生物反应器填埋场产甲烷规律的模拟研究

生物反应器填埋场是一种新型的垃圾卫生填埋场,可以加速填埋场的稳定及甲烷的产生.通过模拟试验探讨了生物反应器填埋场在不同操作条件下的产甲烷情况及COD、pH值的变化趋势.试验证明较高的回灌频率有助于垃圾降解、产甲烷速率的升高及渗滤液中COD浓度的降低;污泥接种起缓冲作用,使垃圾的降解及产气速率更趋向平稳;甲烷的产生与COD的降低是同步进行的,因此可以通过COD的变化趋势来判断产甲烷情况.研究建立了反映垃圾含水率影响填埋场产甲烷的数学模型,该模型具有简便、直观、准确等优点.     

渗滤液回灌频率对生物反应器填埋场的影响研究

通过模拟实验研究了渗滤液回灌周期为1、2、3和5 d的4个模拟垃圾柱的产甲烷过程和渗滤液水质的变化情况.在用NaOH调节回灌渗滤液pH值的前提下,回灌频率越高,模拟厌氧型生物反应器填埋垃圾柱先开始产甲烷,但当回灌周期低于3 d时,开始产甲烷的时间相差不多.从渗滤液水质看,回灌周期为3 d的垃圾柱渗滤液COD、VFA等有机污染物浓度下降最快.综合考虑启动时间、运行费用和填埋场的稳定进程,在厌氧型生物反应器填埋场中,实施3 d/次的渗滤液回灌频率最为合适.     

模拟成藏填埋垃圾有机质稳定化与产气的阶段性

通过人工构建模拟生物气藏的大型模拟生物反应器,研究模拟成藏填埋城市生活垃圾有机质厌氧降解及生物气化规律及其机理。结果表明,自然温度条件下,模拟填埋垃圾有机质降解和生物气化具有明显阶段性,与pH、ORP、温度等指标的阶段性变化存在相关性。产气阶段最佳条件包括:最适温度范围为31.0～36.0℃;最适pH范围为5.47～6.75,pH中性条件下产甲烷速率最高;ORP最适范围为-428～-541 mV,产甲烷高峰期ORP值为-519 mV,低于前人关于甲烷菌最适ORP的界定范围。每千克挥发性固体总生物气和甲烷产量分别为128.5 L和77.7 L,生物气和甲烷最大产气量分别为118.0 L/d和82.0 L/d,甲烷最大浓度为70.4%,产气高峰期与甲烷浓度高峰期同时出现。模拟成藏填埋垃圾有机质的稳定化过程具有明显的可诱导特征,关键因子的优化对有机质的降解及生物气化产生明显促进作用。     

不同好氧预处理方式对餐厨垃圾产甲烷的影响

为了研究不同好氧预处理方式对餐厨垃圾厌氧消化产甲烷的影响,通过建立3个模拟厌氧生物反应器,研究了传统厌氧生物反应器C1、上层好氧预处理-厌氧生物反应器C2和底部好氧预处理-厌氧生物反应器C3 3种不同操作条件下的产甲烷过程.结果表明,挥发性有机酸的累积使C1始终处于产甲烷滞后阶段;而C2、C3的好氧预处理通过加快易水解酸化组分和过量挥发性有机酸的好氧降解,有效缓解了酸性抑制,产甲烷滞后时间明显缩短至10 d内.第32天C2停止上层曝气后,在27 d内甲烷浓度达到了50％以上,同时,产甲烷速率迅速上升,并在第81天可达到峰值773 mL/(kg·d).C3在第11天停止底部曝气后,虽然经过22 d的时间甲烷浓度即上升至50％,但之后产甲烷速率经历回落阶段后再次逐渐上升,在实验结束时仅达到517 mL/(kg·d).上层曝气的好氧预处理方式所需曝气时间相对较长,但其产甲烷启动快,与底部曝气相比,其后期的甲烷化过程更稳定并可达到较高的产甲烷速率.     

