生物同步脱氮除硫工艺研究进展

传统生物脱氮除硫过程中存在着许多问题。近年来,通过对脱氮微生物的深入研究,生物脱氮技术取得了突破性进展,而在生物同步脱氮除硫方面发展相对缓慢。总结了包括反硝化除硫、硫酸盐还原—自养反硝化—硝化、反硝化氨氧化以及硫酸盐型厌氧氨氧化等生物同步脱氮除硫工艺的特点,分析了各自的工艺原理及面临的挑战,并提出了今后的研究方向。     

厌氧铁氨氧化脱氮除磷效能及稳定性研究

为探究厌氧铁氨氧化(Feammox)污水处理效能及稳定性,考察了铁氧化物类型、硫限制和低温(4℃)对Feammox脱氮除磷的影响,并分析了污泥与微生物特性。结果表明,添加硫酸盐和水铁矿的实验组具有较好的脱氮除磷效果,氨氮和总磷去除率分别超过84%和98%,各实验组氨氧化产物均以硝态氮/亚硝态氮为主,并通过反硝化去除。微生物分析表明,添加硫酸盐和水铁矿、硫酸盐和磁铁矿的实验组中具有较高丰度的氨氧化细菌,硫限制和低温条件下则具有较高丰度的异养反硝化细菌。综上,Feammox具有较稳定的脱氮除磷效果,硫限制和磁铁矿作为铁源不影响其氨氧化效率,但低温明显降低氨氧化效率。     

奉化江底泥碳、氮、硫转化功能基因的定量研究

采用荧光定量聚合酶链式反应(PCR)法研究了奉化江4大支流及干流下游底泥样品中碳、氮、硫元素生物地球化学循环过程中关键转化功能基因丰度的变化。结果表明,奉化江干流下游的产甲烷基因mcrA丰度显著高于上游,甲烷氧化基因pmoA的丰度在支流下游、支流汇合处、干流下游均较高;富营养区域采样点底泥中氨氧化细菌硝化基因amoA(AOB)丰度显著高于氨氧化古菌硝化基因amoA(AOA),而其他采样点的AOA丰度大于AOB;干流下游底泥样品中反硝化基因nosZ丰度显著高于上游;居民区附近采样点底泥中存在较多硫氧化菌(soxB基因)和硫酸盐还原菌(dsrB基因)。相关性分析发现,pmoA与TN极显著正相关,AOB与NO-3极显著正相关,而nosZ与总碳(TC)、TN极显著正相关。     

硫自养与异养混合亚硝酸盐反硝化过程铵生成机制

为研究亚硝酸盐型碳、氮、硫同步脱除系统的特性,采用SBBR,以亚硝酸盐、硫化物及乙酸钠为基质,探索6种进水COD/N及5种进水S/N下碳、硫混合亚硝酸盐反硝化过程铵的生成机制。结果表明:在进水COD/N高于2、S/N高于1时,NO_2~--N去除率高达99%;同时,当氧化还原电位(ORP)低于-400 mV时,会出现铵浓度明显升高现象,在此条件下,进水COD/N不变时,较高的S/N会促进铵的生成;控制进水S/N不变,COD/N为3时铵浓度升高最为明显。微生物分析结果表明,该碳、氮、硫混合体系中同时存在硫自养反硝化、异养反硝化及亚硝酸盐异化还原为铵等过程,碳、硫混合亚硝酸盐反硝化过程铵的生成机制可能是低氧化还原电位和过量电子供体存在的情况下亚硝酸盐异化还原为铵的过程。     

