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。     

高温条件下生物炭强化丙酸与乙酸产甲烷的动力学及热力学机制

针对生物炭强化互营产甲烷的动力学及热力学作用机制不明晰的问题,通过乙酸、丙酸的高温降解产甲烷批次实验,结合降解产甲烷动力学、微生物生长动力学和过程热力学分析,探究了生物炭强化乙酸、丙酸互营产甲烷的增效机制。结果表明,与对照组相比,生物炭加快了乙酸、丙酸互营产甲烷过程的降解速率和产甲烷速率,乙酸与丙酸的降解速率分别提高了8.4%和3.7%,产甲烷速率分别提高了31.3%和23.1%。微生物生长分析表明,生物炭可为微生物生长提供适宜的环境,同时也能促进微生物生长,添加生物炭使得丙酸降解过程的产甲烷微生物最大比生长速率提高了113.8%。反应过程热力学分析表明,生物炭降低了乙酸与丙酸互营产甲烷过程40.6%与19.4%的氢分压,从而降低了与氢分压相关反应的自由能,推动了种间氢转移 (interspecies hydrogen transfer,IHT) 反应的进行。此外,生物炭显著提升了体系内的电子传递效率,这可能是由于其自身氧化还原官能团所引发的直接种间电子转移 (direct interspecies electron transfer,DIET) 作用导致的,这不仅可以提高反应的电子转移效率,同时也能改善热力学效能,从而推动IHT反应并进一步强化互营产甲烷。生物炭可以通过促进微生物生长、改善热力学促进IHT以及强化DIET作用,共同提升互营产甲烷过程效能。本研究结果可为生物炭在厌氧消化中进一步的实际应用提供参考。     

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。     

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问题。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。     

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。     

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。     

长链脂肪酸对餐厨垃圾厌氧消化产甲烷的影响

为研究中温条件下长链脂肪酸（LCFA）的含量及代谢对餐厨垃圾厌氧消化过程的影响,考察了LCFA添加量分别为0、0.6、1.2、1.8、2.4、3和3.6 g·L-1条件下产沼气量、累积甲烷产量以及代谢中间产物挥发性脂肪酸/乙醇的浓度和组成。结果表明：在中温餐厨垃圾厌氧产甲烷的过程中,虽然LCFA也能够被微生物代谢转化生成甲烷,但LCFA的存在会对产甲烷过程造成一定程度的抑制作用;当其含量较低时抑制作用较为微弱,当其含量较高（>2.4 g·L-1）时,甲烷产量及产甲烷速率都会受到较大影响;特别是当LCFA含量高于3.6 g·L-1时,体系出现较强的抑制现象。通过实验累积值与理论甲烷产率的对比可以发现,LCFA含量越高的反应器中实验累积值/理论值的比值越低,表明有机物的转化效率越低。通过对厌氧过程中间产物的检测可知,LCFA含量越多的反应器中初期累积的挥发性脂肪酸浓度越高,当反应体系的LCFA浓度超过2.4 g·L-1时,累积的乙酸和丙酸浓度较高,丙酸降解过程和乙酸代谢产甲烷的过程受到一定程度的延滞和抑制作用,降解速率低于正常水平,厌氧发酵的能力和效率受到影响。     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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 in pinon pine (Pinus edulis) nuts from los alamos national laboratory lands and the dose from consumption

Abstract

One of the dominant tree species growing within and around the eastern portion of Los Alamos National Laboratory (LANL), Los Alamos, NM, lands is the pinon pine (Pinus edulis). Pinon pine is used for firewood, fence posts, and building materials and is a source of nuts for food—the seeds are consumed by a wide variety of animals and are also gathered by people in the area and eaten raw or roasted. This study investigated the (1) concentration of ³H, ¹³⁷Cs, ⁹⁰Sr, ^totU, ²³⁸Pu, ^{239, 240}Pu, and²⁴¹ Am in soils (0‐ to 12‐in. [31 cm] depth underneath the tree), pinon pine shoots (PPS), and pinon pine nuts (PPN) collected from LANL lands and regional background (BG) locations, (2) committed effective dose equivalent (CEDE) from the ingestion of nuts, and (3) soil to PPS to PPN concentration ratios (CRs). Most radionuclides, with the exception of ³H in soils, were not significantly higher (p < 0.10) in soils, PPS, and PPN collected from LANL as compared to BG locations, and concentrations of most radionuclides in PPN from LANL have decreased over time. The maximum net CEDE (the CEDE plus two sigma minus BG) at the most conservative ingestion rate (10 lb [4.5 kg]) was 0.0018 mrem (0.018 μSv); this is far below the International Commission on Radiological Protection (all pathway) permissible dose limit of 100 mrem (1000 μSv). Soil‐to‐nut CRs for most radionuclides were within the range of default values in the literature for common fruits and vegetables.     

Degradation and sorption of imidacloprid in dissimilar surface and subsurface soils

Degradation and sorption/desorption are important processes affecting the leaching of pesticides through soil. This research characterized the degradation and sorption of imidacloprid (1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazolidinimine) in Drummer (silty clay loam) and Exeter (sandy loam) surface soils and their corresponding subsurface soils using sequential extraction methods over 400 days. By the end of the incubation, approximately 55% of imidacloprid applied at a rate of 1.0 mg kg^?1 degraded in the Exeter sandy loam surface and subsurface soils, compared to 40% of applied imidacloprid within 300 days in Drummer surface and subsurface soils. At the 0.1 mg kg^?1 application rate, dissipation was slower for all four soils. Water-extractable imidacloprid in Exeter surface soil decreased from 98% of applied at day 1 to > 70% of the imidacloprid remaining after 400 d, as compared to 55% in the Drummer surface soil at day 1 and 12% at day 400. These data suggest that imidacloprid was bioavailable to degrading soil microorganisms and sorption/desorption was not the limiting factor for biodegradation. In subsurface soils > 40% of ¹⁴C-benzoic acid was mineralized over 21 days, demonstrating an active microbial community. In contrast, cumulative ¹⁴CO₂ was less than 1.5% of applied ¹⁴C-imidacloprid in all soils over 400 d. Qualitative differences in the microbial communities appear to limit the degradation of imidacloprid in the subsurface soils.