-
近年来,高碘酸盐(IO4−,PI)作为一种氧化、消毒过程的新型水处理试剂,因其强氧化特性和氧化过程产生无毒、稳定的氧化产物(碘酸盐)[1 − 3],受到环境领域研究者关注[4 − 7]. 随着高级氧化技术(AOPs)的不断发展,活化高碘酸盐产生活性自由基降解有机污染物的研究逐渐成为环境领域研究热点[8 − 10]. 但是,高浓度的高碘酸盐是一类潜在的有毒物质,例如,高碘酸盐引起的碘含量增加可能导致甲状腺毒症,对小鼠腹腔内的半数致死量(LD50)为58 mg·kg−1[11]. 因此,在利用高碘酸盐的氧化特性合成有机物、分析物质浓度及降解污染物的过程中,需要准确量化反应体系中PI的消耗量,以研究高碘酸盐的氧化效能和机理,并防止过量的PI释放到水体中造成污染. 因此,建立经济、简便、高灵敏度、准确的分析方法测定水中微量的高碘酸盐尤为必要.
目前PI的测定方法主要有脉冲极谱法[12]、直接电位法[13]、循环伏安法[14]、碘量法[15]、色谱法[16]、荧光探针法[17]等,但这些分析方法均具有其局限性,无法满足实际应用要求. 例如,经典的碘量法测定PI,滴定步骤过于繁琐和耗时,不适于常规快速分析. 电化学法、色谱法和荧光法灵敏度高,但需要昂贵、操作复杂的仪器,亦不适用于常规分析. 分光光度法由于其分析速度快、操作方便、成本低等优点而被广泛应用[18]. 其中,2, 2-联氮-二(3-乙基-苯并噻唑-6-磺酸)(ABTS)和N, N-二乙基对苯二胺(DPD)因能被氧化剂氧化生成稳定带色自由基,而被普遍用于测定水处理中各种氧化剂(如过氧化氢[19]、过硫酸盐[20]、一氯胺[21]等)的浓度. 尽管目前已有相关的研究使用ABTS和DPD检测水中是否存在PI[22],但基于PI与ABTS或DPD反应,系统建立测定水中微量PI浓度的分光光度法尚未被报道.
本研究基于DPD、ABTS与PI的显色反应,分别建立了两种测定实际水样中微量高碘酸盐浓度的分光光度法,优化了两种方法的最佳反应pH、反应时间、显色剂浓度,并考察了共存离子、腐殖酸、不同水质背景对两种方法的影响,为建立快速,准确、低成本测定水中微量PI浓度的方法提供技术参考.
2,2-联氮-二(3-乙基-苯并噻唑-6-磺酸)(ABTS)和N,N-二乙基对苯二胺(DPD)显色分光光度法测定水中微量高碘酸盐的对比
Comparison of the spectrophotometric determination for trace periodate in water with 2,2’-azino-bis(3-ethylbenzothiazoline-6-sulfonate) (ABTS) and N,N-diethyl phenylene-1,4-diamine (DPD)
-
摘要: 高碘酸盐(IO4−,PI)因具有强氧化性和化学稳定性,被广泛应用于环境污染物的氧化降解,然而传统的PI分析方法具有操作复杂、费用高和检出限高等缺点,不适用于常规分析. 因此如何快速、准确、低成本测定水中微量PI备受环境领域研究者的关注. 本研究基于2,2-联氮-二(3-乙基-苯并噻唑-6-磺酸)(ABTS)和N,N-二乙基对苯二胺(DPD)与PI氧化显色的原理,建立了两种利用分光光度法测定水中低浓度PI的方法. 结果表明,当pH = 3.0时,ABTS与PI的反应化学计量系数接近1: 2,最大吸光值在415 nm处,标准曲线线性范围为0 — 20 μmol·L−1(R2>0.997),灵敏度为(6.45±0.03)× 104 L·mol−1·cm−1,检出限和定量下限分别为1.1 × 10−8 mol·L−1和3.3 × 10−8 mol·L−1;当pH = 6.5时,DPD与PI的反应化学计量系数为1: 2,最大吸光值在551 nm处,标准曲线线性范围为0 — 40 μmol·L−1(R2>0.998),灵敏度为(2.11±0.08)× 104 L·mol−1·cm−1,检出限和定量下限分别为3.7 × 10−7 mol·L−1和1.23 × 10−6 mol·L−1. 最后,研究了水中常见共存离子、腐殖酸、实际水质背景对PI测定的影响以及加标回收率,发现两种方法均具有良好的抗干扰性、稳定性和检测精度. 本研究结果表明两种方法可准确、快速、低成本测定水中微量PI浓度并具有较好的应用前景.
