剩余污泥制备活性炭及其应用研究

以城市污水处理厂二沉池排出的剩余污泥为原料,采用不同活化方法制备活性炭,同时对比活化效果,研究了制备工艺条件对污泥活性炭吸附性能及产率的影响。结合比表面积、孔径分布和扫描电镜表征分析,对制备的污泥活性炭的性能进行评价,并探讨了污泥活性炭作为水处理吸附剂的去除效果。结果表明,以ZnCl₂为活化剂制备的活性炭性能较好,其最佳制备条件为：活化温度550℃,活化时间45 min,ZnCl₂浓度40％,固液比1∶2。制得的污泥活性炭的碘吸附值为496 mg/g,产率为51.8％,比表面积为301.4 m²/g,孔体积为0.37 mL/g,微孔体积为0.08 mL/g,平均孔径为5.78 nm。将该产品用于处理城市污水,投加量为0.8％,吸附平衡时间约为60 min时,对COD的去除率为81％,吸附容量为42.53 mg/g。     

污泥吸附剂对3种染料吸附动力学的研究

以污水厂脱水污泥、锯末和焦油的混合物为原料,选择ZnCl₂为活化剂制备出过渡孔发达、强度大的污泥吸附剂（S-AC）。借助BET、FT-IR等现代分析测试方法对污泥吸附剂进行表征,同时,研究了吸附剂对酸性大红、中性红和碱性品红吸附动力学行为。结果表明,制得的污泥吸附剂BET比表面积为358 m²/g,强度大于89%。吸附剂的动力学数据均符合伪二阶动力学方程、液膜扩散方程和颗粒内扩散方程,其中液膜扩散为吸附剂对酸性大红吸附过程的主控步骤,颗粒内扩散为吸附剂对中性红和碱性品红吸附过程的主控步骤。     

污水污泥裂解及其性能的研究

以碘吸附值为裂解残渣吸附性能的指标,通过单因素实验和正交实验,确定了制备裂解残渣的最佳工艺条件,并对残渣的表面元素组成、孔结构组成、晶相组成和吸附性能等性质进行了表征。结果显示：以浓度均为5 mol/L的ZnCl₂和H₂SO₄作活化剂、复配比2∶1、活化温度600℃、活化时间1 h、固液比1∶2.5,制得的裂解残渣酸洗后碘值平均值可达892.8 mg/g;用制备的裂解残渣对苯酚废水进行处理,室温下振荡5 min,苯酚去除率即可达到87.9%,且符合Langmuir吸附等温线方程和Freundlich吸附等温线方程。     

ZnCl2法污泥含炭吸附剂对模拟烟气中气态汞的吸附

采用改进的ZnCl₂化学活化法制备污泥含炭吸附剂,利用EDS以及氮吸附等多种测试手段对所制得的污泥含炭吸附剂进行表征,并利用其处理模拟烟气汞污染物,实验结果表明,污泥含炭吸附剂对Hg0的吸附包括物理吸附作用和化学吸附作用,以物理吸附作用为主;随着Hg0入口浓度的提高,污泥含炭吸附剂的Hg0饱和吸附容量增大;随着吸附反应温度的升高污泥含炭吸附对Hg0的吸附作用减弱;在吸附反应温度125℃,Hg0入口浓度60.4 μg/m³,污泥含炭吸附剂和选定的活性炭对Hg0的吸附容量分别为81.2 μg/g和53.8 μg/g,污泥含炭吸附剂对Hg0的吸附作用好于选定的活性炭。     

NO2对颗粒污泥甲烷化动力学特性的影响

采用间歇试验方法，以乙酸和乙酸盐混合物为基质，对取自EGSB反应器具有厌氧甲烷化反硝化与厌氧氨氧化活性的颗粒污泥的甲烷化动力学以及NO₂影响进行研究。无NO₂时，最大比基质降解速率为0.158 mg COD/mg VSS·h，半饱和常数为464 mg COD/L，甲烷的产率系数为0.254 mL CH₄/mg COD。添加微量NO₂对甲烷化有抑制作用，抑制程度随着微量NO₂浓度的增高而增大，在NO₂浓度为30.36 mg/m³、50.6 mg/m³、101.2 mg/m³、202.4 mg/m³和303.6 mg/m³条件下，甲烷化抑制程度分别为7.40％、11.87％、27.56％、39.75％和43.24％，外推得NO₂的甲烷化半抑制浓度IC₅₀值为383.8 mg/m³。NO₂气氛下甲烷化动力学可用反竞争性抑制动力学进行描述，最大比基质降解速率为0.148 mg COD/mg VSS·h，半饱和常数为396 mg COD/L，NO₂抑制系数为250 mg/m³。     

污泥基活性炭吸附Cu2+的应用研究

以城市污水处理厂剩余污泥为原料,以ZnCl₂为活化剂制取污泥基活性炭。以此污泥基活性炭为吸附剂,对含Cu²⁺的废水进行了吸附实验研究。考察了溶液pH值、Cu²⁺的起始浓度对Cu²⁺离子吸附量的影响;利用等温吸附实验作出吸附等温线,并考察了污泥基活性炭吸附剂吸附Cu²⁺的动力学方程。实验结果表明,污泥基活性炭对Cu²⁺具有良好的吸附性能。吸附的最佳pH值为5;吸附符合Langmuir和Freundlich吸附等温方程,吸附为优惠吸附,吸附量随着吸附质溶液浓度的增加而增大;吸附平衡时间为4 h,吸附动力学符合二级动力学方程。     

