Mn-Ce/Al_(2)O_(3)催化剂臭氧催化氧化深度处理漂染废水探析

针对某漂染企业生化出水提标改造的需求,以活性氧化铝为载体,以Mn为活性组分并掺杂稀土元素Ce构建复合催化剂,臭氧催化氧化深度处理漂染废水。实验结果表明,分散红模拟废水,CODCr为300 mg/L、废水体积为1 L时,活性组分Mn占催化剂总质量浓度的10%,催化剂投加量为10 g/L,臭氧浓度为250 mg/L,臭氧流量为50 mL/min,臭氧催化氧化60 min后,废水中CODCr、TOC的去除率分别为98.4%、97.1%。采用Mn-Ce/Al_(2)O_(3)催化剂臭氧催化氧化法深度处理实际漂染废水,出水的CODCr均低于50 mg/L,达到企业废水深度处理的要求。     

二氧化氯催化氧化处理印染废水

采用二氧化氯催化氧化法对沉淀后的印染厂废水进行处理,讨论了影响COD和色度去除率的各种因素;确定了该方法最佳的反应条件:二氧化氯投加量100mg/L,催化剂用量1g/L,溶液pH值6.5,反应时间45min。氧化后的废水CODCr120mg/L,色度≤40倍。     

反渗透浓水与生化出水的催化臭氧氧化试验

采用催化臭氧氧化法处理造纸废水反渗透(RO)浓水和二级生化出水,探讨了臭氧用量、反应时间对CODCr去除率的影响。结果表明,采用催化臭氧氧化法处理RO浓水,当臭氧用量为75 mg/(L·h)、反应时间为120 min时,COD_(Cr)去除率超过70%。采用催化臭氧氧化法处理二级生化出水时,当臭氧用量为100 mg/(L·h)、反应时间为90 min时,CODCr去除率超过60%,出水CODCr可稳定在30 mg/L以下,满足河北省地方标准DB 13/2795—2018 《大清河流域污染物排放标准》中关于重点控制区域的排放限值要求。中试和工程运行结果表明,在造纸废水RO浓水和二级生化出水的催化臭氧氧化处理中,工艺运行稳定可靠。     

Al2O3负载ZnO催化臭氧氧化处理造纸废水的研究

将ZnO负载在Al₂O₃上,制备用于催化臭氧降解造纸废水中有机物的催化剂（Al₂O₃@ZnO）;采用场发射扫描电子显微镜（SEM）和X射线衍射仪（XRD）对Al₂O₃@ZnO催化剂进行物相分析;研究了造纸废水的初始pH值、反应时间和催化剂用量对Al₂O₃@ZnO催化臭氧氧化处理造纸废水效果的影响;并进行了自由基捕集剂叔丁醇实验,以探讨降解造纸废水中有机物的主要因素。结果表明,本研究成功制备了具有良好催化性能的Al₂O₃@ZnO催化剂;在造纸废水初始pH值为11、催化剂用量为2.0 g/L、反应时间为60 min的条件下,Al₂O₃@ZnO催化剂对造纸废水中COD_Cr的去除率可达到84.6％,与单独使用臭氧氧化方法相比,COD_Cr去除率明显提高,且COD_Cr的动力学降解反应遵循准一级动力学方程;叔丁醇的实验结果表明,在Al₂O₃@ZnO催化臭氧氧化处理造纸废水有机物的过程中,羟基自由基是降解废水有机物的主要因素。     

基于硫酸根自由基的高级氧化技术深度处理造纸废水的研究

采用零价铁(ZVI)活化过硫酸钠(PS)产生硫酸根自由基的高级氧化技术处理造纸废水二级出水(CODCr为160 mg/L,色度为200度),考察了常温下pH值、ZVI用量、PS用量等因素对CODCr降解率及色度去除率的影响,并对其降解过程动力学进行了探讨,初步确定了硫酸根自由基氧化降解造纸废水的工艺条件,通过采用GC-MS检测分析了废水处理前后的物质变化情况。结果表明,在酸性至中性条件下,硫酸根自由基皆可有效降解有机污染物;在ZVI用量为8 g/L、PS用量为4 g/L时,室温条件下反应3h后,初始pH值为3和未调节pH值废水的CODCr降解率分别达到57.5%和34.2%,色度去除率分别达到83%和89%;通过GC-MS检测分析可知二级出水中含35种有机污染物,经过硫酸根自由基氧化降解后废水中苯类物质得到了一定的降解,相对含量有一定的变化,但种类基本没变。     

