柠檬酸及EDTA对土壤中六价铬的淋洗修复效果研究

主要研究柠檬酸和EDTA淋洗剂对六价铬污染土壤的淋洗修复效果,重点考察淋洗剂浓度、液固比、淋洗时间和淋洗方式对土壤六价铬去除效果的影响。研究结果表明：随着淋洗剂浓度的增加,柠檬酸淋洗剂对供试土壤六价铬的去除率逐渐升高,最高为54．0%,而EDTA淋洗剂对供试土壤的去除率先升高后降低,浓度在0．4 mol·L-1时达到最高,为66．3%;土壤六价铬去除率随液固比的增加呈现先升高后降低的趋势,当液固比为7：1时,0．5 mol·L-1柠檬酸和0．1 mol·L-1 EDTA淋洗剂对供试土壤六价铬的去除率最高,分别为69．6%和61．9%;增加淋洗时间,供试土壤六价铬的去除率逐渐升高,2 h后增幅不大;就清洗方式而言,EDTA淋洗剂一次加入对土壤六价铬的去除效果最好,而柠檬酸淋洗剂宜采用二次加入一次分离的方式。     

Preliminary investigation of phosphorus adsorption onto two types of iron oxide-organic matter complexes

Iron oxide(FeO)coated by natural organic matter(NOM)is ubiquitous.The associations of minerals with organic matter(OM)significantly changes their surface properties and reactivity,and thus affect the environmental fate of pollutants,including nutrients(e.g.,phosphorus(P)).In this study,ferrihydrite/goethite-humic acid(FH/GE–HA)complexes were prepared and their adsorption characteristics on P at various p H and ionic strength were investigated.The results indicated that the Fe O–OM complexes showed a decreased P adsorption capacity in comparison with bare Fe O.The maximum adsorption capacity(Q_(max))decreased in the order of FH(22.17 mg/g)FH-HA(5.43 mg/g)GE(4.67 mg/g)GE-HA(3.27 mg/g).After coating with HA,the amorphous FH–HA complex still showed higher P adsorption than the crystalline GE–HA complex.The decreased P adsorption observed might be attributed to changes of the Fe O surface charges caused by OM association.The dependence of P adsorption on the specific surface area of adsorbents suggests that the Fe O component in the complexes is still the main contributor for the adsorption surfaces.The P adsorptions on Fe O–HA complexes decreased with increasing initial p H or decreasing initial ionic strength.A strong dependence of P adsorption on ionic strength and p H may demonstrate that outer-sphere complexes between the OM component on the surface and P possibly coexist with inner-sphere surface complexes between the Fe O component and P.Therefore,previous over-emphasis on the contributions of original minerals to P immobilization possibly over-estimates the P loading capacity of soils,especially in humic-rich areas.     

Temperature effect on photolysis decomposing of perfluorooctanoic acid

Perfluorooctanoic acid(PFOA)is recalcitrant to degrade and mineralize.Here,the effect of temperature on the photolytic decomposition of PFOA was investigated.The decomposition of PFOA was enhanced from 34% to 99% in 60 min of exposure when the temperature was increased from 25 to 85°C under UV light(201–600 nm).The limited degree of decomposition at 25°C was due to low quantum yield,which was increased by a factor of 12 at 85°C.Under the imposed conditions,the defluorination ratio increased from 8% at 25°C to 50% at85°C in 60 min.Production of perfluorinated carboxylic acids(PFCAs,C7–C5),PFCAs(C4–C3)and TFA(trifluoroacetic acid,C2)accelerated and attained a maximum within 30 to 90 min at 85°C.However,these reactions did not occur at 25°C despite extended irradiation to180 min.PFOA was decomposed in a step-wise process by surrendering one CF2unit.In each cyclical process,increased temperature enhanced the quantum yields of irradiation and reactions between water molecules and intermediates radicals.The energy consumption for removing eachμmol of PFOA was reduced from 82.5 k J at 25°C to 10.9 k J at 85°C using photolysis.Photolysis coupled with heat achieved high rates of PFOA degradation and defluorination.     