微量NO2对厌氧氨氧化甲烷化反硝化耦合影响的动力学分析

采用批试验方法,研究微量NO₂对颗粒污泥厌氧氨氧化、甲烷化和反硝化耦合的影响。基于Haldane模型建立了厌氧氨氧化的NO₂强化函数,估计了强化函数中的最大强化系数（30.55）、NO₂半饱和常数（1.96 mg/L）、NO₂抑制常数（0.0082 mg/L）和基础速率系数（0.0314）。微量NO₂对甲烷化和反硝化动力学可用反竞争性抑制动力学方程进行描述。甲烷化的最大比乙酸盐去除速率为0.15 mg COD/（mg VSS·h）,乙酸盐半饱和常数为395 mg COD/L,NO₂抑制系数为0.623 mg/L。反硝化的亚硝酸盐氮最大去除速率0.00685 h^-1,亚硝酸盐氮半饱和常数 0.214 mg/L,NO₂抑制系数为22.4 mg/L。试验中大部分的NOx气体物质出现损失。     

污泥回流分离工艺（RSSP）除磷脱氮试验研究

介绍了一种新型的脱氮除磷工艺——回流污泥分离工艺（return sludge separate process）,及其运行情况。该工艺在传统的厌氧缺氧好氧（A²/O）的模式下,针对硝酸盐对厌氧释磷的抑制问题进行改进,提出回流污泥的气浮浓缩分离方案,以提高系统的脱氮除磷效果。研究结果表明,在进水COD为250～400 mg/L,NH⁺₄-N为30～45 mg/L,PO^3-₄-P为8～10 mg/L左右时,该工艺对NH⁺₄-N和PO^3-₄-P的去除率分别可达79.3%和95%。该系统与A²/O的平行比较数据表明,该系统能够提高氮磷综合处理效率,解决A²/O处理工艺中存在无效释磷和硝酸根抑制问题。     

脱水污泥制备含炭吸附剂及其应用研究

采用热解炭化法、物理活化法、化学活化法制备污泥含炭吸附剂,通过静态吸附实验研究各种影响污泥含炭吸附剂吸附性能的因素.实验结果表明,采用化学活化法制得的污泥含炭吸附剂吸附性能最好,在以ZnCl2为活化剂、锯末添加剂投加量为脱水污泥质量的1%、ZnCl2为3 mol/L、活化温度为450 ℃、活化时间为1.5 h、固液质量比(干污泥与活化剂溶液的质量比)为1:4的最佳制备条件下,制得的污泥含炭吸附剂碘吸附值在520 mg/g以上,产物收率>60%,比表面积>230 m2/g,总孔容积为0.35 mL/g,其中微孔容积为0.08 mL/g,中孔容积为0.23 mL/g.利用其处理城市污水,其对COD、色度、TP的去除率好于选定的商品颗粒活性炭.     

污泥渗水砖的制备研究

结合压制成型和传统的烧结砖工艺,实验以城市生活污泥、黄河淤泥、煤矸石及砂为原料,制备渗水铺地砖。通过正交试验得到最优工艺参数为w_{(黄河淤泥)}∶ww_(煤矸石)∶w_(污泥)∶w_(砂)＝33％∶22％∶15％∶30％、成型压力为20 MPa、烧结温度为1 100℃、保温时间为1.5 h,骨料砂的粒径为1～2 mm。制备的成品抗压强度为21.8 MPa,渗水系数为1.03×10^－2 cm/s。并对成型压力及烧结温度对渗水砖抗压强度及渗水系数的影响进行了讨论。     

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.     

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.     

Radionuclides in deer and elk from Los Alamos national laboratory and the doses to humans from the ingestion of muscle and bone

Abstract

This paper summarizes radionuclide concentrations (³H, ⁹⁰Sr, ¹³⁷Cs, ²³⁸Pu, ^239,240Pu, ²⁴¹Am, and ^totU) in muscle and bone tissue of mule deer (Odocoileus hemionus) and Rocky Mountain elk (Cervus elaphus) collected from Los Alamos National Laboratory (LANL), Los Alamos, New Mexico, lands from 1991 through 1998. Also, the committed effective dose equivalent (CEDE) and the risk of excess cancer fatalities (RECF) to people who ingest muscle and bone from deer and elk collected from LANL lands were estimated. Most radionuclide concentrations in muscle and bone from individual deer (n = 11) and elk (n = 22) collected from LANL lands were either at less than detectable quantities (where the analytical result was smaller than two counting uncertainties) and/or within upper (95%) level background (BG) concentrations. As a group, most radionuclides in muscle and bone of deer and elk from LANL lands were not significantly higher (p<0.10) than in similar tissues from deer (n = 3) and elk (n = 7) collected from BG locations. Also, elk that had been radio collared and tracked for two years and spent an average time of 50% on LANL lands were not significantly different in most radionuclides from road kill elk that have been collected as part of the environmental surveillance program. Overall, the upper (95%) level net CEDEs (the CEDE plus two sigma for each radioisotope minus background) at the most conservative ingestion rate (50 lbs of muscle and 13 lbs of bone) were as follows: deer muscle = 0.22 mrem y^‐1 (2.2 μSv y^‐1), deer bone = 3.8 mrem y^‐1 (38 μSv y^‐1), elk muscle = 0.12 mrem y^‐1 (1.2 μSv y^‐1), and elk bone = 1.7 mrem y^‐1 (17 μSv y^‐1). All CEDEs were far below the International Commission on Radiological Protection guideline of 100 mrem y^‐1 (1000 μSv y^‐1), and the highest muscle plus bone net CEDE corresponded to a RECF of 2E‐06, which is far below the Environmental Protection Agency upper level guideline of 1E‐04.     

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.