硫酸盐在厌氧生物过程中的行为 Ⅱ.硫酸盐还原行为及对体系抑制作用机理

采用半连续实验方法,研究了中温厌氧条件下硫酸盐的还原行为及产生抑制作用的机理.实验结果表明,SO_4~(2-)在厌氧体系中被硫酸盐还原菌(SRB)全部或部分还原为硫化物,其还原率与SO_4~(2-)累积加入浓度有关.还原产物的形态与体系中pH值有关,较高的pH值(7.6—8.4)使体系中H_3S含量下降.SO_4~(2-)对厌氧体系的抑制与SO_4~(2-)还原过程中SRB与产甲烷菌(MRB)的底物竞争及还原产物的毒性相关.前者受COD/SO_4~(2-)比值的影响,比值大于7,对厌氧体系只产生轻度抑制作用.而后者与沼气中H_2S含量有直接关系,沼气中H_3S含量小于40mg/L时,基本不产生抑制作用.     

基质配比及硫酸盐对AnMBR产甲烷性能的影响

针对厌氧膜生物反应器污泥,研究了不同基质及硫酸盐对厌氧污泥产甲烷活性(SMA)及产甲烷潜能(BMP)的影响,阐述了硫酸盐还原及产甲烷过程的作用机制.结果表明:乙酸/丙酸比值为60%时,乙酸与丙酸的协同作用最佳,其厌氧污泥的SMA最快;乙酸/丙酸比值低于40%时,丙酸转化为乙酸的速率成为甲烷生成的限制因素,其厌氧污泥的SMA减缓;乙酸/丙酸比值高于60%时,SMA受到乙酸的抑制.在硫酸盐存在条件下,当COD/SO_4~(2-)-S20时,SMA和BMP均受到抑制,当COD/SO_4~(2-)-S10时,乙酸代谢受到抑制.从硫代谢情况来看,当COD/SO_4~(2-)-S25时,80%以上的硫酸盐转化为稳定价态的硫(H_2S,HS~-,S~(2-)),硫化氢对产甲烷菌产生抑制作用;当COD/SO_4~(2-)-S25时,仅有14%的硫酸盐转化为稳定价态的硫,硫酸盐还原菌因底物不足而活性受到抑制.     

COD/SO_4~(2-)值对硫酸盐废水厌氧消化的影响

采用间歇试验方式,研究了COD/SO_4~(2-)值对硫酸盐废水厌氧消化的影响。试验结果表明,COD/SO_4~(2-)值是影响厌氧消化处理效果的主要参数。本试验中,COD/SO_4~(2-)>15,硫酸盐还原作用对厌氧反应器影响甚微;COD/SO_4~(2-)=5—15时,硫酸盐还原作用对厌氧反应器产生轻度抑制,相对产甲烷率为79.2％—94.7％;COD/SO_4~(2-)=0.5—5时,反应器受中度抑制,相对产甲烷率为61.6％—79.2％;COD/SO_4~(2-)<0.5时,反应器受严重抑制。COD/SO_4~(2-)≥1时,相对产甲烷率与COD/SO_4~(2-)值之间有很好的线性关系。     

常温下加装脱硫装置的MCAnMBR处理高硫酸盐有机废水试验

研究了加装脱硫装置的沼气循环厌氧膜生物反应器对含高硫酸盐有机废水的处理效能.在26~34℃的室温下,历时63d成功地启动了加装脱硫装置的MCAnMBR反应器.调试初期,通过调节气路平衡和采用甲醇驯化的方法有效解决了MCAnMBR反应器在处理高硫酸盐有机废水时存在的跑泥和pH上升问题.结果表明,当控制HRT为120 h,有机负荷(以COD计)为3.61~4.36 kg·(m~3·d)~(-1),pH为7.18~7.61时,在23.3~25.4℃的室温下,对含SO_4~(2-)浓度为650~5 800 mg·L~(-1)的有机废水处理效果极佳,出水COD浓度最低可至23 mg·L~(-1),COD总去除率稳定在96.23%~99.77%,SO_4~(2-)还原率可达83.83%~95.51%.说明加装脱硫装置可有效解决硫化物的次级抑制作用问题,且通过梯度试验发现本反应器处理高硫酸盐有机废水的上限为:COD浓度18 000~21 000mg·L~(-1)、SO_4~(2-)浓度9082~9600 mg·L~(-1),COD/SO_4~(2-)为2.     

