基于响应面法优化MAP法处理垃圾渗滤液工艺的研究

利用单因素实验以及响应面法(response surface methodology,RSM),对磷酸铵镁法(magnesium ammonium phosphate,MAP)去除垃圾渗滤液氨氮的影响因素进行了分析和探讨。考察了pH值为8.0～11.0、n(Mg)∶n(N)摩尔比为0.8～1.6、n(P)∶n(N)摩尔比为0.8～1.3条件下,分析氨氮去除率的变化,用Design-Expert软件处理实验数据,得到了二次响应曲面模型以及优化的水平值。基于经济和操作简便性的考虑,pH值由优化水平的8.3调整为9.5,n(Mg)∶n(N)、n(P)∶n(N)摩尔比取优化水平分别为1.40、1.19,氨氮去除率平均值为92.2%,虽然该条件比最佳条件下的氨氮去除率降低了2个百分点,但从操作的难易程度以及经济性方面,体现了其优势。通过X衍射与电镜扫描分析沉淀物质的成分与晶形,表明大部分沉淀物质为磷酸铵镁。     

赤泥晶种法磷酸铵镁结晶工艺模拟废水磷的回收

以赤泥为晶种,研究不同工艺条件对磷酸铵镁(MAP)结晶法回收模拟废水中磷的影响。结果表明,在投加赤泥(60～80目)8 g/L,搅拌速度为180 r/min,搅拌时间30 min,沉淀时间30 min,N∶Mg∶P=1∶1∶1的条件下磷酸根离子的回收率随初始磷酸盐浓度的增加而增大,在初始磷酸盐浓度小于90 mg/L时增幅较大,初始磷酸盐浓度大于90 mg/L后增幅减小;pH值对磷酸根离子的回收率影响显著,结合铵根离子、镁离子的回收率变化,pH值为9.5时最优;磷酸根离子的回收率随着Mg∶P摩尔比和N∶P摩尔比增大而呈上升趋势,当Mg∶P摩尔比为1.4∶1、N∶P摩尔比为4∶1时,磷酸盐的回收率可达97.9%。运用扫描电子显微镜(SEM)、X射线能谱仪(EDS)和X射线衍射仪(XRD)对最优工艺条件下的结晶产物进行了表征,表明磷主要以磷酸铵镁形态回收。     

磷酸铵镁沉淀法预处理垃圾渗滤液

探讨了用磷酸铵镁沉淀法预处理垃圾渗滤液时,沉淀剂种类、pH值、物质摩尔配比和反应时间等因素对氨氮去除效果的影响。得出了处理氨氮浓度为2 677.34 mg/L的垃圾渗滤液时,在兼顾所用镁盐量尽量低和处理出水氨氮或磷酸盐的残留量都比较低的较佳实验条件为:沉淀剂种类为:MgSO4.7H2O和Na2HPO4.12H2O,反应时间为20 min,pH=9.5,n(Mg)∶n(P)∶n(N)=1.3∶1.15∶1.0。在较佳实验条件下,垃圾渗滤液的NH3-N去除率为97.05%,处理出水PO34--P含量为8.35 mg/L,NH3-N含量为75.86 mg/L。对所得沉淀物进行了成分分析和X-衍射光谱、扫描电镜表征,表明大部分沉淀物为磷酸铵镁物质。     

铁炭微电解-MAP沉淀法联合预处理垃圾渗滤液

采用铁炭微电解-磷酸氨镁(MAP)沉淀法对垃圾渗滤液进行预处理,实验结果表明,铁炭比为5∶1,pH值为3,反应时间为3 h时,铁炭微电解的COD的去除率为47.5%;在投加药剂n(Mg2+)∶n(PO43-)∶n(NH4+)为1.4∶1∶1,pH值为9,反应时间为1 h的条件下,垃圾渗滤液氨氮去除率达到79.7%。     

混凝沉淀-Fenton-NaClO氧化深度处理垃圾渗滤液

用混凝沉淀-Fenton-NaClO氧化联合深度处理垃圾渗滤液,利用单因素变量法得出:混凝实验在PFS投加量为1.2g/L、pH=6、搅拌时间为30min的条件下进行,COD、氨氮和色度的去除率分别达到56.60%、15.62%和56.52%;混凝出水在初始pH为4、H2O2投加量为80mmol/L、n(H2O2)∶n(F2+)比为1∶1、反应时间为60min的条件下进行Fenton氧化,COD、氨氮和色度的去除率分别达到71.38%、21.43%和95.24%;Fenton氧化出水在pH为6、NaClO投加量为60mmol/L、反应时间为60min的条件下进行NaClO氧化,COD和氨氮去除率分别为83.42%和99.57%;联合工艺COD、氨氮和色度去除率分别为96.68%、99.69%和98.04%,出水浓度分别为63mg/L、0.47mg/L和18倍,均可满足《生活垃圾填埋污染控制标准(GB16889-2008)》中规定的排放标准。     