臭氧/过氧化氢氧化技术应用于2,4-二氯酚废水的实验研究

就O3/H2O2联合氧化工艺对2,4-二氯酚废水的降解效果进行研究。通过试验明确了O3投加浓度、废水初始p H值、H2O2投加浓度等因素对模拟废水中氯酚含量、CODCr两个指标的降解效果,同时应用单独O3氧化法与单独H2O2氧化法与O3/H2O2联合氧化法就降解效果相比较。结果表明,初始p H值对氧化效果有影响,在中性及偏碱性的条件下易达到较高去除率;随着H2O2投加浓度的增加,对CODCr的去除率随之提高,但到了投加浓度1.0m L/L之后,去除率提高不明显;最后,在O3投加浓度为63mg/L,反应时间60min,初始p H7.5,H2O2投加浓度为1.0m L/L时,2,4-DCP的去除率为99%以上,CODCr去除率为60%以上,增大O3投加浓度,CODCr去除率最高可达97%,在反应时间120min之内,CODCr去除率相比于单独O3氧化和单独H2O2氧化提高了15%和85%左右。     

活性炭催化臭氧处理造纸废水的实验研究

用活性炭催化臭氧氧化法处理生化后造纸废水,研究了pH值、活性炭加入量和活性炭回用次数对废水COD和色度的去除效果以及活性炭催化臭氧氧化过程对废水可生化性的改善。结果表明,pH值为7.98,活性炭加入量1g,臭氧化反应12min时,CODCr和色度去除率达到40.2%和91.6%,比单独臭氧氧化处理分别提高了7.6%和7.0%,BOD5/CODCr比值由单独臭氧化过程的0.14提高到0.26,可生化性得到明显改善。回用两次的活性炭参与臭氧化反应12min,废水CODCr去除率为35.4%,去除效果较好。催化臭氧化反应前后活性炭的红外谱图表明其表面吸附有大量有机降解物。     

活性炭负载铈催化臭氧处理桉木制浆废水

通过浸渍法在活性炭(AC)上负载铈(Ce)制备了催化剂(Ce-AC),并用X射线衍射仪(XRD)、扫描电子显微镜(SEM)和比表面积分析仪(BET)对制备的催化剂进行表征,研究了该催化剂催化臭氧处理桉木制浆废水对CODCr和色度的去除效果。结果表明,Ce以CeO_2晶型的形式负载在AC上;Ce负载量为1.0%时,Ce-AC催化臭氧处理桉木制浆废水效果最好;当反应30 min时,废水的色度和CODCr去除率达到95%和55%,分别比单独臭氧氧化过程提高10个和18个百分点,比AC催化臭氧氧化过程提高5个和12个百分点;Ce-AC催化臭氧处理桉木制浆废水极大地提高了对废水CODCr的去除率。动力学分析表明,单独臭氧氧化及AC、Ce-AC催化臭氧处理制浆废水的过程中,CODCr降解的反应符合表观二级动力学方程,负载的Ce提高了反应的动力学速率常数。     

基于两种不同自由基的高级氧化法深度处理造纸废水的对比研究

采用亚铁离子(Fe2+)活化过硫酸钠(PS)产生硫酸根自由基(SO4-.)和传统Fenton氧化法产生羟基自由基(.OH)氧化降解造纸废水中难降解的有机污染物,对比了两种高级氧化法的处理效果,考察了初始pH值、氧化剂用量、催化(活化)剂用量等对处理效果的影响及反应过程的规律。结果表明,与Fenton氧化体系相比,硫酸根自由基对pH值的适宜范围更广,在酸性至中性条件下,硫酸根自由基皆可有效降解有机污染物;在体系催化(活化)剂用量相同的条件下,两种自由基体系可以产生相当的处理效果,且Fe2+用量对PS氧化反应影响更小;两种氧化体系的CODCr降解率和色度去除率随氧化剂用量的增加而增加,达到适宜用量后Fenton氧化的CODCr降解率和色度去除率呈现下降趋势,而PS氧化的CODCr降解率和色度去除率趋于平缓;从氧化反应动力学可以看出,PS氧化反应相对缓慢些,且整个过程呈缓慢上升趋势,更利于氧化剂的完全利用。     

催化臭氧-砂滤联合工艺深度处理印染废水

采用催化臭氧-砂滤联合工艺对印染废水经水解酸化+生物接触氧化出水进行深度处理,考察了催化剂投加量、溶液初始pH、反应时间、砂滤对印染废水深度处理效果的影响。结果表明,溶液初始pH为9.5~10.5,氧化时间为20 min、Fe~(2+)投加量为4.5 mg/L、砂滤水力停留时间为20 min时,经处理后的出水水质稳定,能够满足《纺织染整工业水污染物排放标准》(GB4278-2012)的要求,该工艺具有可行性。     