硫酸盐还原——甲烷化两相厌氧处理工艺中的回流比研究

以硫酸盐还原—产甲烷两相厌氧新型工艺处理含高浓度硫酸盐有机废水,气提塔出水的回流比的操作选择十分关键。根据、电离平衡理论及最佳工艺条件要求(液相中的C_L(H_2S)≥208mg/L,c(S~(2-))≤500mg/L)推导出估算回流比的模型为[Bc_0(SO_4~(2-))/1500-1]/η≤R≤[Bc_0(SO_4~(2-))(1.49×10~(pH-7) 1)~(-1)/588-1]/η。以该模型为依据处理SO_4~(2-)浓度为10000mg/L合成废水时,得到总COD去除率和总硫酸盐还原率分别为92.6％和97.6％。     

COD/SO42-对青霉素菌渣厌氧消化影响

针对抗生素菌渣厌氧消化过程SO_4~(2-)的抑制问题,利用批试实验对不同COD/SO_4~(2-)比青霉素菌渣厌氧消化产气潜能以及产酸相物质利用特性进行了研究.结果表明,COD/SO_4~(2-)≥3时,微生物发生了适应性驯化,产气潜能在发酵10 d后逐渐恢复,累积产甲烷量(以TS计)超过208 m L·g-1,超过71%的COD转化为CH4;COD/SO_4~(2-)≤1.5时,产甲烷分别受到49%及完全抑制,有机物及SO_4~(2-)的去除率分别不足17%和5%,表明较高SO_4~(2-)负荷下产甲烷菌(MPB)及硫酸盐还原菌(SRB)同时发生抑制,COD平衡分析表明,转化为CH4的COD不足9.1%,而还原为SO_4~(2-)的COD保持在5.0%~9.0%,说明MPB比SRB对S2-的抑制更为敏感;S平衡分析表明,还原的SO_4~(2-)大部分以S2-的形式存在于发酵液中,少部分以H2S的形式存在于生物气中;产酸过程物质利用特性分析表明,溶解性蛋白质的甲烷化是在溶解性碳水化物甲烷化之后才开始.     

COD/SO42-对硫酸盐有机废水厌氧处理颗粒污泥活性的影响

为了考察COD/SO_4~(2-)值对硫酸盐有机废水厌氧处理颗粒污泥活性的影响,文章采用五隔室厌氧折流板反应器(ABR),通过逐步降低COD/SO_4~(2-)值,研究了运行过程中各隔室COD和SO_4~(2-)的去除、挥发性脂肪酸(VFA)和硫化物的分布规律以及颗粒污泥活性变化情况。结果表明:(1)在COD/SO_4~(2-)值由12.5降至4.0的过程中,COD的去除主要由第3隔室承担,SO_4~(2-)的去除由第1隔室后移并波及到第1、2、3隔室,COD和SO_4~(2-)总去除率在90%左右;VFA主要在第1、2隔室产生,在第3隔室急剧下降,而硫化物的产生由第1隔室后移至第2隔室;第3隔室颗粒污泥保持较高的比产甲烷活性(SMA)和辅酶F_(420)含量,其平均值分别为55.23 mL CH4/(gVSS·d)和10.45μmol/L,第3、4隔室的颗粒污泥的脱氢酶活性(DHA)随COD/SO_4~(2-)值变化波动较大,同时出现胞外聚合物(EPS)的积累。(2)当COD/SO_4~(2-)值降至3.0,COD的去除主要由第4隔室承担,总去除率降低至40%,SO_4~(2-)的去除则后移并波及到第1、2、3、4隔室,总去除率最终稳定在90%左右;第3隔室VFA去除不明显,出现VFA积累,硫化物的产生后移至第3隔室;第3隔室颗粒污泥的DHA、SMA、辅酶F_(420)含量均急剧下降,其数值分别为0.278μmol TTC/(g·min)、6.84 mL CH_4/(gVSS·d)和5.71μmol/L,第4、5隔室颗粒污泥的DHA和SMA总体升高,但辅酶F_(420)含量和EPS浓度均降低。     

