掺烧污泥型粉煤灰矿化封存二氧化碳

为了探索燃煤电厂掺烧市政污泥并利用该粉煤灰矿化封存CO₂的处理模式,研究掺烧污泥型粉煤灰矿化封存CO₂的能力和影响因素,并对该粉煤灰和矿化灰渣进行表征分析,同时研究其矿化反应机理。结果表明,掺烧污泥型粉煤灰中含有大量的反应活性较强的Ca、Mg元素,矿化封存CO₂能力强,最优反应条件为碳酸钠溶液质量浓度3%、CO₂流量200 mL·min⁻¹、粉煤灰投加量50 g·L⁻¹、温度100 ℃和反应时间80 min,此时单位粉煤灰矿化封存CO₂量可达到最大值125.05 mg·g⁻¹。反应产物矿化灰渣的微观形貌发生了较大改变,掺烧污泥型粉煤灰中钙离子大量溶出并经过碳酸化反应生成了碳酸盐沉淀。该处理模式有望大规模推动市政污泥的无害化、减量化和资源化并就近实现燃煤电厂碳减排,进一步拓宽粉煤灰大规模综合利用领域。     

芬顿与氧化钙联合处理填埋库污泥的力学特性

面对城市生活污泥填埋库容趋于饱和的现状,亟需研究开发城市生活污泥的减量化及资源化技术。以填埋库污泥和新鲜污泥为研究对象,进行岩土工程特性实验,发现填埋库污泥有机质含量及含水率远低于新鲜污泥。通过固结实验和直剪实验,分别对比、分析了未加药剂的填埋库污泥和药剂调质填埋库污泥的固结系数、渗透系数和抗剪强度变化规律。结果表明：填埋库污泥在pH为4时,芬顿试剂(硫酸亚铁和过氧化氢)的最佳配比为Fe²⁺=8%、H₂O₂=12%;当氧化钙投加量增加时,调质污泥的压缩指数减小,抗剪强度略微增大;考虑到联合处理后污泥的资源化利用、强碱性对环境的影响和处理成本,在实际污泥处理工程中,氧化钙投加量15%是较为合适的添加量,且效果优于常用的氯化铁药剂调制污泥。经芬顿与氧化钙联合处理的填埋库污泥抗剪强度满足填埋库要求,能够实现减容减量,对填埋库污泥后续资源化利用具有一定的指导意义。     

铁基污泥炭活化过硫酸盐调理污泥脱水

利用给水厂含铁污泥和污水厂污泥混合热解制备铁基污泥炭 (Iron-SBC) ,作为过硫酸盐活化剂,用于调理污泥脱水。研究了Iron-SBC的最佳制备条件及其活化PDS调理污泥脱水的效果,并探究其活化机制。结果表明,Iron-SBC最佳制备条件为给水厂含铁污泥和污水厂污泥比例3∶1、热解温度800 ℃、热解时间1 h。XRD、FT-IR及BET分析结果表明,与原混合污泥相比,Iron-SBC比表面积和孔容增大,表面负载了Fe⁰和FeO、Fe₂O₃、Fe₃O₄等铁的氧化物,并含有大量官能团。在活化PDS过程中,Iron-SBC表面的Fe⁰、铁的氧化物及官能团等均能有效活化PDS,产生SO₄⁻·和·OH自由基。XPS分析结果表明,Iron-SBC表面部分Fe²⁺被氧化为Fe³⁺,官能团C-C、C-OH和C=O等被氧化,并有Fe-O键生成。经Iron-SBC/PDS调理污泥后,CST、SRF和W_c分别由原泥的19.1 s、14.9×10¹² m·kg⁻¹和85.06%下降到8.4 s、5.4×10¹² m·kg⁻¹和73.48%。本研究结果可为含铁污泥和剩余污泥资源化及污泥深度脱水提供参考。     

污泥脱水滤液有机磷污染特征及强化去除

针对污水处理厂污泥脱水滤液有机磷污染现状,采用树脂分级、傅里叶红外光谱和气相色谱质谱等方法解析其污染特征和组分结构,进而开展强化去除研究,并初步探究OP的降解转化过程。结果表明：WX-A污泥脱水滤液OP和出水OP平均含量分别为10.1 mg·L⁻¹和0.16 mg·L⁻¹,脱水滤液的回流可能影响出水稳定;亲水性OP和疏水性OP平均含量分别为8.58 mg·L⁻¹和1.59 mg·L⁻¹,OP的生物利用度仅为23.8%,表明以难生物降解形态为主,进一步的组分解析结果验证了该推测;强化去除研究表明,最佳条件是O₃投加量为30 mg·L⁻¹、pH为12.0和H₂O₂投加量为1.5 mL,去除率高达82.9%。O₃/H₂O₂氧化技术可实现脱水滤液难降解OP的高效去除,从而保证出水达标排放。     