模拟生物反应器加速产甲烷过程研究

渗滤液原液回灌易导致填埋垃圾产甲烷过程的滞后,从而对甲烷收集利用产生不利影响。通过3根实验室模拟生物反应器,研究了原液回灌(C1)、渗滤液好氧预处理后回灌(C2)和原液回灌+垃圾层上部通风曝气(C3)3种填埋方式下的填埋气产气规律。结果表明,C1甲烷浓度经历短暂上升,达到19.5%后开始逐渐降低,产甲烷速率和产甲烷总量均很低;C2甲烷浓度逐渐上升,在第121天时甲烷浓度达到50%,产甲烷最高速率和产甲烷总量分别为0.31 L/(kg·d)和25.2 L/kg。在停止上部垃圾层通风曝气后,C3甲烷浓度迅速上升,在81 d时甲烷浓度便达到50%以上,最大产甲烷速率和产甲烷总量分别为0.22 L/(kg·d)和16.0 L/kg。对各模拟柱填埋气可回收性评价结果表明,C3填埋气可回收利用比例最高,C2略低,C1在实验期间内则无可回收利用气体产生。     

机械淋滤-厌氧生物组合工艺处理有机生活垃圾中试研究

采用机械淋滤/厌氧生物组合工艺,充分发挥机械淋滤反应器的水解酸化功能和厌氧生物反应器的产甲烷功能,对有机生活垃圾进行了中试规模处理。厌氧生物反应器经过接种,15 d驯化完成。厌氧反应器出水回流淋洗水量对机械淋滤反应器运行特征有较大影响,当回流淋洗水量为3.0 m3/d时,淋滤液COD、VFA第8天时浓度分别为41 000 kg/L和2 000 kg/L。对机械淋滤反应器/厌氧反应器组合工艺进行了多批次实验,每吨有机生活垃圾平均产生沼气87.2 m3,甲烷含量稳定在75%,平均产沼系数为0.46 m3/kg COD,厌氧生物反应器出水COD平均值为560 mg/L,在对有机生活垃圾处理的同时实现有机生活垃圾资源化利用。     

曝气频率对生物反应器渗滤液与填埋气的影响

传统生物反应器填埋场长期以来存在酸化阶段过长和能源回收利用率低等同题.上层垃圾好氧处理可有效实现垃圾快速降解与集中甲烷化.为探究好氧处理阶段不同曝气频率对生物反应器填埋场运行效果的影响,设置厌氧生物反应器A1作为对照,曝气频率不同的上层曝气式生物反应器C1和C2为实验组进行实验.结果表明,上层垃圾好氧处理可有效改善填埋柱内高浓度挥发性脂肪酸(VFA)累积现象,缩短酸化阶段,促进甲烷化环境建立.至曝气结束,C1和C2填埋柱内渗滤液COD低于30 000 mg/L,VFA浓度降也降低到10 000 mg/L以下.好氧处理阶段,增大曝气频率可提高填埋垃圾对渗滤液pH的缓冲作用,扩大甲烷化面积,促进高浓度甲烷化过程的快速发生.与C1相比,曝气频率较高的C2反应器提前15 d达到pH为7的预处理要求,曝气阶段氨氮浓度经历先上后下,填埋柱日产甲烷量700 mL,约为C1产气能力的2倍.但考虑到实际氧气利用率与经济性能问题,曝气频率的选择不宜过大.     

高氨氮对厌氧生物法处理城市垃圾渗沥液的影响

研究了高浓度氨氮对厌氧膜生物法处理城市垃圾渗沥液的影响。结果表明，COD去除率、沼气产量、沼气产率、辅酶F420和最大比产甲烷活性均随氨氮浓度的增加而减小；当氨氮浓度〈3600mg/L时，不会对厌氧膜生物反应器的运行产生明显的影响；氨氮对厌氧污泥产甲烷活性的50％抑制浓度为4350mg／L；高浓度氨氮会造成系统VFA浓度增加；当氨氮浓度由4800mg／L降低到2000mg/L后，受重度抑制的厌氧微生物的活性可以在20d里恢复到未受抑制时的活性水平。     

生物接触氧化处理渗滤液有机物的动力学模型研究

以重庆黑石子垃圾填埋场渗滤液生物接触氧化工艺为依托,针对其处理效果的局限性,设计了强化预处理-生物接触氧化反应器,并进行生物接触氧化反应器试验及其有机物降解动力学模型研究,旨在优化运行参数,提高渗滤液处理效果.结果表明,改进后系统比原工艺处理效果好,COD、NH4 -N、TN平均去除率分别达到95.83%、97.60%、85.60%;出水水质得到大幅度提高,出水COD、NH4 -N、TN平均质量浓度分别为235、35、199 mg/L.对生物接触氧化反应器内垃圾渗滤液有机物降解生化反应过程进行量化研究,得到微生物生长动力学模型为1/θc=0.918 7q-0.002 5;根据生物接触氧化反应器内基质消耗过程的物料平衡,得到生物接触氧化反应器处理垃圾渗滤液有机物生物降解的动力学模型为q=1.09S/(10 230 S).试验结果为生物接触氧化反应器的优化控制、设计与放大提供了参考依据.     