两级自养反硝化实现垃圾渗滤液的深度脱氮

针对目前生物工艺难以解决垃圾渗滤液深度脱氮的问题,探究了短程硝化反硝化-厌氧氨氧化-硫自养反硝化(两级自养)工艺处理高氨氮、低C/N比垃圾渗滤液的脱氮效果。结果表明,当进水垃圾渗滤液中氨氮平均浓度为2 560 mg·L~(-1),COD值为4 000～5 000 mg·L~(-1)时,经过短程硝化反硝化-厌氧氨氧化处理后,总氮去除负荷可达1.19 kg·(m~3·d)~(-1)、总氮去除率可达93.1%(出水TN=176.3 mg·L~(-1))、COD去除率可达52.2%。但是,厌氧氨氧化反应器出水中NO_x~--N浓度为154.5 mg·L~(-1),仍未达到我国生活垃圾填埋场垃圾渗滤液处理排放标准(TN≤40 mg·L~(-1))。在厌氧氨氧化反应器之后串联硫自养反硝化,整体工艺最终出水NH_4~+-N、NO_2~--N、NO_3~--N平均浓度分别为1.9、0.6、9.7 mg·L~(-1),TN≤15 mg·L~(-1),进水总氮去除率为99.5%。在短程硝化反硝化-厌氧氨氧化-硫自养反硝化两级自养深度脱氮反应系统中实现了垃圾渗滤液深度脱氮。     

硫自养反硝化协同固定化微生物技术修复城市黑臭水体

固定化微生物技术可促进城市黑臭水体中氮磷污染物去除,但硫自养反硝化协同固定化微生物技术修复黑臭水体研究较少。通过向改性载镧膨润土基复合微生物菌剂(La-Bt基复合菌剂)中添加经S₂O₃^2-驯化培养的硫自养反硝化菌(NR-SOB),试图引入硫自养反硝化协同固定化微生物技术修复黑臭水体。在La-Bt基复合菌剂投加量为1.5 g/L时,向黑臭水体中分梯度投加不同浓度NR-SOB,研究NR-SOB协同La-Bt基复合菌剂去除黑臭水体污染物效果,并通过高通量测序分析底泥微生物群落结构变化。结果表明,当NR-SOB投加量为0.3 g/L时,对黑臭水体和底泥处理效果较好：上覆水氨氮、TN和TP去除率分别为87.42%、69.85%和71.11%;底泥酸可挥发性硫(AVS)去除率为34.76%,底泥TN和TP去除率分别为45.22%、45.04%;实验结束时底泥中厚壁菌门(Firmicutes)相对丰度从11.76%降至9.84%,硫杆菌属(Thiobacillus)相对丰度达2.82%,氮硫去除相关微生物菌属比例提升约0.95%。     

有机物对自养脱氮工艺影响的研究进展

自养脱氮工艺中同时存在亚硝酸化、硝酸化、厌氧氨氧化和反硝化4个过程,而有机物增加了自养脱氮工艺4个过程的脱氮复杂性,但也增加了更多的可能性。综述了有机物对亚硝酸化、硝酸化、厌氧氨氧化和反硝化的影响,整理了同步亚硝化/厌氧氨氧化/反硝化(SNAD)工艺和反硝化氨氧化(DEAMOX)工艺的最新研究进展。     

投加硝酸钙对城市黑臭河道底泥氮迁移转化的影响

投加硝酸钙是目前河道黑臭底泥原位治理常用的方法,然而,投加硝酸钙会造成底泥硝态氮和氨氮的过量释放,而其影响机制尚未明确。因此有必要对投加硝酸钙后硝态氮在底泥中的迁移转化规律及其促进氨氮释放的机理进行研究。结果发现,硝酸盐在间隙水的迁移距离取决于硝态氮反硝化速率,而在黑臭底泥中硫化物氧化是影响反硝化速率的关键因素。当硝酸钙投加量为20 g/kg时,硝态氮的迁移距离小于6 cm,且在14 d后消耗光;可见,通过控制硝酸钙在底泥中的投加位置可避免硝态氮的二次释放。另一方面,投加硝酸钙会促进底泥氨态氮向间隙水释放,投加当天释放率可高达101%,且会在间隙水中发生累积迁移。其中,氨氮的增加量和底泥氨态氮解吸量呈一级线性关系(r=0.986)、和硝酸钙投加量关系符合cubic曲线;据此可推测,氨氮的急剧释放与钙离子对底泥铵态氮的化学浸提有关。     

厌氧硫酸盐还原-氨氧化的研究

采用厌氧序批式反应器,在无机营养条件下培养历时354 d,成功实现了SO2-4和NH+4的同步生物去除。结果表明,提高进水的TN负荷有利于促进硫酸盐还原-氨氧化的发生,当进水TN负荷提高到120 mg/(L·d)时,对TN的平均去除速率和硫酸盐硫的平均去除速率达到了最大,分别为64.43 mg/(L·d)和44.82 mg/(L·d);在同步生物脱氮除硫前期生成了大量的NO-3-N,平均浓度为53.88 mg/L,远大于由Anammox反应生成的量,推测部分NO-3是直接由NH+4和SO2-4发生氧化还原反应生成。该体系中存在单质硫的自养反硝化,可以解释反应后期硫酸盐重生成的现象。     

