SAPS处理酸性矿山废水的模拟应用研究

根据硫酸盐还原菌(SRB)的生物矿化原理设计了一套连续碱度产生系统(SAPS)反应器,以市政污水处理厂的活性污泥为SRB提供源,南方常见的香芋柄为有机物碳源,选用石灰石为反应器中碱度层填充物,进行实验室模拟SAPS处理酸性矿山废水(AMD)的应用研究,实验结果表明,SAPS处理酸性矿山废水的方法是具有技术可行的:SRB利用有机碳源生长代谢,产生碱度、还原SO2-4和降解COD。最终废水p H从进水4.0左右上升到出水7.0左右;出水COD降低到约200 mg/L;SO2-4还原为各种硫化物,其还原率约为61%;不同金属离子在有机层和碱度层发生反应产生沉淀,其中Fe2+、Cu2+和Zn2+的去除效率分别约为76%、78.5%和82%,而主要靠物理吸附作用的Mn2+去除率较低;初次模拟SAPS运行到56 d时,系统最终因有机碳源不足而各项指标不再改变。     

玉米芯为碳源固定化硫酸盐还原菌污泥代谢特性

以聚乙烯醇为包埋载体,饱和硼酸为交联剂,制作了玉米芯为内聚缓释碳源的固定化硫酸盐还原菌污泥颗粒。通过厌氧批实验研究了在模拟酸性矿山废水(AMD)条件下玉米芯含量、初始SO2-4和Mn2+负荷以及p H对固定化颗粒代谢特性的影响,初步分析了固定化颗粒处理AMD的机理及可行性。实验结果表明,玉米芯在微生物作用下快速水解并产生有机物累积后,固定化颗粒才能迅速还原SO2-4,且玉米芯含量≤5%时硫酸盐还原率与玉米芯含量成正相关,玉米芯的水解会略微降低体系的p H;初始SO2-4浓度通过改变体系中COD/SO2-4和颗粒内外的浓度差影响固定化颗粒的代谢过程,而对玉米芯水解的影响不显著。初始p H为2~6和Mn2+浓度≤55 mg/L时对固定化颗粒活性抑制作用不明显,初始p H越低越利于玉米芯的水解和颗粒形成良好的孔隙结构;颗粒对Mn2+的去除机理是一种不依赖微生物活性的快速化学吸附作用,可用伪二级动力学模型描述吸附过程(R2=0.995)。     

混合硫酸盐还原菌代谢过程的影响因素

采用间歇实验,研究不同初始pH、Fe2+投加量、COD/SO24-及NO3-/SO24-比值等因素对SRB还原硫酸盐效果与速率的影响。实验结果表明:中性条件下(pH=7),硫酸盐的去除效果最佳,去除率达到84.66%,还原速率为15.07 mg/(L.h),在初始pH为4～9的范围内,体系具有较好的缓冲能力;当COD/SO24-比值为3时,反应209 h,硫酸盐去除率为85.33%,还原速率为8.16 mg/(L.h),随着反应的进行,体系的pH趋于中性;当溶液中有亚铁离子存在,且浓度为0～200 mg/L时可促进硫酸盐还原菌的生长,提高其对硫酸盐的去除率;NO3-对硫酸盐的还原有明显的抑制作用。     

甘蔗渣为缓释碳源负载SRB处理模拟矿山淋滤水

以甘蔗渣为缓释碳源及载体,负载硫酸盐还原菌(SRB)处理含低浓度Cu~(2+)离子的模拟矿山淋滤水,研究了缓释碳源、p H、ORP、SO2-4、COD等对矿山淋滤水中Cu~(2+)去除效果的影响,并探讨了处理过程中铜元素的形态及归趋模式。结果表明:在处理过程中p H呈现缓慢升高趋势,ORP全部降至-100 m V以下;硫酸根还原率可达92.4%;甘蔗渣作为缓释碳源释放稳定,COD可稳定保持200~300 mg/L之间;负载在甘蔗渣载体上的菌群可耐受高浓度Cu~(2+)的毒性抑制,并利用缓释碳源甘蔗渣释放出的小分子物质将硫酸根持续还原;至实验期结束,20 mg/L的Cu~(2+)浓度降至0.5 mg/L以下,较高浓度的Cu~(2+)拟通过多级反应器串联进行逐级去除;SO2-4和Cu~(2+)的反应速率比表明,SRB每还原约15 mg SO2-4,就有1 mg Cu~(2+)得到去除;Cu~(2+)主要是以硫化物的形式得以去除。     

玉米芯为碳源铁屑协同生物麦饭石活化颗粒的硫酸盐还原动力学及其锰离子响应实验

利用聚乙烯醇和饱和硼酸,添加30%SRB污泥、5%玉米芯、2%铁屑和3%麦饭石包埋制备内聚营养源的SRB固定颗粒,将完全活化的SRB颗粒作为研究对象,探究活化颗粒对SO2-4反应动力学过程及其对高浓度Mn2+离子响应机制。结果表明:活化颗粒还原SO2-4的过程符合一级动力学模型,最大还原速率为94.88 mg/(L·h);高浓度Mn2+可抑制活化颗粒的p H提升能力,延缓碳源的水解速率及SO2-4的还原速率,而不会抑制水解过程并延长缓滞期,更不能降低最终去除效果。可见,以玉米芯为碳源的铁屑协同生物麦饭石颗粒处理煤矿酸性废水是有效并可行性的。     

微氧环境下无色硫细菌和硫酸盐还原菌脱硫

通过间歇曝气形成微氧环境让SRB和CSB实现共生,使含硫酸盐有机废水中硫酸根最终转化成单质硫达到脱硫目的.研究考察了曝气量对SRB还原和CSB氧化的影响,确定了合适的曝气强度和水力停留时间,使得单质硫占系统内总硫比值最大.实验结果显示,在进水COD/SO42-=2000/1500 mg/L、曝气开关时间为2 s/2 min、生化时间为10 h时,单质硫产率最大,为89.53％,SO42-浓度降至最低值72.7 mg/L,还原率达95.1％,此时脱硫效果较好.     