-
关键词:
- 高碘酸盐 /
- 分光光度法 /
- 2,2-联氮-二(3-乙基-苯并噻唑-6-磺酸)(ABTS) /
- N,N-二乙基对苯二胺(DPD) /
- 水处理.
Abstract: Periodate (IO4−, PI) is widely used in the oxidative degradation of environmental pollutants due to its strong oxidation and chemical stability. However, traditional methods for PI analysis have the disadvantages of complicated operation, high cost and high detection limit, which are not suitable for routine analysis. Therefore, detecting trace PI in water quickly, accurately and cheaply has attracted much attention from environmental researchers. Two new spectrophotometric methods for the determination of trace PI in water were proposed based on the oxidative coloration of 2,2’-azino-bis(3-ethylbenzothiazoline-6-sulfonate) (ABTS) or N,N-diethyl-p-phenylenediamine (DPD) and PI in this study. Results show that the stoichiometric coefficient of ABTS and PI is close to 1:2, and the maximum absorption value is 415 nm at pH = 3.0. The linear range of the standard curve was 0—20 µmol·L−1 (R2>0.997), and the sensitivity was (6.45±0.03) × 104 L·mol−1·cm−1. The limit of detection and lower limit of quantitation were 1.1 × 10−8 mol·L−1 and 3.3 × 10−8 mol·L−1, respectively. The stoichiometric coefficient of DPD and PI reaction was 1:2, the maximum absorption value was 551 nm in pH = 6.5. The linear range of the standard curve was 0 — 40 µmol·L−1 (R2>0.998), and the sensitivity was (2.11±0.08) × 104 L·mol−1·cm−1. The limit of detection and lower limit of quantitation were 3.7 × 10−7 mol·L−1 and 1.23 × 10−6 mol·L−1, respectively. Finally, the influence of common coexisting ions, the actual water quality background and the recovery rate were studied. It was found that two methods have good anti-interference performance, stability and detection accuracy. The results of this study indicate that the two methods can accurately, rapidly and cheaply determine the concentration of trace PI in water, and have a good application prospect. -
图 6 (A)ABTS浓度对ABTS·+在415 nm处生成速率的影响;(B)ABTS浓度对ABTS溶液在415 nm处吸光度值的影响;(C) DPD浓度对DPD溶液在551 nm处吸光度值的影响
Figure 6. (A) Effect of ABTS concentration on the rate of ABTS·+ formation at 415 nm; (B) Effect of ABTS concentration on the absorbance at 415 nm; (C) Effect of DPD concentration on the absorbance at 551 nm
表 1 不同实际水样的主要水质参数
Table 1. Major water parameters of different real water samples
水质背景
Water matrixespH DOC/
(mg·L−1)碱度/(mg·L−1)*
Alkalinity自来水 7.36 0.83 49.82 水库水 7.69 10.63 117.43 地下水 7.26 6.35 68.75 污水 6.72 53.62 42.53 注:* 以CaCO3计算. Note:* Calculated as CaCO3 . 表 2 不同峰值剂量干扰离子条件下两种PI浓度测定方法的回收试验
Table 2. Recovery test of two methods for PI determination with different spiking dosages of interference ions
共存离子
Interference ion[PI]/[干扰离子]
Interference ion回收率/%
Recovery rateABTS DPD PI — 100.1±0.87 101.1±0.95 Fe3+ 1:500 104.6±1.23 99.7±0.0.89 1:1000 117.6±1.14 103.4±0.76 Co2+ 1:200 108.7±1.33 101.2±0.84 1:500 130.3±1.28 104.4±0.79 Cu2+ 1:50 240.3±1.68 103.4±0.54 1:100 251.2±1.55 106.7±1.22 Ca2+ 1:500 102.5±0.98 101.3±0.56 1:1000 105.7±1.24 104.6±0.85 Mg2+ 1:200 103.3±1.54 101.9±1.25 1:500 107.5±1.03 105.6±1.11 Na+ 1:500 102.3±1.26 101.9±1.63 1:1000 106.6±0.93 105.6±1.45 NO3− 1:500 102.7±1.59 102.6±1.68 1:1000 104.6±1.66 105.8±1.57 SO42− 1:500 102.3±1.74 101.7±1.25 1:1000 104.2±1.57 106.4±1.23 CO32− 1: 200 100.8±2.05 101.5±1.36 1:500 104.7±2.37 106.4±1.49 Cl− 1:500 102.5±1.84 103.4±1.39 1:1000 105.4±1.69 106.3±1.35 Br− 1:500 109.6±1.79 102.4±1.84 1:1000 120.9±1.94 105.5±1.58 腐殖酸(HA) 1:5 101.5±1.64 102.7±1.42 1:10 103.3±1.38 104.8±1.86 表 3 不同高碘酸根分析方法的检出限对比