接种物对厌氧同步脱硫反硝化特性的影响实验研究

分别以厌氧污泥、脱氮硫杆菌菌悬液和厌氧污泥并添加脱氮硫杆菌菌悬液为接种物,以硫化物和硝酸盐为进水基质,考察不同接种物条件下,各反应器的硫化物氧化特性、反硝化特性、生化反应机理及微生物特性。结果表明,在无菌条件下,硫化物不能被硝酸盐化学氧化。接种脱氮硫杆菌菌悬液的2#反应器的硫氧化速率为1.98 g S/(m3.h),停留24 h硫化物的去除率高达97%,脱硫能力最强,该接种条件下以硝酸盐氧化硫化物为主反应,优势菌为杆菌,进水的NO3--N/S应控制在0.4以下,可以实现高效生物脱硫。接种厌氧污泥的1#和3#反应器的脱氮效果比2#反应器好,停留时间为24 h时,硝酸盐的平均去除率为96%。单独接种厌氧污泥的1#反应器的硫氧化速率为1.78 g S/(m3.h),其优势菌为球菌,该接种条件下以硝酸盐氧化硫化物和硝酸盐氧化单质硫为主反应,进水的NO3--N/S应控制在0.8左右。以厌氧污泥联合脱氮硫杆菌为接种物时,硫氧化速率为1.71 g S/(m3.h),反应器以硝酸盐氧化硫化物、硝酸盐氧化单质硫以及异养反硝化为主反应,驯化后优势菌为球形、卵圆形和短杆状,应控制进水NO3--N/S为1.2,可以实现同步脱硫反硝化,该工艺既可以用于含硫废水的处理,也可以用于C/N低的硝酸盐废水的处理。     

Sorption and desorption of Cu and Cd by macroalgae and microalgae

The sorption and desorption of Cu and Cd by two species of brown macroalgae and five species of microalgae were studied. The two brown macroalgae, Laminaria japonica and Sargassum kjellmanianum, were found to have high capacities at pHs between 4.0 and 5.0 while for microalgae, optimum pH lay at 6.7. The presence of other cations in solution was found to reduce the sorption of the target cation, suggesting a competition for sorption sites on organisms. Sorption isotherms obeyed the Freundlich equation, suggesting involvement of a multiplicity of mechanisms and sorption sites. For the microalgae tested, Spirulina platensis had the highest capacity for Cd, followed by Nannochloropsis oculata, Phaeodactylum tricornutum, Platymonas cordifolia and Chaetoceros minutissimus. The reversibility of metal sorption by macroalgae was examined and the results show that both HCl and EDTA solutions were very effective in desorbing sorbed metal ions from macroalgae, with up to 99.5% of metals being recovered. The regenerated biomass showed undiminished sorption performance for the two metals studied, suggesting the potential of such material for use in water and wastewater treatment.     

Dioxin- and POP-contaminated sites—contemporary and future relevance and challenges