污泥与餐厨垃圾联合厌氧发酵产氢余物产甲烷过程底物指标变化

将污泥与餐厨垃圾联合厌氧发酵产氢余物进一步产甲烷,产甲烷量比污泥与餐厨垃圾单独或直接联合厌氧发酵产甲烷大.研究污泥与餐厨垃圾联合厌氧发酵产氢余物产甲烷过程中产甲烷量与底物指标变化的关系,实验结果表明,整个消化过程中,累积产甲烷量为613 L,最大产气速率和产甲烷速率分别为2.12 L/(kg·d)和1.46 L/(kg·d),最大甲烷含量为72.5％,消化系统的pH在总挥发性脂肪酸(TVFA)以及氨氮、CO32-和HCO3-等碱度的共同作用下基本维持在适宜产甲烷的范围内,在不同的消化阶段,厌氧发酵产甲烷过程起主要作用的物质不同,先后顺序依次为糖类、蛋白质和TVFA,并且累积产甲烷量与COD、总糖、总蛋白质的显著相关性大小依次为:COD＞总糖＞总蛋白质,COD去除率高达79.54％.     

Evaluation of trichloroethene recovery processes in heterogeneous aquifer cells flushed with biodegradable surfactants

The ability of two biodegradable surfactants, polyoxyethylene (20) sorbitan monooleate (Tween 80) and sodium dihexyl sulfosuccinate (Aerosol MA), to recover a representative dense non-aqueous-phase liquid (DNAPL), trichloroethene (TCE), from heterogeneous porous media was evaluated through a combination of batch and aquifer cell experiments. An aqueous solution containing 3.3% Aerosol MA, 8% 2-propanol and 6 g/l CaCl(2) yielded a weight solubilization ratio (WSR) of 1.21 g TCE/g surfactant, with a corresponding liquid-liquid interfacial tension (IFT) of 0.19 dyn/cm. Flushing of aquifer cells containing a TCE-DNAPL source zone with approximately two pore volumes of the AMA formulation resulted in substantial (>30%) mobilization of TCE-DNAPL. However, a TCE mass recovery of 81% was achieved when the aqueous-phase flow rate was sufficient to displace the mobile TCE-DNAPL toward the effluent well. Aqueous solutions of Tween 80 exhibited a greater capacity to solubilize TCE (WSR=1.74 g TCE/g surfactant) and exerted markedly less reduction in IFT (10.4 dyn/cm). These data contradict an accepted empirical correlation used to estimate IFT values from solubilization capacity, and indicate a unique capacity of T80 to form concentrated TCE emulsions. Flushing of aquifer cells with less than 2.5 pore volumes of a 4% T80 solution achieved TCE mass recoveries ranging from 66 to 85%, with only slight TCE-DNAPL mobilization (<5%) occurring when the total trapping number exceeded 2 x 10(-5). These findings demonstrate the ability of Tween 80 and Aerosol MA solutions to efficiently recover TCE from a heterogeneous DNAPL source zone, and the utility of the total trapping number as a design parameter for a priori prediction of DNAPL mobilization and bank angle formation when flushing with low-IFT solutions. Given their potential to stimulate microbial reductive dechlorination at low concentrations, these surfactants are well-suited for remedial action plans that couple aggressive mass removal followed by enhanced bioremediation to treat chlorinated solvent source zones.     

Chloroaromatic pollutants in mussels incubated in two finnish watercourses polluted by industry

Concentrations of different chlorinated compounds were measured in mussels incubated in two polluted watercourses, a river (the River Kymijoki) and a lake (Lake Vanaja) for four weeks in summer 1995. The sum concentrations of polychlorinated phenols (PCP) and biphenyls (PCB) were both about 1 μg/g lipid weight (lw) in Lake Vanaja mussels, while in the River Kymijoki mussels PCPs were non-detectable and PCBs were measured 120 ng/g lIw. The concentrations of toxic polychlorinated dibenzo-p-dioxin (PCDD) and dibenzofuran (PCDF) congeners ranged between <17 and 370 pg/g Iw in Lake Vanaja mussels and between <38 and 11,000 pg/g lw in the River Kymijoki mussels. Polychlorinated diphenyl ethers (PCDE) were detected in the mussels incubated in the River Kymijoki (0.4–1.1 ng/g Iw), but not in those incubated in Lake Vanaja. Polychlorinated phenoxyanisoles (PCPA) were measured 33 ng/g lw and polychlorinated phenoxyphenols (PCPP) 300 ng/g lw in the mussels incubated in the River Kymijoki. PCPAs were also detected in reference samples, which were sediment and pike from the River Kymijoki and Baltic salmon, seal and white-tailed sea eagle.     