Sorption of tylosin and sulfamethazine on solid humic acid

Tylosin(TYL) and sulfamethazine(SMT) are ionizable and polar antimicrobial compounds,which have seeped into the environment in substantial amounts via fertilizing land with manure or sewage. Sorption of TYL and SMT onto humic acid(HA) may affect their environmental fate. In this study, the sorption of TYL and SMT on HA at different conditions(pH, ionic strength) was investigated. All sorption isotherms fitted well to the Henry and Freundlich models and they were highly nonlinear with values of n between 0.5 and 0.8, which suggested that the HA had high heterogeneity. The sorption of TYL and SMT on HA decreased with increasing p H(2.0–7.5), implying that the primary sorption mechanism could be due to cation exchange interactions between TYL~+/SMT~+ species and the functional groups of HA.Increasing ionic strength resulted in a considerable reduction in the K_d values of TYL and SMT,hinting that interactions between H bonds and π–π EDA might be an important factor in the sorption of TYL and SMT on HA. Results of Fourier transform infrared(FT-IR) and ~13C-nuclear magnetic resonance(NMR) analysis further demonstrated that carboxyl groups and O-alkyl structures in the HA could interact with TYL and SMT via ionic interactions and H bonds,respectively. Overall, this work gives new insights into the mechanisms of sorption of TYL and SMT on HA and hence aids us in assessing the environmental risk of TYL and SMT under diverse conditions.     

氮添加对亚热带森林土壤有机碳氮组分的影响

为了研究氮添加对森林土壤有机碳氮组分稳定性的影响,选取我国亚热带典型常绿阔叶林(浙江桂天然林和罗浮栲天然林)和针叶林(杉木人工林),开展为期5年的野外模拟氮沉降试验,分别设置对照〔0 kg/(hm2·a),以NH₄NO₃中的N计,下同〕、低氮〔75 kg/(hm2·a)〕和高氮〔150 kg/(hm2·a)〕3个氮添加水平,用H₂SO₄分2步酸水解获得LPⅠ(活性有机库Ⅰ)、LPⅡ(活性有机库Ⅱ)和RP(惰性有机库),定量研究土壤活性和惰性有机碳氮组分以及微生物生物量碳氮对氮添加的响应. 结果表明:氮添加仅对w(LPⅡ-C)(LPⅡ-C为活性有机碳Ⅱ)有显著影响,而对其他活性和惰性有机碳氮组分的影响不显著,并且对不同林分的影响存在差异. 与对照处理相比,低氮处理下浙江桂天然林、罗浮栲天然林和杉木人工林土壤w(LPⅡ-C)的增幅分别为15.3%、29.8%、68.8%;高氮处理下杉木人工林土壤w(LPⅠ-C)(LPⅠ-C为活性有机碳Ⅰ)、w(LPⅠ-N)(LPⅠ-N为活性有机氮Ⅰ)和w(RP-C)(RP-C为惰性有机碳)的增幅分别为32.4%、78.6%、28.7%;氮添加使得土壤w(SMB-C)(土壤微生物生物量碳)的增幅为18.1%~202.5%、w(SMB-N)(土壤微生物生物量氮)的增幅为0%~103.6%;在氮添加处理下,除杉木人工林土壤SMB-N/LPⅠ-N〔w(SMB-N)/w(LPⅠ-N)〕是随着氮添加水平的增加而降低外,微生物对其他林分土壤活性有机氮的利用均表现为随着氮添加水平的增加而增加. 研究显示,氮添加对阔叶林和针叶林土壤活性和惰性有机碳氮组分的影响存在差异,但差异不显著,这与它们归还土壤的凋落物性质差异有关,并且凋落物的分解差异也可能是影响土壤不同碳氮组分变化的原因.      

含铝酸性农药废水合成聚合硫酸铝混凝剂

采用农药三唑醇生产过程中产生的含铝酸性废水为原料,合成了聚合硫酸铝(PAS)液体混凝剂,并用于厂区污水站好氧池出水的混凝处理。考察了碱化剂用量、聚合温度、聚合时间等合成条件及PAS加入量、混凝pH等混凝条件对混凝效果的影响,并比较了PAS与商售聚合氯化铝(PAC)的混凝效果。实验结果表明:在n(碱化剂)∶n(硫酸铝)为2.1∶1、聚合温度为80℃、聚合时间为60 min的条件下,所得PAS液体混凝剂产品的w(Al2O3)为7.8%~9.0%,盐基度为45%~60%,pH为3.5~4.0,产量为0.75 t/t(以废水计);在PAS加入量为2.0 m L/L、混凝pH为10.0时,COD和SS的去除率则分别达到14.6%和83.0%;该PAS可替代厂区常规使用的商售PAC,日节约废水处理成本5 922元。     

