichloropropene (1,3-D) degradation in water and soil, yet the process is not well understood. Experiments were conducted to investigate the effect of various environmental factors on the rate of 1,3-D hydrolysis. Cis-, trans-1,3-D and their isomeric mixture were spiked into water and Arlington soil (coarse-loamy, mixed, thermic Haplic Durixeralfs) and incubated under different conditions. The rate of 1,3-D hydrolysis in water and soil were evaluated based on its residual amount and Cl- release, respectively. 1,3-D hydrolyzed rapidly in deionized water, with a half-life of 9.8 d at 20 degrees C. The hydrolysis was pH dependent, with low pH inhibiting and high pH favoring the reaction. Other factors such as isomeric differences, photo irradiation, suspended particles, and small amounts of co-solutes had little effect on the reaction. In soil, 1,3-D hydrolyzed following pseudo first-order kinetics. The hydrolysis rate constant increased with soil moisture content and decreased with the initial 1,3-D concentration. At 20 degrees C, > 60% of the 1,3-D applied at < 0.61 g kg(-1) in 10% moisturized soil hydrolyzed within 30 d. The soil particle size and mineralogy had little effect on the reaction rate. Organic matter promoted 1,3-D degradation via direct substitution reactions, and the trans-isomer showed preference over the cis- to react with certain organic molecules. Microbial contributions were initially insignificant, and became important as soil microorganisms adapted to the fumigant. The results suggest that to accelerate 1,3-D degradation, pH, soil moisture, and organic amendment should be considered.     

Removal of selenate from water by zerovalent iron

Zerovalent iron (ZVI) has been widely used in the removal of environmental contaminants from water. In this study, ZVI was used to remove selenate [Se(VI)] at a level of 1000 microg L(-1) in the presence of varying concentrations of Cl-, SO(2-)4, NO(-)3, HCO(-)3, and PO(3-)4. Results showed that Se(VI) was rapidly removed during the corrosion of ZVI to iron oxyhydroxides (Fe(OH)). During the 16 h of the experiments, 100 and 56% of the added Se(VI) was removed in 10 mM Cl- and SO(2-)4 solutions under a closed contained system, respectively. Under an open condition, 100 and 93% of the added Se(VI) were removed in the Cl- and SO(2-)4 solutions, respectively. Analysis of Se species in ZVI-Fe(OH) revealed that selenite [Se(IV)] and nonextractable Se increased during the first 2 to 4 h of reaction, with a decrease of Se(VI) in the Cl- experiment and no detection of Se(VI) in the SO(2-)4 experiment. Two mechanisms can be attributed to the rapid removal of Se(VI) from the solutions. One is the reduction of Se(VI) to Se(IV), followed by rapid adsorption of Se(IV) to Fe(OH). The other is the adsorption of Se(VI) directly to Fe(OH), followed by its reduction to Se(IV). The results also show that there was little effect on Se(VI) removal in the presence of Cl- (5, 50, and 100 mM), NO(-)3 (1, 5, and 10 mM), SO(2-)4 (5 mM), HCO(-)3 (1 and 5 mM), or PO(3-)4 (1 mM) and only a slight effect in the presence of SO(2-)4 (50 and 100 mM), HCO(-)3 (10 mM), and PO(3-)4 (5 mM) during a 2-d experiment, whereas 10 mM PO(3-)4 significantly inhibited Se(VI) removal. This work suggests that ZVI may be an effective agent to remove Se from Se-contaminated agricultural drainage water.     

Leaching from organic matter-rich soils by rain of different qualities: I. Concentrations

Soil monoliths from an area exposed to acid precipitation and from an unpolluted area were used in a lysimeter experiment to study effects of different rain qualities on the chemical composition of the leachate from shallow soils rich in organic matter. The vegetation was either dominated by moorgrass [Molinia caerulea (L.) Moench] or heather [Calluna vulgaris (L.) Hull]. The lysimeters received either "acid rain" (pH 4.3) or "normal rain" (pH 5.3). High concentrations of dissolved organic carbon (DOC) were characteristic of the leachate. The different "rain" qualities had no significant influence on the DOC concentration. More DOC was, however, leached from lysimeters with heather vegetation. Roughly 50% of the aluminum (Al) was in complex with organic material and the Al charge was calculated to be between +1.4 and +2.0. Sulfate (SO4(2-)) was the only component that was significantly influenced by the treatment, as more was leached from lysimeters receiving "acid rain." Sulfate was poorly correlated with pH, suggesting that reduced SO4(2-) input would not necessarily lead to reduced acidity. Differences in the pH of the leachate due to the treatments were less than 0.15 pH units. Nitrate (NO3-) was only leached in very low concentrations and of little consequence for the leachate acidity. Some observations do, however, suggest that NO3- may contribute to acidification in episodes with high precipitation. High concentrations of Cl- in the leachate and a significant positive correlation between Cl-, H+, and base cations indicate that sea salt episodes may be important for soil acidification and acidity of the leachate.     

我国南方主要酸沉降区临界负荷研究

以马尾松为指示植物,对韶关的土壤进行了长期淋溶模拟并记录其化学状态。结果发现,土壤溶液的pH值下降到4.0,Bs值下降到几乎为零,有较大量的A1离子溶出。最后选取土壤溶液pn〉4.0、KS〉10％和[Al^3＋]〈0.1mmol／L为临界化学指标,参考国内外应用广泛的MAGIC模型和SMART模型,确定韶关酸沉降临界负荷（S的临界负荷）为14.1keq／hm^2.a。