测定高氯废水CODcr的方法探讨——硫酸汞添加法

化学需氧量是评价水体中有机物污染的重要指标,通常采用CODcr来表示。在其测定过程中氯离子是影响结果准确性的重要因素。由于氯离子的干扰,高氯废水中化学需氧量测定误差较大,尤其对于高氯低化学需氧量的水样,其干扰更为严重。本文对高氯废水化学需氧量的测定方法以及原理进行了阐述,针对不同范围的化学需氧量,对应采用高浓度重铬酸钾氧化法、低浓度重铬酸钾氧化法来测定,最终确定了一种最直接、简便、准确的方法-硫酸汞添加法来测定高氯废水的CODcr。     

COD_(CH_4)/COD值评价垃圾渗滤液厌氧可生化性的研究

基于理论分析,提出CODCH4/COD值作为废水厌氧可生化性的评价指标,确定了CODCH4/COD值表示厌氧可生化性的数值界限。同时,在BMP分析的基础上,采用CODCH4/COD值考察了垃圾渗滤液的厌氧可生化性,并与BOD5/COD值评价结果进行了对比。实验结果显示,CODCH4/COD值与BOD5/COD值用于垃圾渗滤液可生化性的评价,得出的结论具有相似性,但CODCH4/COD值大于BOD5/COD值。究其原因:好氧条件下,总的生化耗氧量(BOD)u小于理论完全需氧量(COD);厌氧条件下,有机物完全去除时CODCH4(理)等于理论完全需氧量。此外,BOD5测试时间仅5 d,而BMP测试时间一般在30 d以上,从而使微生物有足够的时间去适应废水水质,故能较好地反映废水的可生化性。     

Carbon dioxide emissions from spring ploughing of grassland in Ireland

Grassland re-seeding or land-use change requires ploughing, which may enhance carbon dioxide (CO₂) emissions from soil. This study observed the short to intermediate-term (37 days) effects of ploughing on CO₂ emissions from poorly drained grassland using automated soil respiration chambers. Immediately after ploughing, a brief peak in CO₂ emissions from soil occurred with a maximum observed flux of 6.91 g CO₂ m⁻² h⁻¹. Contradictory to other reported results, ecosystem respiration after ploughing was lower on the ploughed than on the grass site. After including estimates of photosynthesis in the analysis, ploughing led to significantly higher net CO₂ emissions than from grassland. The main mechanism of C loss during ploughing was most likely due to a reduction in gross primary production rather than enhanced soil respiration.     

Humic acid and metal ions accelerating the dechlorination of 4-chlorobiphenyl by nanoscale zero-valent iron

Transformation of polychlorinated biphenyls (PCBs) by zero-valent iron represents one of the latest innovative technologies for environmental remediation. The dechlorination of 4-chlorobiphenyl (4-ClBP) by nanoscale zero-valent iron (NZVI) in the presence of humic acid or metal ions was investigated. The results showed that the dechlorination of 4-ClBP by NZVI increased with decreased solution pH. When the initial pH value was 4.0, 5.5, 6.8, and 9.0, the dechlorination efficiencies of 4-ClBP after 48 hr were 53.8%, 47.8%, 35.7%, and 35.6%, respectively. The presence of humic acid inhibited the reduction of 4-ClBP in the first 4 hr, and then significantly accelerated the dechlorination by reaching 86.3% in 48 hr. Divalent metal ions, Co2+, Cu2+, and Ni2+, were reduced and formed bimetals with NZVI, thereby enhanced the dechlorination of 4-ClBP. The dechlorination percentages of 4-ClBP in the presence of 0.1 mmol/L Co2+, Cu2+ and Ni2+ were 66.1%, 66.0% and 64.6% in 48 hr, and then increased to 67.9%, 71.3% and 73.5%, after 96 hr respectively. The dechlorination kinetics of 4-ClBP by the NZVI in all cases followed pseudo-first order model. The results provide a basis for better understanding of the dechlorination mechanisms of PCBs in real environment.     

固定在活性炭聚砜中空纤维膜中的Pseudomonas putida菌对四氯苯酚的共代谢降解

以苯酚-四氯苯酚共代谢体系为对象,研究了中空纤维聚砜膜作为细菌固定化材料对该共代谢过程的强化作用.结果表明,该膜具有内、中、外3层的结构,Pseudomonas putida菌可被固定在膜的表面和中间层;固定化后,细菌对高浓度有毒底物的忍受限度增强,从而得以持续生长,并在29 h内将600　mg/L和120　mg/L的苯酚和四氯苯酚完全降解.在膜的制作过程中添加了一定量的活性炭后,发现膜对苯酚和四氯苯酚的吸附能力增强,同时结构上更疏松,对四氯苯酚的降解效率得到了提高.固定在活性碳中空纤维膜中的Pseudomonas putida可以将1 000　mg/L和200　mg/L的苯酚和四氯苯酚在51 h内完全降解,比不加活性炭的情况缩短了37 h,中空纤维膜可以连续多次使用,对相同浓度的四氯苯酚的降解速度保持稳定.     