不同臭氧催化氧化体系处理老龄垃圾渗滤液的效果及能耗分析

老龄垃圾渗滤液因其成分复杂且可生化性差,故传统技术无法对其进行有效降解,且利用臭氧催化氧化体系处理垃圾渗滤液缺乏系统性评估报道。为解决上述问题,采用臭氧/过二硫酸盐(${{\rm{S}}_2}{{\rm{O}}_8^{2 - }}$,PS)、臭氧/过一硫酸盐(${\rm{HS}}{{\rm{O}}_5^ -} $,PMS)和臭氧/过氧化氢(H₂O₂)氧化体系,探讨了处理老龄垃圾渗滤液的可行性,考察了初始pH、温度、O₃及H₂O₂、Na₂S₂O₈、KHSO₅的投加量等因素对其处理效果的影响,并对其能源效率进行了分析。结果表明,优化条件下,O₃/PMS、O₃/H₂O₂和O₃/PS的单位数量级能耗(electrical energy per order,EE/O)分别为1 007.5、1 233.7、662.6 kWh·m⁻³,O₃/PMS氧化体系处理老龄垃圾渗滤液的效果与O₃/H₂O₂氧化体系相似,且优于O₃/PS。由综合处理效果与能耗评估结果可知,O₃/H₂O₂氧化体系最佳,在温度为25 ℃,pH=6,O₃和H₂O₂投加量分别为3 g·h⁻¹和2 125 mg·L⁻¹,反应时间为60 min条件下,能耗最低,EE/O降至443.9 kWh·m⁻³,且TOC去除率和反应速率常数分别为27.1%和0.005 3 min⁻¹,BOD₅/COD也由0.18增至0.26。综合上述结果,基于臭氧体系的高级氧化法能耗较高,可将臭氧催化氧化与低成本的生物处理技术相结合,从而实现对污染物高效经济降解。上述研究结果可为臭氧高级氧化技术的工程化应用提供参考。     

硫酸钙对含电镀污泥渣料水泥基材料性能的影响

为了提高危险废物电镀污泥的高值化利用程度，研究了掺加CaSO₄对含磨细粉(由电镀污泥协同建筑渣土高温处理渣料磨细得到)水泥基材料力学性能、微观结构特征及重金属浸出的影响及机理。结果表明：CaSO₄掺量(基于其在胶凝材料的质量占比)为0.6%时，其长期力学性能较优，含磨细粉水泥基材料养护60 d后抗压强度和抗折强度比未掺加CaSO₄时分别提升20.1%和22.2%。适量的CaSO₄可以补充含磨细粉水泥基材料基体中Ca²⁺含量，促进水泥和磨细粉中具有潜在水化活性的组分充分进行水化，同时使基体中生成更多的钙矾石填充孔隙，从而增强了基体结构密实度。研究还发现多余钙矾石的形成对重金属离子的固结起到了正向作用，适量的CaSO₄掺加能明显降低含磨细粉水泥基材料基体中有害重金属离子的浸出浓度。当CaSO₄掺量为0.6%时，含磨细粉水泥基材料养护28 d后，Cu、Ni、Zn的浸出率比未掺加CaSO₄时分别降低了33.6、31.0、...     

市政污泥处理处置技术经济性分析与评价

针对由污泥处理处置成本核算复杂导致的技术路线抉择困难的问题,从经济性角度对市政污泥土地、建材2类资源化利用路径典型技术路线进行评估,以帮助决策者权衡污泥处理处置全工艺链条的选择。通过生命周期成本评价方法评价了市政污泥处理处置典型技术路线,并利用敏感性分析方法对产业布局、土地利用季节性、建材产业生产波动与污泥处理处置成本的动态响应机制进行了探究。生命周期成本评价结果表明,土地利用路径生命周期成本为310~523元·t⁻¹,经济效益为100~255元·t⁻¹;建材利用的生命周期成本为123~238元·t⁻¹,经济效益为24~78元·t⁻¹。综合生命周期成本、经济效益以及绿色低碳原则,市政污泥处理处置路线应以土地利用为主、建材利用为辅。敏感性分析结果表明,在保证污泥处置含水率达标的前提下,降低污泥脱水率、缩短污水处理厂到污泥处理处置中心的运输距离有利于减少成本;好氧发酵-土地利用路线的污泥处置成本对污泥产品临时储存量的敏感度最高,超过30%,故有必要设置储存仓库以稳定成本波动。本研究结果可为市政污泥资源化利用路径选择、成本评估和产业布局优化有参考意义。     