The variation of street air levels of PAH and other mutagenic PAC in relation to regulations of traffic emissions and the impact of atmospheric processes

The occurrence of particle associated PAH and other mutagenic PAC was determined in 1996 in the street air of Copenhagen. In addition, particle extracts were tested for mutagenicity. The measurements were compared with previous measurements in 1992/1993. The levels had decreased in this period. The decrease was caused by an implementation of light diesel fuels for buses and the exchange of older petrol-driven passenger cars with catalystequipped new ones. About 65% of the reduction was caused by the application of the light diesel fuels. Under special conditions, chemical processes in the atmosphere produced many more mutagens than the direct emissions. The concentrations of S-PAC and N-PAC were 10 times lower than those of PAH, while the levels of oxy-PAH were in the same order of magnitude as those of PAH. Benzanthrone, an oxy-PAH, is proposed to be formed in the atmosphere in addition to direct emissions. Benzo(a)pyrene, often applied as an air quality criteria indicator, was photochemically degraded in the atmosphere. A strong increase in the mutagenic activities was observed to coincide with a depletion of benzo(a)pyrene.     

Teratological effects of pesticides in vertebrates: a review

Abstract

In the last decades, the use and misuse of pesticides in the agriculture have increased, having a severe impact on ecosystems and their fauna. Although the various effects of pesticides on biodiversity have been already documented in several studies, to our knowledge no consistent overview of the impact of pesticides in vertebrates, both terrestrial and aquatic, is available. In this review, we try to present a concise compilation of the teratogenic effects of pesticides on the different classes of vertebrates – mammals, birds, reptiles, amphibians and fish.     

Radionuclides and trace elements in fish collected upstream and downstream of Los Alamos national laboratory and the doses to humans from the consumption of muscle and bone

Abstract

The purpose of this study was to determine radionuclide and trace element concentrations in bottom‐feeding fish (catfish, carp, and suckers) collected from the confluences of some of the major canyons that cross Los Alamos National Laboratory (LANL) lands with the Rio Grande (RG) and the potential radiological doses from the ingestion of these fish. Samples of muscle and bone (and viscera in some cases) were analyzed for ³H, ⁹⁰Sr, ¹³⁷Cs, ^totU, ²³⁸Pu, ^239,240Pu, and ²⁴¹Am and Ag, As, Ba, Be, Cr, Cd, Cu, Hg, Ni, Pb, Sb, Se, and Tl. Most radionuclides, with the exception of ⁹⁰Sr, in the muscle plus bone portions of fish collected from LANL canyons/RG were not significantly (p<0.05) higher from fish collected upstream (San Ildefonso/background) of LANL. Strontium‐90 in fish muscle plus bone tissue significantly (p<0.05) increases in concentration starting from Los Alamos Canyon, the most upstream confluence (fish contained 3.4E‐02 pCi g^‐1 [126E‐02 Bq kg^‐1]), to Frijoles Canyon, the most downstream confluence (fish contained 14E‐02 pCi g^‐1 [518E‐02 Bq kg^‐1]). The differences in ⁹⁰Sr concentrations in fish collected downstream and upstream (background) of LANL, however, were very small. Based on the average concentrations (±2SD) of radionuclides in fish tissue from the four LANL confluences, the committed effective dose equivalent from the ingestion of 46 lb (21 kg) (maximum ingestion rate per person per year) of fish muscle plus bone, after the subtraction of background, was 0.1 ± 0.1 mrem y^‐1 (1.0 ± 1.0 μSv y^‐1), and was far below the International Commission on Radiological Protection (all pathway) permissible dose limit of 100 mrem y^‐1 (1000 μSv y^‐1). Of the trace elements that were found above the limits of detection (Ba, Cu, and Hg) in fish muscle collected from the confluences of canyons that cross LANL and the RG, none were in significantly higher (p<0.05) concentrations than in muscle of fish collected from background locations.     

Book review

The Pesticide Manual ‐ A World Compendium, 8th Edition, C.R. Worthing, Editor and S.B. Walker, Assistant Editor, British Crop Protection Council, BCPC Publications Sales, Bear Farm, Binfield, Bracknell, Berkshire RG12 5QE, England. 1987, 1100 pp., UK £50; Overseas £56. ISBN 0–948404–01–9.     