不同共基质条件下上流式厌氧污泥床反应器中硝基酚的降解研究

用实验室规模的2个UASB反应器,分别研究了以葡萄糖和乙酸钠为共基质条件下3-硝基酚(3-NP)和2,6-二硝基酚（2,6-DNP）的降解效果.结果表明,对3-NP的降解,用葡萄糖作共基质的效果明显好于以乙酸钠为共基质;而对2,6-DNP的降解,乙酸钠作共基质效果更好.在含3-NP废水厌氧降解实验中,保持进水COD浓度为2 500 mg/Ｌ左右,HRT为26 h,以葡萄糖为共基质时,进水3-NP浓度可提高到254.6 mg/Ｌ,3-NP的去除率保持在99.0%以上;以乙酸钠为共基质时,保持HRT为30 h,3-NP浓度可提高到71.6 mg/Ｌ,3-NP去除率在90.0%以上.在含2,6-DNP废水厌氧降解实验中,保持进水COD浓度在2 500 mg/Ｌ左右,HRT为35 h,以葡萄糖为共基质时,2,6-DNP浓度可提高到170.0 mg/Ｌ,2,6-DNP的去除率保持在98.0%以上;以乙酸钠为共基质时,保持HRT为30 h,2,6-DNP最大浓度可提高到189.5 mg/Ｌ,2,6-DNP的去除率在99.2%以上.     

纳米FeO作用下4-氯酚的脱氯特性及机理

采用化学还原法制备了纳米Fe^O, ESEM测定结果表明其颗粒在1～100 nm内. 实验表明这些纳米Fe^O能在20 h内将初始浓度为20 mg/L的4-氯酚完全降解, Fe^O对4-CP的还原脱氯是主要去除途径. 苯酚是脱氯反应的主要产物. 当4-CP的初始浓度由20　mg/L增大到50, 100, 150　mg/L时, 其相对去除率明显降低, 但绝对降解量有较大提高. 温度不仅影响脱氯速率, 而且影响4-CP去除的途径. 30℃时, 脱氯反应为主要反应; １０℃时, 较易产生氧化产物. Fe原子的迁移过程在4-CP的降解中也是一个重要的限速步骤. 此外, 纳米Fe^O具有很好的稳定性, 在受试的379　h内, 纳米Fe^O能够应对不同浓度冲击及反复投加的4-氯酚冲击的能力.     

离子液体双水相气浮溶剂浮选分离/富集水样中的盐酸多西环素研究

建立了以亲水性离子液体1-丁基-3-甲基咪唑四氟硼酸[Bmim]BF4和Na H2PO4形成的二元双水相作为气浮溶剂分离/富集水样中盐酸多西环素的新方法,并采用紫外分光光度法对盐酸多西环素进行测定。考察了离子液体的初始加入量、盐的种类及浓度、p H值、浮选时间及N2流速等因素对体系浮选分离盐酸多西环素的影响。结果表明,改变离子液体和无机盐的加入量,会使体系的富集倍数发生变化,从而使体系的浮选效率和浓集系数发生变化;随浮选时间增加,体系的浮选效率先增加后略微下降;过大或过小的N2流速都会使体系对盐酸多西环素的浮选效率降低;而p H值对体系浮选盐酸多西环素影响不大。当[Bmim]BF4溶液加入量为3 m L、Na H2PO4加入量为25 g(质量分数为33.3%)、气浮时间为40 min、气浮速率为50 m L/min时,体系的浮选效率最高,可达95.8%,浓集系数可达23.95,此时体系的p H值为4.38。与离子液体双水相萃取(ILATPE)相比,该方法的优点在于不仅有较高的浮选率、浓集系数,还有效减少了离子液体的用量,同时操作更简单、环境友好。     

Oxidation of diesel soot on binary oxide CuCr(Co)-based monoliths

Binary oxide systems (CuCr₂O₄, CuCo₂O₄), deposited onto cordierite monoliths of honeycomb structure with a second support (finely dispersed Al₂O₃), were prepared as filters for catalytic combustion of diesel soot using internal combustion engine's gas exhausts (O₂, NO_x, H₂O, CO₂) and O³ as oxidizing agents. It is shown that the second support increases soot capacity of aforementioned filters, and causes dispersion of the particles of spinel phases as active components enhancing thereby catalyst activity and selectivity of soot combustion to CO₂. Oxidants used can be arranged with reference to decreasing their activity in a following series: O₃ >> NO₂ > H₂O > NO > O₂ > CO₂. Ozone proved to be the most efficient oxidizing agent: the diesel soot combustion by O₃ occurs intensively (in the presence of copper chromite based catalyst) even at closing to ambient temperatures. Results obtained give a basis for the conclusion that using a catalytic coating on soot filters in the form of aforementioned binary oxide systems and ozone as the initiator of the oxidation processes is a promising approach in solving the problem of comprehensive purification of automotive exhaust gases at relatively low temperatures, known as the "cold start" problem.     

土壤粒径、氮素及重金属对填埋场覆土CH_4氧化的影响

采用批式培养试验重点研究了土壤粒径、NH4+-N和NO3--N及重金属〔Zn和Cr(Ⅵ)〕含量对填埋场砂性覆土及一般砂土CH4氧化能力的影响.结果表明:合适的土壤粒径能显著提高砂性覆土和一般砂土的CH4氧化能力(P0.05),当粒径为1.00~2.00 mm时,砂性覆土和一般砂土的CH4氧化速率分别高达0.24和0.12μmol/(g·h).低浓度NH4+-N或NO3--N均可以促进砂性覆土和一般砂土的CH4氧化,而高浓度则会明显抑制CH4氧化.砂性覆土和一般砂土的外源氨氮和外源NO3--N的投加量(以w计)临界值均为200 mg/kg,砂性覆土对NH4+-N浓度的波动有更好的适应能力;重金属Zn、Cr(Ⅵ)对砂性覆土和一般砂土CH4氧化的抑制作用均随浓度的升高而增强,Zn对砂性覆土CH4氧化的抑制作用程度大于Cr,并且Zn对一般砂土CH4氧化的抑制程度明显强于砂性覆土.为此,筛选合适粒径级配的土壤,同时控制覆土中氮素及重金属的本底含量,有利于填埋场CH4氧化.