Fe~0协同生物麦饭石的PRB系统井下原位处理煤矿酸性废水

针对煤矿酸性废水(AMD)具有污染组分多、危害程度严重、地面处理成本高等特点,以固定SRB污泥的生物麦饭石作为PRB活性填料,并添加Fe0构建生物-非生物协同去污的新型PRB井下原位修复系统,对AMD开展了连续动态、变负荷的模拟修复研究。实验结果表明,3个动态柱对p H均具有较强的调节能力,同时仅以麦饭石作为活性填料的PRB-3对Fe2+、Mn2+、NH3-N具有较好的去除效果,最大去除速率分别为45.77、9.23和12.10 mg/(L·d);以Fe0协同生物麦饭石的PRB-2在碳源充足时对SO2-4、Fe2+、Mn2+、NH3-N最高去除速率分别为552.29、57.64、14.51和7.05mg/(L·d),而相同条件下只以生物麦饭石作为活性填料的PRB-1对上述污染物的最高去除速率分别为446.62、57.20、10.87和3.53 mg/(L·d);应用PRB-2系统处理AMD不仅可以实现多种污染物的同步去除,还能实现无外加碳源的井下原位长效修复。     

内聚乙醇固定化硫酸盐还原菌同步处理废水中硫酸盐和铬

含Cr(Ⅵ)和硫酸盐废水对生态环境构成严重威胁。以聚乙烯醇和海藻酸钠为交联剂制备一种内聚已醇固定化硫酸盐还原菌(SRB)小球(简称固定化小球),探讨这种新型吸附剂对Cr(Ⅵ)、SO2-4分别为100、200mg/L废水的处理效果。结果表明,固定化小球对废水中Cr(Ⅵ)和SO2-4具有较好去除效果,Cr(Ⅵ)和SO2-4去除量分别高达341.87、1 680μg/g,去除率分别高达97.43%、99.30%。红外谱图、电子扫描图分析表明,固定化小球网状结构构成了细菌免受环境因素干扰的亲水微环境,硫酸盐还原在去除Cr(Ⅵ)和SO2-4过程中发挥了重要作用。     

抗菌处理对含硫煤矸石污染物释放的原位控制作用

自然堆放过程中,矿山环境微生物对大量含硫矿物的氧化产酸发挥着重要作用,为评价抗菌处理对暴露于空气中煤矸石污染物质释放的影响,设置十二烷基硫酸钠(SDS)抗菌处理、苯甲酸钠(SBZ)抗菌处理和对照(CK)3种处理条件对含硫煤矸石进行连续淋溶实验。结果表明,对照处理煤矸石淋溶液具有较强的酸度(pH=2.2~2.8)、较高的电导率(EC=4 426~24 925μS/cm)和氧化还原电位(Eh=334~499 mV),并富含Fe、Mn、Cu、Zn等金属离子和高浓度SO2-4和F-(其中,总铁平均为636 mg/L、Mn=16 mg/L、硫酸根=4 297 mg/L),呈现出煤矿酸性废水(AMD)的典型污染特征。相对于对照处理,SDS和SBZ抗菌剂处理对暴露于空气中的煤矸石污染的释放具有极显著的抑制作用,抗菌处理后,煤矸石淋溶液的pH(pHSDS=3.30~3.47、pHSBZ=5.13~5.64)、电导率(ECSDS=6 703~1 177μS/cm、ECSBZ=669~19 335μS/cm)、氧化还原电位(EhSDS=338~285 mV、EhSBZ=118~230 mV)和溶出离子Fe(总铁平均SDS=227 mg/L、SBZ=7.0 mg/L)、Mn(MnSDS=5.9 mg/L、MnSBZ=6.9 mg/L)、Cu、Zn等金属离子及阴离子SO2-4和F-等特征污染物的浓度均与对照存在极显著的差异(p0.01);且抗菌处理能显著抑制亚铁向高价铁的转化(pSDS=0.0012;pSBZ=0.0014)。2种抗菌剂处理均可极显著抑制暴露于空气中含硫煤矸石的氧化产酸和自身有毒有害污染物质的释放,且SBZ抗菌处理明显优于SDS抗菌处理。因此,SDS和SBZ等抗菌剂处理可用于含硫煤矸石等尾矿堆场污染的原位控制。     

PVA降解混合菌系生长和产酶的营养条件分析

研究碳源、氮源以及不同金属离子对PVA降解混合菌系生长和产酶的影响。结果表明,混合菌系生长过程中无机氮源优于有机氮源;补充碳源可促进混合菌系的生长,但酶活比不添加时稍有降低。金属离子对酶活影响的正交实验表明Mg2＋浓度影响最大,其次是Fe2＋和K＋浓度,Ca2＋、Mn2＋、Zn2＋和Cu2＋浓度影响较小;最佳浓度分别为Mg2＋0.05 g/L、Fe2＋0.04 g/L、K＋2 g/L和Ca2＋0.05 g/L。     

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.     

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.     

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.