Table 3. Comparison of detection limits of different analysis methods for periodate
表 4 回收试验结果(n=5)
Table 4. Results of recovery experiment (n=5)
水质
Water matrixes加标量/(μmol·L−1)
Spiked测量值/(μmol·L−1)
MeasuredRSD/% 回收率/%
RecoveryABTS DPD ABTS DPD ABTS DPD 超纯水 5.0 4.82±0.07 4.89±0.12 1.45 2.45 96.4 97.6 10.0 10.12±0.12 9.98±0.08 1.18 1.82 101.2 99.3 20.0 19.76±0.18 20.16±0.42 0.91 2.01 98.8 100.8 自来水 5.0 4.92±0.05 5.08±0.13 1.01 2.61 98.5 101.6 10.0 9.96±0.12 9.93±0.34 1.20 3.42 99.6 99.3 20.0 19.48±0.19 20.78±0.45 0.97 2.16 97.4 103.9 水库水 5.0 5.07±0.07 5.23±0.16 1.38 3.06 101.4 104.6 10.0 9.93±0.16 10.25±0.24 1.61 2.34 99.3 102.5 20.0 19.58±0.21 20.56±0.36 1.07 1.75 97.9 102.8 地下水 5.0 4.93±0.06 4.98±0.14 1.21 2.81 98.6 99.7 10.0 9.67±0.12 10.06±0.19 1.24 1.89 96.7 100.6 20.0 19.86±0.21 19.36±0.37 1.05 1.91 99.3 96.8 污水 5.0 5.21±0.11 7.03±0.19 2.11 2.71 104.2 140.6 10.0 10.39±0.16 11.51±0.21 1.54 1.82 103.9 115.1 20.0 19.88±0.29 22.08±0.48 1.56 2.17 99.4 110.4 -
[1] MOZAFARI H, HOJJATOLESLAMY M, MOHAMMADIZADEH M. Optimizing the properties of Zodo gum and examining its potential for amino acid binding by periodate oxidation[J]. International Journal of Biological Macromolecules, 2021, 167: 1517-1526. doi: 10.1016/j.ijbiomac.2020.11.106 [2] PANDEIRADA C O, ACHTERWEUST M, JANSSEN H G, et al. Periodate oxidation of plant polysaccharides provides polysaccharide-specific oligosaccharides[J]. Carbohydrate Polymers, 2022, 291: 119540. doi: 10.1016/j.carbpol.2022.119540 [3] LI J J, ZHANG J, XU M M, et al. Advances in glycopeptide enrichment methods for the analysis of protein glycosylation over the past decade[J]. Journal of Separation Science, 2022, 45(16): 3169-3186. doi: 10.1002/jssc.202200292 [4] ALI SHAH S N, KHAN M, REHMAN Z U. A prolegomena of periodate and peroxide chemiluminescence[J]. TrAC Trends in Analytical Chemistry, 2020, 122: 115722. doi: 10.1016/j.trac.2019.115722 [5] LIU F Y, LI Z M, DONG Q Q, et al. Catalyst-free periodate activation by solar irradiation for bacterial disinfection: Performance and mechanisms[J]. Environmental Science & Technology, 2022, 56(7): 4413-4424. [6] ZHANG K T, ZHANG S Q, YE C S, et al. Sunlight-activated periodate oxidation: A novel and versatile strategy for highly efficient water decontamination[J]. Chemical Engineering Journal, 2023, 451: 138642. doi: 10.1016/j.cej.2022.138642 [7] SUN H W, HE F, CHOI W. Production of reactive oxygen species by the reaction of periodate and hydroxylamine for rapid removal of organic pollutants and waterborne bacteria[J]. Environmental Science & Technology, 2020, 54(10): 6427-6437. [8] LI R X, WANG J Q, WU H, et al. Periodate activation for degradation of organic contaminants: Processes, performance and mechanism[J]. Separation and Purification Technology, 2022, 292: 120928. doi: 10.1016/j.seppur.2022.120928 [9] FANG G G, LI J L, ZHANG C, et al. Periodate activated by manganese oxide/biochar composites for antibiotic degradation in aqueous system: Combined effects of active manganese species and