Reliable identification of grapevine rootstock varieties using RAPD PCR on woody samples

Since grapevine ( Vitis spp .) rootstock material is being traded increasingly as disbudded woody material a lack of distinctive morphological features on such material necessitates an alternative and reliable means of identification. Methods described here were developed for rapid and efficient extraction of DNA from woody samples rich in phenolic compounds and polysaccharides, and for subsequent identification of varieties by RAPD PCR. Using these methods, and with the application of only one selected RAPD primer, we were able to differentiate sixteen rootstock varieties, including the seven varieties most commonly used in Germany. Problems commonly encountered with reproducibility of RAPD patterns were avoided by choosing primers with a dinucleotide sequence and a high G/C content that allowed a rather high annealing temperature of 45°C. Methods described here should also be useful for other horticultural crops, especially those with woody tissues rich in phenolic compounds and polysaccharides.     

An internet compendium of analytical methods and spectroscopic information for monomers and additives used in food packaging plastics

An internet website (http://cpf.jrc.it/smt/) has been produced as a means of dissemination of methods of analysis and supporting spectroscopic information on monomers and additives used for food contact materials (principally packaging). The site which is aimed primarily at assisting food control laboratories in the European Union contains analytical information on monomers, starting substances and additives used in the manufacture of plastics materials. A searchable index is provided giving PM and CAS numbers for each of 255 substances. For each substance a data sheet gives regulatory information, chemical structures, physico-chemical information and background information on the use of the substance in particular plastics, and the food packaging applications. For monomers and starting substances (155 compounds) the infra-red and mass spectra are provided, and for additives (100 compounds); additionally proton NMR are available for about 50% of the entries. Where analytical methods have been developed for determining these substances as residual amounts in plastics or as trace amounts in food simulants these methods are also on the website. All information is provided in portable document file (PDF) format which means that high quality copies can be readily printed, using freely available Adobe Acrobat Reader software. The website will in future be maintained and up-dated by the European Commission's Joint Research Centre (JRC) as new substances are authorized for use by the European Commission (DG-ENTR formerly DGIII). Where analytical laboratories (food control or other) require reference substances these can be obtained free-ofcharge from a reference collection housed at the JRC and maintained in conjunction with this website compendium.     

Aroma characterization of various apricot varieties using headspace–solid phase microextraction combined with gas chromatography–mass spectrometry and gas chromatography–olfactometry

The characterization of the aromatic profile of several apricot cultivars with molecular tracers in order to obtain objective data concerning the aromatic quality of this fruit was undertaken using headspace–solid phase microextraction (HS–SPME). Six apricot cultivars were selected according to their organoleptic characteristics: Iranien, Orangered, Goldrich, Hargrand, Rouge du Roussillon and A4025. The aromatic intensity of these varieties measured by HS–SPME–Olfactometry were defined and classified according to the presence and the intensity of grassy, fruity and apricot like notes. In the six varieties, 23 common volatile compounds were identified by HS–SPME–GC–MS. Finally, 10 compounds, ethyl acetate, hexyl acetate, limonene, β-cyclocitral, γ-decalactone, 6-methyl-5-hepten-2-one, linalool, β-ionone, menthone and (E)-hexen-2-al were recognized by HS–SPME–GC–O as responsible of the aromatic notes involved in apricot aroma and considered as molecular tracers of apricot aromatic quality which could be utilized to discriminate apricot varieties.     

Tests of potential functional barriers for laminated multilayer food packages. Part I: Low molecular weight permeants

The advent of the functional barrier concept in food packaging has brought with it a requirement for fast tests of permeation through potential barrier materials. In such tests it would be convenient for both foodstuffs and materials below the functional barrier (sub-barrier materials) to be represented by standard simulants. By means of inverse gas chromatography, liquid paraffin spiked with appropriate permeants was considered as a potential simulant of sub-barrier materials based on polypropylene (PP) or similar polyolefins. Experiments were performed to characterize the kinetics of the permeation of low molecular weight model permeants (octene, toluene and isopropanol) from liquid paraffin, through a surrogate potential functional barrier (25 μm-thick oriented PP) into the food simulants olive oil and 3% (w/v) acetic acid. These permeation results were interpreted in terms of three permeation kinetic models regarding the solubility of a particular model permeant in the post-barrier medium (i.e. the food simulant). The results obtained justify the development and evaluation of liquid sub-barrier simulants that would allow flexible yet rigorous testing of new laminated multilayer packaging materials.     