COD/SO2-4值对硫酸盐还原率的影响

研究利用UASB反应器考察了COD和硫酸盐浓度的比值对硫酸盐还原的影响,同时分析了硫酸盐还原菌和产甲烷菌对COD的竞争情况.发现在HRT为3.8h,SO2-4负荷为6～7kg·(m3·d)-1,SO2-4浓度为1000mg·L-1条件下:①在COD不足时,SRB与MPB在竞争中占微弱优势;对于产甲烷活性比较好的厌氧污泥要经过较长的时间,SRB才能确立优势菌种的地位.②COD/SO2-4比值决定了SO2-4的去除率.比值等于2时,SO2-4的还原率在95%以上;当比值为1.5时,SO2-4还原率为75%;当比值为1时,SO2-4的还原率为60%.     

不同碳硫比条件下底物类型对硫酸盐去除的差异性

为探索底物和碳硫比(COD_(Cr)/SO_4~(2-))对硫酸盐去除的影响,分别以乙醇、乳酸、丙酸、丁酸、乙酸为底物,采用静态试验考察了不同COD_(Cr)/SO_4~(2-)条件下利用不同底物去除硫酸盐的差异性。结果表明,在35℃条件下,COD_(Cr)/SO_4~(2-)为2.0时,硫酸盐还原菌(SRB)对乙醇的适应性最好;COD_(Cr)/SO_4~(2-)为2.5时,以乳酸、乙醇、丙酸为底物的系统中硫酸盐去除率分别可达90.29%、81.27%和80.69%;COD_(Cr)/SO_4~(2-)为3.0也可维持较高的硫酸盐去除率,以丁酸、乙酸为底物的系统中硫酸盐去除率分别可达88.78%和73.69%。研究表明,COD_(Cr)/SO_4~(2-)对SRB可利用的底物类型影响较大,根据底物类型选择最优的COD_(Cr)/SO_4~(2-),能够显著提高硫酸盐的去除效果,可为缩短厌氧脱硫反应器的启动时间提供新的思路。     

COD/SO_4~(2-)值对硫酸盐还原率的影响

研究利用 UASB反应器考察了 COD和硫酸盐浓度的比值对硫酸盐还原的影响 ,同时分析了硫酸盐还原菌和产甲烷菌对COD的竞争情况 .发现在 HRT为 3.8h,SO2 -4 负荷为 6～ 7kg· ( m3· d) - 1 ,SO2 -4 浓度为 1 0 0 0 mg· L- 1 条件下 :1在 COD不足时 ,SRB与 MPB在竞争中占微弱优势 ;对于产甲烷活性比较好的厌氧污泥要经过较长的时间 ,SRB才能确立优势菌种的地位 .2 COD/ SO2 -4 比值决定了 SO2 -4 的去除率 .比值等于 2时 ,SO2 -4 的还原率在 95%以上 ;当比值为 1 .5时 ,SO2 -4 还原率为 75% ;当比值为 1时 ,SO2 -4 的还原率为 60 % .     

