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、PO34-∶NH4+、Mg2+∶NH4+、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、PO43-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+∶NH4+∶PO34-=1.3∶1.0∶1.0。最佳工艺条件下尿液中的NH4+-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。     

诱导结晶法去除地下水中氟离子

针对现行高氟地下水处理工艺中存在的工艺复杂、运行管理困难等问题,提出采用诱导结晶法除氟。其技术核心是在高氟水中投加氟磷灰石作为晶种,并投加磷酸盐和钙盐使水中氟离子在晶种表面生成氟磷酸钙(Ca10(PO4)6F2)结晶。通过单因素实验得出最佳工艺条件:投加8g/L氟磷灰石,并投加NaH2PO4和CaCl2,使钙离子、磷酸根离子和氟离子的摩尔比为10∶5∶1,搅拌速度为100 r/min,反应时间1 h。反应中磷酸根离子和钙离子的利用率分别达到98%和25%以上。电子扫描显微镜(SEM)表征晶种在参与反应后,表面有结晶生成。研究表明,采用诱导结晶法可将水中氟离子浓度从5~10 mg/L降至1 mg/L以下,达到饮用水水质标准。     

磷酸铵镁碱促(Mg(OH)_2)热解产物氨氮去除性能

磷酸铵镁热解循环技术可以有效降低磷酸铵镁结晶技术的药剂费用。同时,在磷酸铵镁热解过程中添加Mg(OH)2碱促媒介,能阻止磷酸氢镁向焦磷酸镁的转化,并降低热解产物氨氮去除过程中上清液磷酸盐的残留。在Mg(OH)2∶NH+4摩尔比为1∶1,热解温度为110℃条件下,热解产物沉氨效率接近84%,上清液磷酸盐残留量为0.02 mg/L。     

诱导结晶法去除地下水中氟离子简

针对现行高氟地下水处理工艺中存在的工艺复杂、运行管理困难等问题，提出采用诱导结晶法除氟。其技术核心是在高氟水中投加氟磷灰石作为晶种，并投加磷酸盐和钙盐使水中氟离子在晶种表面生成氟磷酸钙（Ca₁₀（PO₄） ₆F₂）结晶。通过单因素实验得出最佳工艺条件：投加8g/L氟磷灰石，并投加NaH₂PO₄和CaCl₂，使钙离子、磷酸根离子和氟离子的摩尔比为10：5：1，搅拌速度为100 r/min，反应时间1 h。反应中磷酸根离子和钙离子的利用率分别达到98%和25%以上。电子扫描显微镜（SEM）表征晶种在参与反应后，表面有结晶生成。研究表明，采用诱导结晶法可将水中氟离子浓度从5~10 mg/L降至1 mg/L以下，达到饮用水水质标准。     

MAP沉淀法去除渗滤液中低浓度氨氮

考察了pH值、搅拌时间、Mg∶N和N∶P摩尔比对鸟粪石化学沉淀法(MAP)去除垃圾渗滤液中低浓度氨氮的影响,使用Design Expert 7.1.3进行3水平4因素响应曲面中心复合设计优化实验,并通过二次多项式拟合和参数优化,得到:当pH为10,搅拌时间为30 min,Mg∶N摩尔比为1.41,N∶P摩尔比为1.34时,氨氮去除率(Y1)可以达到最大值71.2%,体系中的残留PO34--P浓度(Y2)趋近于零,达到我国《生活垃圾填埋场污染控制标准排放标准》的排放标准。此外,X射线衍射图谱的分析表明大部分沉淀物质为磷酸铵镁。     

赤泥投加控制河道底泥磷释放的影响因素

通过对不同赤泥投加比例下河道底泥磷释放作用的研究,发现底泥中铁铝磷与钙磷的比值(Fe/Al-P∶Ca-P)、铁磷比(Fe∶TP)及有机质含量(OM)是赤泥能否应用于河道底泥磷释放控制中的决定性因素。实验结果表明,只有当河道底泥中Fe/Al-P∶Ca-P小于0.88,Fe∶TP小于16.1,且有机质含量低于1.87%时,投加适量赤泥才能起到抑制河道底泥内源磷释放的作用;反之,赤泥的投加则有可能促进底泥内源磷的释放。在实际工程应用中,推荐赤泥与底泥的接触时间不低于7d,从而使赤泥的效能发挥到最佳状态。     