biochar[J]. Environmental Pollution, 2022, 300: 118939. doi: 10.1016/j.envpol.2022.118939 [10] LONG Y K, DAI J A, ZHAO S Y, et al. Atomically dispersed cobalt sites on graphene as efficient periodate activators for selective organic pollutant degradation[J]. Environmental Science & Technology, 2021, 55(8): 5357-5370. [11] LENT E M, CROUSE L C B, ECK W S. Acute and subacute oral toxicity of periodate salts in rats[J]. Regulatory Toxicology and Pharmacology, 2017, 83: 23-37. doi: 10.1016/j.yrtph.2016.11.014 [12] ELMOSALAMY M A F, MOODY G J, THOMAS J D R, et al. Poly (vinyl chloride) matrix membrane electrodes responsive to thiocyanate, perchlorate and periodate[J]. Analytical Letters, 1987, 20(10): 1541-1555. doi: 10.1080/00032718708078025 [13] OTHMAN A M. PVC membrane sensor based on periodate—Cetylpyridinium ion pair for the potentiometric determination of periodate[J]. Journal of Analytical Chemistry, 2010, 65(11): 1191-1197. doi: 10.1134/S106193481011016X [14] GÖKÇEL H İ, NIŞLI G. Static and flow-injection voltammetric determination of periodate by reduction at a rotating platinum wire electrode[J]. Analytica Chimica Acta, 1994, 292(1/2): 99-105. [15] VEELAERT S, de WIT D, TOURNOIS H. An improved kinetic model for the periodate oxidation of starch[J]. Polymer, 1994, 35(23): 5091-5097. doi: 10.1016/0032-3861(94)90670-X [16] GUPTA M, JAIN A, VERMA K K. Optimization of experimental parameters in single-drop microextraction-gas chromatography-mass spectrometry for the determination of periodate by the Malaprade reaction, and its application to ethylene glycol[J]. Talanta, 2007, 71(3): 1039-1046. doi: 10.1016/j.talanta.2006.05.083 [17] HONG K I, CHOI W H, JANG W D. Hydroxythiophene-bearing benzothiazole: Selective and sensitive detection of periodate and its application as security ink[J]. Dyes and Pigments, 2019, 162: 984-989. doi: 10.1016/j.dyepig.2018.11.026 [18] SHI Z N, CHOW C W K, FABRIS R, et al. Applications of online UV-vis spectrophotometer for drinking water quality monitoring and process control: A review[J]. Sensors, 2022, 22(8): 2987. doi: 10.3390/s22082987 [19] ZOU J, CAI H H, WANG D Y, et al. Spectrophotometric determination of trace hydrogen peroxide via the oxidative coloration of DPD using a Fenton system[J]. Chemosphere, 2019, 224: 646-652. doi: 10.1016/j.chemosphere.2019.03.005 [20] ZOU J, HUANG Y X, ZHU L R, et al. Multi-wavelength spectrophotometric measurement of persulfates using 2, 2’-azino-bis(3-ethylbenzothiazoline-6-sulfonate) (ABTS) as indicator[J]. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2019, 216: 214-220. doi: 10.1016/j.saa.2019.03.019 [21] 陶辉, 王玲, 李星, 等. 饮用水氯胺法消毒过程中一氯胺的水杨酸分光光度法测定[J]. 环境化学, 2009, 28(1): 126-131. doi: 10.3321/j.issn:0254-6108.2009.01.027 TAO H, WANG L, LI X, et al. Monochloramine testing method in chloramination process—Salicylate spectrophotometric method[J]. Environmental Chemistry, 2009, 28(1): 126-131 (in Chinese). doi: 10.3321/j.issn:0254-6108.2009.01.027
[22] LIIMATAINEN H, SIRVIÖ J, PAJARI H, et al. Regeneration and recycling of aqueous periodate solution in dialdehyde cellulose production[J]. Journal of Wood Chemistry and Technology, 2013, 33(4): 258-266. doi: 10.1080/02773813.2013.783076 [23] 黄丽萍, 马华, 潘雨, 等. 石墨烯对漆酶/介体系统降解碱木素的影响[J]. 环境化学, 2018, 37(4): 704-712. doi: 10.7524/j.issn.0254-6108.2017082305 HUANG L P, MA H, PAN Y, et al. Effects of graphene on the degradation of alkali lignin by laccase-mediator system[J]. Environmental Chemistry, 2018, 37(4): 704-712 (in Chinese). doi: 10.7524/j.issn.0254-6108.2017082305