Toxic effects of acetochlor, methamidophos and their combination on nifH gene in soil

Toxic effects of two agrochemicals on nifH gene in agricultural black soil were investigated using denaturing gradient gel electrophoresis （DGGE） and sequencing approaches in a microcosm experiment. Changes of soil nifH gene diversity and composition were examined following the application of acetochlor, methamidophos and their combination. Acetochlor reduced the nifH gene diversity （both in gene richness and diversity index values） and caused changes in the nifH gene composition. The effects of acetochlor on nifH gene were strengthened as the concentration of acetochlor increased. Cluster analysis of DGGE banding patterns showed that nifH gene composition which had been affected by low concentration of acetochlor （50 mg/kg） recovered firstly. Methamidophos reduced nifH gene richness that except at 4 weeks. The medium concentration of methamidophos （150 mg/kg） caused the most apparent changes in nifH gene diversity at the first week while the high concentration of methamidophos （250 mg/kg） produced prominent effects on nifH gene diversity in the following weeks. Cluster analysis showed that minimal changes of nifH gene composition were found at 1 week and maximal changes at 4 weeks. Toxic effects of acetochlor and methamidophos combination on nifH gene were also apparent. Different nifH genes （bands） responded differently to the impact of agrochemicals： four individual bands were eliminated by the application of the agrochemicals, five bands became predominant by the stimulation of the agrochemicals, and four bands showed strong resistance to the influence of the agrochemicals. Fifteen prominent bands were partially sequenced, yielding 15 different nifH sequences, which were used for phylogenetic reconstructions. All sequences were affiliated with the alpha- and beta-proteobacteria, showing higher similarity to eight different diazotrophic genera.     

Arsenic uptake by arbuscular mycorrhizal maize （Zea mays L.） grown in an arsenic-contaminated soil with added phosphorus

The effects of arbuscular mycorrhizal (AM) fungus (Glomus mosseae) and phosphorus (P) addition (100 mg/kg soil) on arsenic (As) uptake by maize plants (Zea mays L.) from an As-contaminated soil were examined in a glasshouse experiment.Non-mycorrhizal and zero-P addition controls were included.Plant biomass and concentrations and uptake of As,P,and other nutrients,AM colonization,root lengths,and hyphal length densities were determined.The results indicated that addition of P significantly inhibited root colonization and development of extraradical mycelium.Root length and dry weight both increased markedly with mycorrhizal colonization under the zero-P treatments,but shoot and root biomass of AM plants was depressed by P application.AM fungal inoculation decreased shoot As concentrations when no P was added,and shoot and root As concentrations of AM plants increased 2.6 and 1.4 times with P addition,respectively.Shoot and root uptake of P,Mn,Cu,and Zn increased,but shoot Fe uptake decreased by 44.6%,with inoculation, when P was added.P addition reduced shoot P,Fe,Mn,Cu,and Zn uptake of AM plants,but increased root Fe and Mn uptake of the nonmycorrhizal ones.AM colonization therefore appeared to enhance plant tolerance to As in low P soil,and have some potential for the phytostabilization of As-contaminated soil,however,P application may introduce additional environmental risk by increasing soil As mobility.     

Potential of plant polyphenol oxidases in the decolorization and removal of textile and non-textile dyes

In this study an effort has been made to use plant polyphenol oxidases; potato （Solanum tuberosum） and brinjal （Solanum melongena）, for the treatment of various important dyes used in textile and other industries. The ammonium sulphate fractionated enzyme preparations were used to treat a number of dyes under various experimental conditions. Majority of the treated dyes were maximally decolorized at pH 3.0. Some of the dyes were quickly decolorized whereas others were marginally decolorized. The initial first hour was sufficient for the maximum decolorization of dyes. The rate of decolorization was quite slow on long treatment of dyes. Enhancement in the dye decolorization was noticed on increasing the concentration of enzymes. The complex mixtures of dyes were treated with both preparations of polyphenol oxidases in the buffers of varying pH values. Potato polyphenol oxidase was significantly more effective in decolorizing the dyes to higher extent as compared to the enzyme obtained from brinjal polyphenol oxidase. Decolorization of dyes and their mixtures, followed by the formation of an insoluble precipitate, which could be easily removed simply by centrifugation.     