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。     

改性蛭石结合鸟粪石沉淀法回收垃圾渗滤液中氨氮的实验研究

研究了使用氯化镁改性蛭石,利用磷酸铵镁沉淀的原理,在垃圾渗滤液中按比例加入PO43-,处理垃圾渗滤液中氨氮的同时,在蛭石上生成磷酸铵镁沉淀,以便于磷酸铵镁沉淀的回收利用。结果表明,筛取蛭石粒径为60～80目,配制浓度20%的氯化镁溶液浸泡改性蛭石20 min,取25 g改性蛭石,100 mL垃圾渗滤液调节pH为9,按n(NH4+)∶n(PO34-)=1∶1.2的比例加入PO43-离子,垃圾渗滤液中氨氮去除率为85.06%,实验并对磷酸铵镁沉淀进行了结构成分分析,为垃圾渗滤液中氨氮的处理及磷酸铵镁沉淀的回收提供了一种新的方法。     

pH对磷酸铵镁结晶介稳区、诱导期和反应速率的影响

以p H为控制参数,利用自组装激光测量装置测定了4、20、30和40℃时,磷酸铵镁在水溶液中的溶解度、超饱和度和介稳区宽度等基础数据,分析了不同温度和p H下磷酸铵镁结晶介稳区的变化规律,考察了p H对磷酸铵镁结晶诱导期和结晶反应速率的影响。结果表明,提高溶液的p H,可降低磷酸铵镁在水溶液中的溶解度和超饱和度,但同时磷酸铵镁结晶介稳区宽度有所增加;磷酸铵镁的溶解度和超饱和度随温度的升高呈现上升的趋势,而磷酸铵镁的结晶介稳区宽度则随温度的升高而变窄,提高溶液中MAP的物质浓度也会压缩结晶介稳区宽度;随着溶液p H的升高,磷酸铵镁的结晶诱导期逐渐缩短,同时其结晶反应速率也有明显的提升。在磷酸铵镁结晶除磷过程中,可以通过控制p H来优化反应工艺条件,促进磷酸铵镁结晶反应的进行。     

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.     

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.     

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.     

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.     

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.     

Knowledge transfer initiative between molecular biologists and environmental researchers and regulators

A Natural Environment Research Council (NERC) funded Knowledge Transfer (KT) workshop was held in the United Kingdom (UK) to identify the needs and opportunities in the application of molecular biology and ‘omics’ techniques to environmental monitoring and risk assessment. Attendees highlighted a lack of effective communication between end-users and researchers as well as difficulties with data interpretation as reasons behind the slow uptake of molecular biology and omics techniques. A number of promising areas in which new techniques could be implemented at a practical level in the very near future were identified, thereby raising the profile of these recent technologies and providing vital proof of concept work. Molecular taxonomy, bacterial source tracking and pre-screening of chemicals for potential toxicities were all viewed as areas in which omics and molecular techniques could have immediate value, with the aim of reducing cost, increasing efficiency and providing more comprehensive data of improved quality.     

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.     

Sorption and predicted mobility of herbicides in Baltic soils

This study was undertaken to determine sorption coefficients of eight herbicides (alachlor, amitrole, atrazine, simazine, dicamba, imazamox, imazethapyr, and pendimethalin) to seven agricultural soils from sites throughout Lithuania. The measured sorption coefficients were used to predict the susceptibility of these herbicides to leach to groundwater. Soil-water partitioning coefficients were measured in batch equilibrium studies using radiolabeled herbicides. In most soils, sorption followed the general trend pendimethalin > alachlor > atrazine～ amitrole～ simazine > imazethapyr > imazamox > dicamba, consistent with the trends in hydrophobicity (log K_ow) except in the case of amitrole. For several herbicides, sorption coefficients and calculated retardation factors were lowest (predicted to be most susceptible to leaching) in a soil of intermediate organic carbon content and sand content. Calculated herbicide retardation factors were high for soils with high organic carbon contents. Estimated leaching times under saturated conditions, assuming no herbicide degradation and no preferential water flow, were more strongly affected by soil textural effects on predicted water flow than by herbicide sorption effects. All herbicides were predicted to be slowest to leach in soils with high clay and low sand contents, and fastest to leach in soils with high sand content and low organic matter content. Herbicide management is important to the continued increase in agricultural production and profitability in the Baltic region, and these results will be useful in identifying critical areas requiring improved management practices to reduce water contamination by pesticides.