赤泥晶种法诱导磷酸铵镁结晶回收模拟废水中磷的可行性研究

对赤泥的理化性质进行了分析,探索了以赤泥为晶种磷酸铵镁(MAP)结晶法从模拟废水中回收磷工艺。结果表明,经过研磨的赤泥颗粒属无孔物质或者大孔物质;将赤泥溶于水时有碱液和离子溶出,赤泥的主要化学成分为Ca、Al、Si和Mg等元素。投加赤泥晶种有利于磷酸铵镁结晶的形成。在初始磷酸盐浓度为90 mg/L、N∶Mg∶P摩尔比为1∶1∶1、不调节pH值、搅拌时间30 min、搅拌速度180 r/min、沉淀时间30 min条件下,赤泥粒径为60～80目、投加量为8 g/L时,以赤泥作为晶种诱导磷酸铵镁结晶回收磷的效果最优。干燥晶种的使用次数对磷酸根离子的回收率影响不大。所得结晶产物是一种很好的缓释肥。     

磷酸铵镁法处理焦化厂高浓度氨氮废水

介绍了酸铵镁(magnesiumammoniumphosphate,MAP)法处理高浓度氨氮废水的技术,研究了药剂配比、反应pH值以及药剂选择等因素对氨氮去除率的影响。试验结果表明,当在剩余氨水中投加MgCl2·6H2O和Na2HPO4·12H2O药剂,Mg2+∶NH+4∶PO3-4的摩尔比为1.4∶1∶0.9,反应pH值为8.5~9.5的条件下,原水的氨氮浓度可由2000mg/L降到15mg/L。并通过对反应沉淀物的结构成分分析,探讨了MAP作为有效缓释肥开发利用的可行性。     

甲胺生产废水中氨氮资源化的试验研究

利用MgSO4·7H2O和Na2HPO4·12H2O作为试验药剂,通过正交试验和单因素优化试验,对化学沉淀法处理甲胺生产废水中氨氮的工艺条件进行优化.结果表明,在pH=9.4、反应时间15 min、搅拌速度150 r/min、Mg:N(摩尔比值)=1.1、P:N(摩尔比值)=1.0时,化学沉淀法处理300 mL甲胺生产废水,氨氮去除率维持在92%以上,COD去除率可达37%以上.同时为验证工艺条件适应性和沉淀物(MgNH4PO4)作为农作物肥料使用的价值性,对最优条件下得到的沉淀物进行研究.与MgNH4PO4纯度为100%相比,沉淀物MgNH4PO4纯度达到86%以上.因此,化学沉淀法处理氨氮不仅具有良好的效果,而且得到的MgNH4PO4含有较高N、P,可以用作农作物肥料.     

磁性聚合硫酸铁混凝—NaClO氧化处理垃圾渗滤液

采用化学还原法制备的纳米Fe3O4与聚合硫酸铁(PFS)复合制备磁性聚合硫酸铁(MPFS)混凝剂,利用MPFS混凝—NaClO氧化组合工艺处理垃圾渗滤液,用单因素实验确定最佳运行参数。结果表明:MPFS对COD的去除效果优于PFS,在纳米Fe3O4与PFS的质量比为1∶3、MPFS投加质量浓度为3.5g/L、pH为6.5、混凝时间为25 min时,混凝效果最佳;混凝出水在NaClO投加摩尔浓度为140mmol/L、pH为6.0、氧化温度为50℃、氧化时间为65 min时,氧化效果最佳。在最佳运行条件下,MPFS混凝—NaClO氧化组合工艺对垃圾渗滤液COD、色度和氨氮的去除率分别达到88.2%、77.4%、80.3%。     

磷酸铵镁沉淀法回收尿液中N和P的实验研究

以源分离尿液为研究对象,在氨氮含量为2 850 mg N/L的微稀释尿液中,投加MgCl2·6H2O和Na2HPO4·12H2O,以磷酸铵镁沉淀法回收N和P。通过正交实验确定影响磷酸铵镁沉淀反应的因素依次为: pH值、PO3-4∶NH+4、Mg2+∶NH+4、温度。在搅拌速度=100 r/min、反应温度=15℃、反应时间=10 min的条件下,实验分别考察了pH值、PO3-4投加量、Mg2+投加量对磷酸铵镁沉淀法去除N、P的影响,结果表明最佳工艺条件为pH=9.5,Mg2+∶NH+4∶PO3-4=1.3∶1.0∶1.0。最佳工艺条件下尿液中的NH+4-N可从2 850 mg/L降低到约125 mg/L;剩余磷酸盐浓度约7 mg/L。SEM及XRD分析表明,沉淀物的主要成分为呈斜方晶系的磷酸铵镁晶体。     

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.