Removal of heavy metals from sewage sludge by low costing chemical method and recycling in agriculture

ＲｅｍｏｖａｌｏｆｈｅａｖｙｍｅｔａｌｓｆｒｏｍｓｅｗａｇｅｓｌｕｄｇｅｂｙｌｏｗｃｏｓｔｉｎｇｃｈｅｍｉｃａｌｍｅｔｈｏｄａｎｄｒｅｃｙｃｌｉｎｇｉｎａｇｒｉｃｕｌｔｕｒｅＷｕＱｉｔａｎｇ，ＮｙｉｒａｎｄｅｇｅＰａｓｃａｓｉｅ，ＭｏＣｅｈｕｉＦ...     

Single and joint effects of pesticides and mercury on soil urease

The influence of two pesticides including chlorimuron-ethyl and furadan and mercury （Hg） on urease activity in 4 soils （meadow burozem and phaeozem） was investigated. The soils were exposed to various concentrations of the two pesticides and Hg individually and simultaneously. Results showed that there was a close relationship between urease activity and organic matter content in soil. Chlorimuron-ethyl and furadan could both activate urease in the 4 soils. The maximum increment of urease activity by chlorimuronethyl was up to 14%-18%. There was almost an equal increase （up to 13%-21%） in the urease activity by furadan. On the contrary, Hg markedly inhibited soil urease activity. A logarithmic equation was used to describe the relationship （P〈0.05） between the concentration of Hg and the activity of soil urease in the 4 tested soils. Semi-effect dose （ED50） values by the stress of Hg based on the inhibition of soil urease in the 4 soils were 88, 5.5, 24 and 20 mg/kg, respectively, according to the calculation of the corresponding equations. The interactive effect of chlorimuron-ethyl or furadan with metal Hg on soil urease was mainly synergic at the highest tested concentrations.     

Isolation and preliminary characterization of a 3-chlorobenzoate degrading bacteria

A study was conducted to compare the diversity of 2-, 3-, and 4-chlorobenzoate degraders in two pristine soils and one contaminated sewage sludge. These samples contained strikingly different populations of mono-chlorobenzoate degraders. Although fewer cultures were isolated in the uncontaminated soils than contaminated one, the ability of microbial populations to mineralize chlorobenzoate was widespread. The 3- and 4-chlorobenzoate degraders were more diverse than the 2-chlorobenzoate degraders. One of the strains isolated from the sewage sludge was obtained. Based on its phenotype, chemotaxonomic properties and 16S rRNA gene, the organism S-7 was classified as Rhodococcus erythropolis. The strain can grow at temperature from 4 to 37℃. It can utilize several （halo）aromatic compounds. Moreover, strain S-7 can grow and use 3-chlorobenzoate as sole carbon source in a temperatures range of 10-30℃ with stoichiometric release of chloride ions. The psychrotolerant ability was significant for bioremediation in low temperature regions. Catechol and chlorocatechol 1,2-dioxygenase activities were present in cell free extracts of the strain, but no （chloro）catechol 2,3- dioxygenase activities was detected. Spectral conversion assays with extracts from R. erythropolis S-7 showed accumulation of a compound with a similar UV spectrum as chloro-cis,cis-muconate from 3-chlorobenzoate. On the basis of these results, we proposed that S-7 degraded 3-chlorobenzoate through the modified ortho-cleave pathway.     

Organochlorine pesticides in soils under different land usage in the Taihu Lake region, China

A field study was conducted in the Taihu Lake region, China in 2004 to reveal the organochlorine pesticide concentrations in soils after the ban of these substances in the year 1983. Thirteen organochlorine pesticides (OCPs) were analyzed in soils from paddy field, tree land and fallow land. Total organochlorine pesticide residues were higher in agricultural soils than in uncultivated fallow land soils. Among all the pesticides, ΣDDX (DDD, DDE and DDT) had the highest concentration for all the soil samples, ranging from 3.10 ng/g to 166.55 ng/g with a mean value of 57.04 ng/g and followed by ΣHCH, ranging from 0.73 ng/g to 60.97 ng/g with a mean value of 24.06 ng/g. Dieldrin, endrin, HCB and α-endosulfan were also found in soils with less than 15 ng/g. Ratios of p,p'-(DDD DDE)/DDT in soils under three land usages were: paddy field ＞ tree land ＞ fallow land, indicating that land usage inlfuenced the degradation of DDT in soils. Ratios of p,p'-(DDD DDE)/DDT ＞1, showing aged residues of DDTs in soils of the Taihu Lake region. The results were discussed with data from a former study that showed very low actual concentrations of HCH and DDT in soils in the Taihu Lake region, but according to the chemical half-lives and their concentrations in soils in 1980s, the concentration of DDT in soils seemed to be underestimated. In any case our data show that the ban on the use of HCH and DDT resulted in a tremendous reduction of these pesticide residues in soils, but there are still high amounts of pesticide residues in soils, which need more remediation processes.     