Patterns of volatile metabolites and nonvolatile trichothecenes produced by isolates of <Emphasis Type="Italic">Stachybotrys,Fusarium, Trichoderma,Trichothecium</Emphasis> and <Emphasis Type="Italic">Memnoniella</Emphasis>

We reported previously that trichodiene, a volatile trichothecene derivative, was produced by a Stachybotrys isolate, also known to produce highly cytotoxic, non-volatile, macrocyclic trichothecenes (satrotoxins). We investigated the relationship between the production of trichodiene and various non-volatile trichothecenes for several molds. Volatile metabolites were concentrated by adsorption on Tenax TA and analyzed by GC/MS, while non-volatile metabolites were separated by HPLC, derivatized and analyzed by GC/MS. Stachybotrys chartarum isolates producing macrocyclic trichothecenes secreted significantly larger amounts of trichodiene and other sesquiterpenes than isolates which only produced simple trichothecenes. The amounts of secreted trichodiene were relatively small in all cases. With the exception of Memnoniella, which excreted small amounts of sesquiterpenes, the other isolates produced varying amounts of sesquiterpenes, including trichodiene, as well as simple tricothecenes, no detectable trichodiene, but large amounts of griseofulvin derivatives. In Stachybotrys there is apparently a correlation between trichodiene and macrocyclic trichothecene production. In the remaining isolates, there was no simple relationship between trichodiene and non-volatile trichothecene synthesis. Trichodiene is produced in larger amounts by Stachybotrys isolates, which also produce satratoxins, but it will be difficult to utilize this metabolite to detect toxic isolates in buildings due to the relatively small amounts excreted.     

Observations on the influence of water and soil pH on the persistence of insecticides

Abstract

The pH‐disappearance rate profiles were determined at ca. 25°C for 24 insecticides at 4 or 5 pH values over the range 4.5 to 8.0 in sterile phosphate buffers prepared in water‐ethanol (99: 1 v/v). Half‐lives measured at pH 8 were generally smaller than at lower pH values. Changes in half lives between pH 8.0 and 4.5 were largest (>1000x) for the aryl carbamates, carbofuran and carbaryl, the oxime carbamate, oxamyl, and the organophosphorus insecticide, trichlorfon. In contrast, half lives of phorate, terbufos, heptachlor, fensulfothion and aldicarb were affected only slightly by pH changes. Under the experimental conditions described half lives at pH8 varied from 1–2 days for trichlorfon and oxamyl to >1 year for fensulfothion and cyper‐methrin. Insecticide persistence on alumina (acid, neutral and basic), mineral soils amended with aluminum sulfate or calcium hydroxide to different pH values and four natural soils of different pH was examined. No correlation was observed between the measured pH of these solids and the rate of disappearance of selected insecticides applied to them. These observations demonstrate the difficulty of extrapolating the pH dependent disappearance behaviour observed in homogeneous solution to partially solid heterogeneous systems such as soil.     

The chemical stability of formulations of some hydrolyzable insecticides in aqueous mixtures with hydrolysis catalysts

Abstract

The active ingredients in commercial formulations of malathion, oxamyl, carbaryl, diazinon, and chlorpyrifos diluted to “spray tank”; concentrations with buffered distilled or natural water of pH 4–9 were stable for at least 24 hr. Formulations of trichlorfon were not stable at pH 7 or above but disappearance rates were slower than for the pure chemical in homogeneous solution. Cupric ion was observed to be an effective catalyst for the hydrolysis of a variety of pure organophosphorus insecticides but did not catalyze hydrolysis of the active ingredients of the formulations examined. Increasing the dilution of the formulation increased the susceptibility of malathion, oxamyl, and carbaryl to hydrolysis.     

Organochlorine compounds in a three-step terrestrial food chain

The concentrations of 15 organochlorine chemicals (PCBs and pesticides) were studied in a Central European oak wood food chain system: Great tit (Parus major), caterpillars (Tortrix viridana, Operophtera brumata, Erannis defoliaria), and oak-leaves (Quercus robur). Juvenile tits receive organochlorines from the mother via egg transfer and, eventually to a greater extent, from the caterpillar food source during nestling period. The concentrations of PCB 153 (2,2′,4,4′,5,5′-hexachlorobiphenyl, the most abundant in this study) was found in leaf material at ca. 1 ng/g, in caterpillars 10 ng/g, and in bird eggs 170 ng/g on an average and on a dry mass basis.