BACKGROUND, AIM AND SCOPE: Once they have been generated, polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) and other persistent organic pollutants (POPs) can persist in soils and sediments and in waste repositories for periods extending from decades to centuries. In 1994, the US EPA concluded that contaminated sites and other reservoirs are likely to become the major source of contemporary pollution problems with these substances. With this in mind, this article is the first in a new series in ESPR under the title 'Case Studies on Dioxin and POP Contaminated Sites--Contemporary and Future Relevance and Challenges', which will address this important issue. The series will document various experiences from sites contaminated with PCDD/F and other POPs. This article provides an overview of the content of the articles comprising the series. In addition, it provides a review of the subject in its own right and identifies the key issues arising from dioxin/POP-contaminated sites. Additionally, it highlights the important conclusions that can be drawn from these examples. The key aim of this article and of the series as a whole is to provide a comprehensive overview of the types of PCDD/F contaminated sites that exist as a result of historical activities. It details the various processes whereby these sites became contaminated and attempts to evaluate their contemporary relevance as sources of PCDD/Fs and other POPs. It also details the various strategies used to assess these historical legacies of contamination and the concepts developed, or which are under development, to effect their remediation. MAIN FEATURES: Special sessions on 'Contaminated sites--Cases, remediation, risk and policy' were held at the DIOXIN conferences in 2006 and 2007, and this theme will be continued at DIOXIN 2008 to be held in Birmingham. Selected cases from the approximately 70 contributions made to these sessions, together with some additional invited case studies are outlined together with the key issues they raise. By evaluating these cases and adding details of experiences published in the current literature, an overview will be given of the different features and challenges of dioxin and POP-contaminated sites. RESULTS: This article provides a systematic categorisation of types of PCDD/F and POP-contaminated sites. These are categorised according to the chemical or manufacturing process, which generated the PCDD/Fs or POPs and also includes the use and disposal aspects of the product life cycle in question. The highest historical PCDD/F and dioxin-like polychlorinated biphenyl (PCB) contamination burdens have arisen as a result of the production of chlorine and of chlorinated organic chemicals. In particular, the production of chlorinated pesticides, PCBs and the related contaminated waste streams are identified being responsible for historical releases of toxic equivalents (TEQs) at a scale of many tonnes. Along with such releases, major PCDD/F contaminated sites have been created through the application or improper disposal of contaminated pesticides, PCBs and other organochlorine chemicals, as well through the recycling of wastes and their attempted destruction. In some extreme examples, PCDD/F contaminated sites have also resulted from thermal processes such as waste incinerators, secondary metal industries or from the recycling or deposition of specific waste (e.g. electronic waste or car shredder wastes), which often contain chlorinated or brominated organic chemicals. The examples of PCDD/F and dioxin-like PCB contamination of fish in European rivers or the impact of contaminated sites upon fishing grounds and upon other food resources demonstrate the relevance of these historical problems to current and future human generations. Many of the recent food contamination problems that have emerged in Europe and elsewhere demonstrate how PCDD/F and dioxin like PCBs from historical sources can directly contaminate human and animal feedstuffs and indeed highlight their considerable contemporary relevance in this respect. Accordingly, some key experiences and lessons learnt regarding the production, use, disposal and remediation of POPs from the contaminated sites are summarised. DISCUSSION: An important criterion for evaluating the significance and risks of PCDD/Fs and other POPs at contaminated sites is their present or future potential for mobility. This, in turn, determines to a large degree their propensity for off-site transport and environmental accessibility. The detailed evaluation of contaminated site cases reveals different site-specific factors, which influence the varied pathways through which poor water-soluble POPs can be mobilised. Co-contaminants with greater water solubility are also typically present at such sites. Hence, pumping of groundwater (pump and treat) is often required in addition to attempting to physically secure a site. At an increasing number of contaminated sites, securing measures are failing after relatively short time spans compared to the time horizon, which applies to persistent organic pollutant contamination. Due to the immense costs and challenges associated with remediation of contaminated sites 'monitored natural attenuation' is increasingly gaining purchase as a conceptual remediation approach. However, these concepts may well prove limited in their practical application to contaminated sites containing persistent organic pollutants and other key pollutants like heavy metals. CONCLUSIONS: It is inevitable, therefore, that dioxin/POP-contaminated sites will remain of contemporary and future relevance. They will continue to represent an environmental issue for future generations to address. The securing and/or remediation of dioxin/POP-contaminated sites is very costly, generally in the order of tens or hundreds of millions of dollars. Secured landfills and secured production sites need to be considered as constructions not made for 'eternity' but built for a finite time scale. Accordingly, they will need to be controlled, supervised and potentially repaired/renewed. Furthermore, the leachates and groundwater impacted by these sites will require ongoing monitoring and potential further remediation. These activities result in high maintenance costs, which are accrued for decades or centuries and should, therefore, be compared to the fully sustainable option of complete remediation. The contaminated site case studies highlight that, while extensive policies and established funds for remediation exist in most of the industrialised western countries, even these relatively well-regulated and wealthy countries face significant challenges in the implementation of a remediation strategy. This highlights the fact that ultimately only the prevention of contaminated sites represents a sustainable solution for the future and that the Polluter Pays Principle needs to be applied in a comprehensive way to current problems and those which may emerge in the future. RECOMMENDATIONS AND PERSPECTIVES: With the continuing shift of industrial activities in developing and transition economies, which often have poor regulation (and weak self-regulation of industries), additional global challenges regarding POPs and other contaminated sites may be expected. In this respect, a comprehensive application of the "polluter pays principle" in these countries will also be a key to facilitate the clean-up of contaminated areas and the prevention of future contaminated sites. The threats and challenges of contaminated sites and the high costs of securing/remediating the problems highlight the need for a comprehensive approach based upon integrated pollution prevention and control. If applied to all polluting (and potentially polluting) industrial sectors around the globe, such an approach will prove to be both the cheapest and most sustainable way to underpin the development of industries in developing and transition economies.     