Sorption of 1-naphthol by plant cuticular fractions

The contribution of aliphatic-rich plant biopolymer to sorption of hydrophobic organic compounds is significantly important because of their preservation and accumulation in the soil environment,but sorption mechanism is still not fully understood.In this study, sorption of 1-naphthol by plant cuticular fractions was examined to better understand the contributions of respective fraction.Toward this end,cuticular materials were isolated from the fruits of tomato by chemical method.The tomato cuticle sheet consisted of waxes (6.5 wt%),cuticular monomer (69.5 wt%),and polysaccharide (24.0 wt%).Isotherms of l-naphthol to the cuticular fractions were nonlinear (N value (0.82-0.90)) at the whole tested concentration ranges.The KodKow ratios for bulk cuticle (TC1),dewaxed cuticle (TC2),cutin (TC4),and desugared cuticle (TC5) were larger than unity,suggested that tomato bulk cuticle and cutin are much powerful solption medium.Sorption capability of cutin (TC4) was 2.4 times higher than the nonsaponifiable fraction (TC3).The 1-naphthol interactions with tomato cuticular materials were governed by both hydrophobic-type interactions and polar (H-bonding) interactions. Removal of the wax and polysaccharide materials from the bulk tomato cuticle caused a significant increase in the sorption ability of the cuticular material.There was a linear negative trend between K_(oc) values and the amount of polysaccharides or fraction's polarities ((N O)/C);while a linear positive relationship between K_(oc) values and the content of cutin monomer (linear R~2=0.993) was observed for present in the cuticular fractions.Predominant sorbent of the hydrophobic organic compounds (HOCs) in the plant cuticular fraction was the cutin monomer,contributing to 91.7% of the total sorption of tomato bulk cuticle.     

Alterations of organ histopathology and metallolhionein mRNA expression in silver barb, Puntius gonionotus during subchronic cadmium exposure

Common silver barb,Puntius gonionotus,exposed to the nominal concentration of 0.06 mg/L Cd for 60 d,were assessed for histopathological alterations(gills,liver and kidney),metal accumulation,and metallothionein(MT)mRNA expression.Fish exhibited pathological symptoms such as hypertrophy and hyperplasia of primary and secondary gill lamellae,vacuolization in hepatocytes,and prominent tubular and glomerular damage in the kidney.In addition,kidney accumulated the highest content of cadmium,more than gills and liver.Expression of MT mRNA was increased in both liver and kidney of treated fish.Hepatic MT levels remained high after fish were removed to Cd-free water.In contrast,MT expression in kidney was peaked after 28 d of treatment and drastically dropped when fish were removed to Cd-free water.The high concentrations of Cd in hepatic tissues indicated an accumulation site or permanent damage on this tissue.     

Seed selections for crystallization of calcium phosphate for phosphorus recovery

Seed induces and promotes the crystallization of calcium phosphate, and acts as carrier of the recovered phosphorus （P）. In order to select suitable seed for P recovery from wastewater, three seeds including Apatite （AP）, Juraperle （JP） and phosphate-modified Juraperle （M-JP） were tested and compared. Batch and fixed-bed column experiments of seeded crystallization of calcium phosphate were undertaken by using synthetic wastewater with 10 mg/L P phosphate. It shows that AP has bad enduring property in the crystallization process, while JP has better performance for multiple uses, and M-JP is a hopeful seed for P recovery by crystallization of calcium phosphate.