[24] 张司雨, 董仕鹏, 高士祥, 等. 漆酶/ABTS介体系统催化氧化羟基化多溴联苯醚[J]. 环境化学, 2022, 41(12): 3855-3865. doi: 10.7524/j.issn.0254-6108.2022062702 ZHANG S Y, DONG S P, GAO S X, et al. Transformation of hydroxylation polybrominateddiphenyl ethers in laccase-ABTS system[J]. Environmental Chemistry, 2022, 41(12): 3855-3865 (in Chinese). doi: 10.7524/j.issn.0254-6108.2022062702
[25] GRAMSS G. Reappraising a controversy: Formation and role of the azodication (ABTS2+) in the laccase-ABTS catalyzed breakdown of lignin[J]. Fermentation, 2017, 3(2): 27. doi: 10.3390/fermentation3020027 [26] ALBERTI A, BOLOGNINI L, MACCIANTELLI D, et al. The radical cation of N, N-diethyl-para-phenylendiamine: A possible indicator of oxidative stress in biological samples[J]. Research on Chemical Intermediates, 2000, 26(3): 253-267. doi: 10.1163/156856700X00769 [27] CODOLÀ Z, M S CARDOSO J, ROYO B, et al. Highly effective water oxidation catalysis with iridium complexes through the use of NaIO4[J]. Chemistry - A European Journal, 2013, 19(22): 7203-7213. doi: 10.1002/chem.201204568 [28] CAI H H, LIU X, ZOU J, et al. Multi-wavelength spectrophotometric determination of hydrogen peroxide in water with peroxidase-catalyzed oxidation of ABTS[J]. Chemosphere, 2018, 193: 833-839. doi: 10.1016/j.chemosphere.2017.11.091 [29] FAN W J, QIAO J L, GUAN X H. Multi-wavelength spectrophotometric determination of Cr(VI) in water with ABTS[J]. Chemosphere, 2017, 171: 460-467. doi: 10.1016/j.chemosphere.2016.11.153 [30] LABRINEA E P, GEORGIOU C A. Stopped-flow method for assessment of pH and timing effect on the ABTS total antioxidant capacity assay[J]. Analytica Chimica Acta, 2004, 526(1): 63-68. doi: 10.1016/j.aca.2004.09.040 [31] GOKULAKRISHNAN S, MOHAMMED A, PRAKASH H. Determination of persulphates using N, N-diethyl-p-phenylenediamine as colorimetric reagent: Oxidative coloration and degradation of the reagent without bactericidal effect in water[J]. Chemical Engineering Journal, 2016, 286: 223-231. doi: 10.1016/j.cej.2015.10.058 [32] PINKERNELL U, NOWACK B, GALLARD H, et al. Methods for the photometric determination of reactive bromine and chlorine species with ABTS[J]. Water Research, 2000, 34(18): 4343-4350. doi: 10.1016/S0043-1354(00)00216-5 [33] BADER H, STURZENEGGER V, HOIGNÉ J. Photometric method for the determination of low concentrations of hydrogen peroxide by the peroxidase catalyzed oxidation of N, N-diethyl-p-phenylenediamine (DPD)[J]. Water Research, 1988, 22(9): 1109-1115. doi: 10.1016/0043-1354(88)90005-X [34] LI T, DAI L, HUANG Y X, et al. Spectrophotometric determination of Cr(VI) in water using N, N-diethyl-p-phenylenediamine (DPD) as the indicator[J]. Journal of Environmental Chemical Engineering, 2021, 9(5): 105517. doi: 10.1016/j.jece.2021.105517 [35] LIU X, FU Q, XU P, et al. Rapid determination of monopersulfate with bromide ion-catalyzed oxidation of 2, 2’-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid (ABTS)[J]. Chemical Engineering Journal, 2022, 433: 133551. doi: 10.1016/j.cej.2021.133551