基于化石碳的污泥干化焚烧处置碳排放分析

通常认为,污泥焚烧产生的CO₂是生物成因,不计入碳排放核算清单。但石油加工化学品的广泛使用会导致污泥化石碳质量分数增加。为符合实际情况,采用放射性碳测年法测定污泥化石碳质量分数。基于浙江省某2 500 t·d⁻¹污泥能源化利用热电联产项目运营数据,以1 t干基污泥 (DS) 为核算对象,构建碳排放及碳补偿核算方法,得出污泥干化焚烧-灰渣综合利用路径的碳排放因子,并与深度脱水-应急填埋路径的理论碳排放水平比较。结果表明,污泥有机碳中化石碳质量分数为64.94%,并非100%的生源碳。因此,污泥焚烧时计入碳排放核算清单的直接碳排放会增大,同时数据准确性和可靠度也有所增加。干化焚烧-灰渣综合利用路径中,1 t干基污泥的碳排放为0.32 tCO_2eq,约为深度脱水-应急填埋路径的1/6,更具减排潜力。本研究结果可为污泥低碳化处理处置提供参考。     

电絮凝耦合DSA或过氧化氢强化污泥脱水性能的比较与机理分析

为解决电絮凝法调理污泥期间电场无法有效破解污泥絮体、改善污泥脱水问题,分别将电絮凝与尺寸稳定阳极 (DSA,Dimensionally-stable anodes) 电极、H₂O₂进行耦合,比较和分析2种耦合工艺对污泥过滤性能、絮体破解程度、胞外聚合物 (EPS) 组分改变和污泥脱水性能的差异。结果表明,电絮凝耦合H₂O₂形成的间接氧化体系中,由于电致·OH在非均相体系中能无选择性地破坏污泥絮体、破解污泥细胞并降解胞外聚合物 (EPS),从而促使阳极释放的铁离子通过吸附架桥、网捕等作用与絮体碎片和EPS片段重聚并沉淀,使15 min内污泥毛细吸水时间 (CST) 和污泥含水率 (MC) 分别下降了73.9%和31.4%;然而电絮凝耦合DSA直接氧化法同期的污泥CST和MC仅分别下降了64.9%和26.4%。此外,间接氧化法可以同时降解松散结合层 (LB-EPS) 和紧密结合层 (TB-EPS) ,破坏EPS蛋白质亲水基团与水的作用力,并改善传统电化学法主要降解LB-EPS的不足,实现了提高电化学方法在同步污泥破解与沉降脱水方面的双重效能。本研究结果可为电化学预处理改善污泥脱水提供参考。     

Mn-Ce复合金属氧化物催化氧化甲苯性能

通过等体积浸渍法制备了一系列Mn-Ce/γ-Al₂O₃催化剂, 并考察不同CeO₂负载量对MnO₂/γ-Al₂O₃催化剂催化氧化甲苯性能的影响。利用XRD、N₂吸脱附曲线、TEM、H₂-TPR、XPS和O₂-TPD等方法表征催化剂比表面积、表面形貌及氧化还原性能。结果表明,CeO₂的负载一定程度上降低了MnO₂/γ-Al₂O₃催化剂的比表面积, 且催化剂仍保持介孔结构。CeO₂的存在增加了催化剂表面的化学吸附氧含量,其良好的储放氧能力促进了Mn³⁺向Mn⁴⁺的转化;Mn和Ce之间存在较强的协同作用, 与MnO_x相邻的CeO₂更容易打开Ce—O键释放活性氧, 加速氧化还原进程,Mn_0.6Ce_0.4/γ-Al₂O₃催化剂T₁₀和T₉₀与MnO₂/γ-Al₂O₃催化剂相比分别降低20和40 ℃。本研究可为VOCs催化氧化技术中低成本金属催化剂的开发提供参考。     

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.     

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.     

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.     

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.