Textural Properties of Cold-set Gels Induced from Heat-denatured Whey Protein Isolates

A 9% whey protein (WP) isolate solution at pH 7.0 was heat-denatured at 80°C for 30 min. Size-exclusion HPLC showed that native WP formed soluble aggregates after heat-treatment. Additions of CaCl2 (10–40 mM), NaCl (50–400 mM) or glucono-delta-lactone (GDL, 0.4–2.0%, w/v) or hydrolysis by a protease from Bacillus licheniformis caused gelation of the denatured solution at 45°C. Textural parameters, hardness, adhesiveness, and cohesiveness of the gels so formed changed markedly with concentration of added salts or pH by added GDL. Maximum gel hardness occurred at 200 mM NaCl or pH 4.7. Increasing CaCl2 concentration continuously increased gel hardness. Generally, GDL-induced gels were harder than salt-induced gels, and much harder than the protease-induced gel.     

Occurrence of bisphenol-F-diglycidyl ether (BFDGE) in fish canned in oil

The levels of bisphenol-F-diglycidyl ether (BFDGE) were quantified as part of a European survey on the migration of residues of epoxy resins into oil from canned fish. The contents of BFDGE in cans, lids and fish collected from all 15 Member States of the European Union and Switzerland were analysed in 382 samples. Cans and lids were separately extracted with acetonitrile. The extraction from fish was carried out with hexane followed by re-extraction with acetonitrile. The analysis was performed by reverse phase HPL C with fluorescence detection. BFDGE could be detected in 12% of the fish, 24% of the cans and 18% of the lids. Only 3% of the fish contained BFDGE in concentrations considerably above 1mg/kg. In addition to the presented data, a comparison was made with the levels of BADGE (bisphenol-A-diglycidyl ether)analysed in the same products in the context of a previous study.     

Analysis of benzo[a]pyrene in spiked fatty foods by second derivative synchronous spectrofluorimetry after microwave-assisted treatment of samples

A simple, rapid and inexpensive method has been developed for the determination of benzo[a     

The development of reference materials for paralytic shellfish poisoning toxins in lyophilized mussel. II: Certification study

This paper describes the second part of a project undertaken to develop certified mussel reference materials for paralytic shellfish poisoning toxins. In the first part two interlaboratory studies were undertaken to investigate the performance of the analytical methodology for several PSP toxins, in particular saxitoxin and decarbamoyl-saxitoxin in lyophilized mussels, and to set criteria for the acceptance of results to be applied during the certification exercise. Fifteen laboratories participated in this certification study and were asked to measure saxitoxin and decarbamoyl-saxitoxin in rehydrated lyophilized mussel material and in a saxitoxin-enriched mussel material. The participants were allowed to use a method of their choice but with an extraction procedure to be strictly followed. The study included extra experiments to verify the detection limits for both saxitoxin and decarbamoyl-saxitoxin. Most participants (13 of 15) were able to meet all the criteria set for the certification study. Results for saxitoxin.2HCl yielded a certified mass fraction of <0.07 mg/kg in the rehydrated lyophilized mussels. Results obtained for decarbamoyl-saxitoxin.2HCl yielded a certified mass fraction of 1.59+/-0.20 mg/kg. The results for saxitoxin.2HCl in enriched blank mussel yielded a certified mass fraction of 0.48 +/- 0.06 mg/kg. These certified reference materials for paralytic shellfish poisoning toxins in lyophilized mussel material are the first available for laboratories to test their method for accuracy and performance.     

Contribution of European research to risk analysis

The European Commission's, Quality of Life Research Programme, Key Action 1—Health, Food & Nutrition is mission-oriented and aims, amongst other things, at providing a healthy, safe and high-quality food supply leading to reinforced consumer confidence in the safety of European food. Its objectives also include the enhancing of the competitiveness of the European food supply. Key Action 1 is currently supporting a number of different types of European collaborative projects in the area of risk analysis. The objectives of these projects range from the development and validation of prevention strategies including the reduction of consumers risks; development and validation of new modelling approaches; harmonization of risk assessment principles, methodologies, and terminology; standardization of methods and systems used for the safety evaluation of transgenic food; providing of tools for the evaluation of human viral contamination of shellfish and quality control; new methodologies for assessing the potential of unintended effects of genetically modified (genetically modified) foods; development of a risk assessment model for Cryptosporidium parvum related to the food and water industries; to the development of a communication platform for genetically modified organism, producers, retailers, regulatory authorities and consumer groups to improve safety assessment procedures, risk management strategies and risk communication; development and validation of new methods for safety testing of transgenic food; evaluation of the safety and efficacy of iron supplementation in pregnant women; evaluation of the potential cancer-preventing activity of pro- and pre-biotic ('synbiotic') combinations in human volunteers. An overview of these projects is presented here.