分步沉淀法处理酸性矿山废水

采用分步沉淀工艺处理酸性矿山废水,考察了工艺条件对废水中有价金属元素回收效果的影响。实验结果表明:Ca(OH)_2为适宜的废水pH调节剂;调节废水pH至4.00左右并投加0.05 mL/L的H_2O_2,可首先去除Fe~(2+)及Fe~(3+),得到富Fe渣(w(Fe)=51.00%);调节废水pH至6.00~6.50,先投加50 mg/L的Na_2S,去除废水中的Cu~(2+),获得富Cu渣(w(Cu)=10.89%),再将Na_2S的投加量增至100 mg/L,去除废水中的Zn与Mn,获得富Zn-Mn渣(w(Cu)=2.37%,w(Mn)=6.79%,w(Pb)=1.61%);进一步调节废水pH至8.40,可去除剩余的Zn、Mn及其他重金属。分步沉淀工艺处理后的废水可达标排放,产生的富Fe渣、富Cu渣及富Zn-Mn渣可直接出售或具有利用价值。分步沉淀工艺可实现有价金属元素的高效回收,大幅度降低废水处理的实际成本,值得工程应用与推广。     

安徽某铁矿酸性矿山废水夏季和秋季微生物群落结构特征

分别采集了夏秋两季安徽某铁矿的酸性矿山废水样品,分析其物理化学参数,并利用分子生物学方法研究了该酸性矿山废水中微生物群落结构随时间和空间的变化规律.结果表明:该矿山废水酸性极强,夏季所采样品pH在2.80左右,且阴阳离子含量很高,Al~(3+)为1108~1138mg·L~(-1),SO_4~(2-)则高达19.80~23.79 g·L~(-1).秋季样品p H没有明显变化,但由于两次采样期间的大量降水,样品中各离子含量明显低于夏季.值得注意的是,该极端酸性的矿山废水中叶绿素a含量较高,夏季达63.8~94.2μg·L~(-1),秋季则降至16.6~32.7μg·L~(-1).无论是在夏季还是秋季,Alphaproteobacteria在绝大多数位点的细菌群落中占据着优势地位.化能异养菌Acidiphilium是最主要的细菌菌属,它在夏季和秋季各位点群落中所占比例都达20%左右,这应该与其丰富的代谢方式有关.对于真核微生物群落,夏季主要为尖毛虫和小球藻,秋季主要为棕鞭藻和小球藻.小球藻是该酸性生态系统主要的生产者,尖毛虫和棕鞭藻则扮演着顶级消费者的角色.该酸性废水应处于酸水形成末期,所以细菌群落中化能异养菌占据着优势地位,化能自养菌比例较少.由于温度等理化性质的不同,微生物群落结构随时间和空间发生了一定变化,其中以真核微生物群落结构变化最为显著.     

高效重金属捕集剂EDTC的结构表征及对酸性络合铜的去除特性研究

以乙二胺和二硫化碳为反应物,无水乙醇和去离子水的混合溶液为溶剂,制备了一种巯基类重金属捕集剂N,N-双(二硫代羧基)乙二胺(EDTC),采用紫外光谱、红外光谱和元素分析对其结构进行表征,重点研究了其对EDTA络合铜、柠檬酸络合铜和酒石酸铜3种酸性模拟络合铜的去除性能及螯合沉淀物的溶出特性,并探讨了EDTC脱除络合铜的机理.研究结果表明,处理50 mg·L-1的含铜废水,p H值范围为3~9,EDTC投加量为mEDTC/mCu=8(质量比),反应时间3 min,PAM投加量为1 mg·L-1,此时出水Cu2+浓度均低于0.25 mg·L-1,去除率达到99.5%以上.螯合沉淀物在弱酸性和弱碱性条件下很稳定,不易产生二次污染.红外光谱图分析结果表明,EDTC与Cu会发生螯合反应,即EDTC直接脱出络合铜中Cu2+,并与Cu2+生成难溶的螯合产物EDTC-Cu,进而有效地去除废水中Cu.     

基于PLFA法分析亚硝氮、硝氮和氨氮对厌氧微生物细菌群落的影响

利用磷脂脂肪酸(PLFA)技术研究了亚硝氮、硝氮和氨氮在不同浓度水平下对中温厌氧颗粒污泥中厌氧细菌群落结构的影响.结果表明,高浓度亚硝氮(360 mg·L-1,以N计)、硝氮(300 mg·L-1,以N计)和氨氮(3000 mg·L-1,以N计)使系统COD去除率分别下降至3.49%、10.85%和71.53%,并使污泥表面主要细菌由杆菌变为球状菌;亚硝氮和硝氮引起厌氧细菌和革兰氏阳性菌的含量下降,氨氮引起革兰氏阴性菌的含量下降;PLFA香农-威尔多样性指数随着亚硝氮和硝氮浓度的升高从1.12分别下降至0.96和1.03,氨氮对PLFA香农-威尔多样性指数无明显影响.