Persistence and dissipation kinetics of trifloxystrobin and tebuconazole in onion and soil

The persistence and dissipation kinetics of trifloxystrobin and tebuconazole on onion were studied after application of their combination formulation at a standard and double dose of 75 + 150 and 150 + 300 g a.i. ha^?1. The fungicides were extracted with acetone, cleaned-up using activated charcoal (trifloxystrobin) and neutral alumina (tebuconazole). Analysis was carried out by gas chromatograph (GC) and confirmed by gas chromatograph mass spectrometry (GC-MS). The recovery was above 80% and limit of quantification (LOQ) 0.05 mg kg^?1 for both fungicides. Initial residue deposits of trifloxystrobin were 0.68 and 1.01 mg kg^?1 and tebuconazole 0.673 and 1.95 mg kg^?1 from standard and double dose treatments, respectively. Dissipation of the fungicides followed first-order kinetics and the half life of degradation was 6–6.6 days. Matured onion bulb (and field soil) harvested after 30 days was free from fungicide residues. These findings suggest recommended safe pre-harvest interval (PHI) of 14 and 25 days for spring onion consumption after treatment of Nativo 75 WG at the standard and double doses, respectively. Matured onion bulbs at harvest were free from fungicide residues.     

Kinetic and structural relationships of transition monomeric and oligomeric carboxyl- and choline-esterases

The kinetic and structural relationships of eight electrophoretically pure mammalian serum and liver serine carboxylesterases (CE) and cholinesterases (ChE) have been studied. Eight CE's and ChE's, which were fully resolved but only partially purified, provided additional information. Five of the electrophoretically pure esterases were monomeric, and of these, four belonged to a new and widely distributed class. These four monomeric esterases hydrolyzed choline esters, but at widely differing rates. Thus two were termed monomeric butyrylcholinesterases, mBuChE I and II, and two were monomeric CE's (mCE). The rabbit liver mCE was not a subunit of the oligomeric CE (oCE), although the oCE also hydrolyzed choline esters at a very low rate. The complex kinetics of the mCE's, mBuChE's, oCE's, and of the oligomeric BuChE's of horse and human serum could be interpreted according to a single reaction scheme involving an allosteric site and the equation derived from it. Thus activation and inhibition at high substrate concentrations, together with sigmoidal activity versus substrate concentration plots, all of which characterize the reactions of these esterases, could be interpreted by a single scheme and equation. Structural and kinetic comparisons showed a progressive transition of properties from the oCE's through the mCE's to the oBuChE's. One of the purified mCE's was from horse serum, and it exhibited physical and kinetic properties unlike those of the liver mCE's or oCE's.     

Sorption and Desorption Behavior of Chloroanilines and Chlorophenols on Montmorillonite and Kaolinite

The bioavailability of pollutants, pesticides and/or their degradation products in soil depends on the strength of their sorption by the different soil components, particularly by the clay minerals. This study reports the sorption-desorption behavior of the environmentally hazardous industrial pollutants and certain pesticides degradation products, 3-chloroaniline, 3,4-dichloroaniline, 2,4,6-trichloroaniline, 4-chlorophenol, 2,4-dichlorophenol and 2,4,6-trichlorophenol on the reference clays kaolinite KGa-1 and Na-montmorillonite SWy-l. In batch studies, 2.0 g of clay were equilibrated with 100.0 mL solutions of each chemical at concentrations ranging from 10.0 to 200.0 mg/L. The uptake of the compounds was deduced from the results of HPLC-UV-Vis analysis. The lipophilic species were best retained by both clay materials. The most lipophilic chemical used in the study, 2,4,6-trichloroaniline, was also the most strongly retained, with sorption of up to 8 mg/g. In desorption experiments, which also relied on HPLC-UV-Vis technique, 2,4,6-trichloroaniline was the least desorbed from montmorillonite. However, on kaolinite all of the compounds under study were irreversibly retained. The experimental data have been modelled according to the Langmuir and Freundlich isotherms. A hypothesis is proposed concerning the sorption mechanism and potential applications of the findings in remediation strategies have been suggested.     

Sorption and desorption behavior of chloroanilines and chlorophenols on montmorillonite and kaolinite

The bioavailability of pollutants, pesticides and/or their degradation products in soil depends on the strength of their sorption by the different soil components, particularly by the clay minerals. This study reports the sorption-desorption behavior of the environmentally hazardous industrial pollutants and certain pesticides degradation products, 3-chloroaniline, 3,4-dichloroaniline, 2,4,6-trichloroaniline, 4-chlorophenol, 2,4-dichlorophenol and 2,4,6-trichlorophenol on the reference clays kaolinite KGa-1 and Na-montmorillonite SWy-l. In batch studies, 2.0 g of clay were equilibrated with 100.0 mL solutions of each chemical at concentrations ranging from 10.0 to 200.0 mg/L. The uptake of the compounds was deduced from the results of HPLC-UV-Vis analysis. The lipophilic species were best retained by both clay materials. The most lipophilic chemical used in the study, 2,4,6-trichloroaniline, was also the most strongly retained, with sorption of up to 8 mg/g. In desorption experiments, which also relied on HPLC-UV-Vis technique, 2,4,6-trichloroaniline was the least desorbed from montmorillonite. However, on kaolinite all of the compounds under study were irreversibly retained. The experimental data have been modelled according to the Langmuir and Freundlich isotherms. A hypothesis is proposed concerning the sorption mechanism and potential applications of the findings in remediation strategies have been suggested.     

Bacterial and archaeal diversity in oil fields and reservoirs and their potential role in hydrocarbon recovery and bioprospecting

Environmental Science and Pollution Research - Hydrocarbon is a primary source of energy in the current urbanized society. Considering the increasing demand, worldwide oil productions are declining...     

Synthesis and characterization of m- and p-methylbenzyl-mercapturic acids derived from m- and p-xylenes

Chemical synthesis and physical properties of two mercapturic acids suggested as urinary metabolites of m- and p-xylenes ace described. These compounds may be used for the identification and quantivative determination by high-performance liquid chromatography of the corresponding mercapturic acids in urine.     

Sources and fate of PCDD and PCDF

PCDD and PCDF were found in urban air particulates from St. Louis and Washington, D.C., and in sediments from the Great Lakes and Siskiwit Lake, Isle Royale. The similarity between the PCDD and PCDF found in air particulates and sediment samples and the presence of PCDD and PCDF in sediment from Siskiwit Lake (a location which can receive only atmospheric inputs) suggest that these compounds are emitted to the atmosphere from combustion sources. The historical input of PCDD and PCDF to dated sediment cores shows a strong increase since 1940, and this suggests that the incineration of chlorinated organic compounds is an important source of PCDD and PCDF to the environment.     

Levels of PCDDs and PCDFs in products and effluent from the Swedish pulp and paper industry and chloralkali process

Within the Swedish Dioxin Survey various samples from the pulp and paper industry and the chloralkali process have been analyzed by congener specific analytical methods. In addition to the generally discussed “bleaching pattern” of the tetrachlorinated congeners, these samples also contained higher chlorinated congeners like hexa-CDDs, hepta-CDFs, octa-CDD and octa-CDF. Consequently it is recommended that samples from the pulp industry should be analyzed for all PCDDs and PCDFs (tetra- through octa-). Counted as Nordic Toxic Equivalents (NTEQ), the recycled pulp samples had the highest contamination level followed by TMP, unbleached sulfite and bleached softwood and hardwood. In addition to the bleaching process, various chemicals used in the pulping, bleaching and wastewater treatment can contribute to the contamination.