A Review on Detection Methods of Chemical Oxygen Demand in Water Bodies
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摘要: 化学需氧量(COD)是反映水体受有机物污染的重要指标，其环境污染问题引起了广泛关注。2012年我国长江、黄河等十大流域的972个国控断面中有10.2%的断面为劣Ⅴ类水质，COD是主要污染指标之一,因此对水体中COD进行准确监测具有重要的意义。目前我国采用的COD标准方法具有操作繁琐、效率低、检测成本高、对环境容易造成二次污染等问题。针对传统检测方法存在的缺点，研究者对所用仪器设备(样品消解及测定)、消解试剂、检测方法等进行优化与改进。在此基础上，检测效率及准确性更高、环境友好的检测技术也相继被开发与应用。本文总结了近年来COD标准检测方法的改进与优化、新检测技术研究的主要进展。传统检测方法可检测COD含量为30~700 mg/L的轻度、中度污染水样；基于标准方法改进的检测方法将检出下限降低至8.6 mg/L，检出上限则扩展到1600 mg/L。这些方法可显著缩短检测时间，降低检测成本，但不能避免试剂对环境的污染，且对难降解有机物的氧化能力不足。在药物及免疫分析、矿物岩石分析等其他领域或指标检测中成熟的技术方法，如化学发光法、流动注射法或多种技术结合的新的检测方法，已经被应用于COD检测，检出下限仅为0.16 mg/L，检测时间进一步缩短，试剂污染也大幅降低。随着科技的发展，臭氧氧化法、电化学法等不拘泥于传统检测方法的新方法，特别是基于以羟基自由基(·OH)为主要氧化剂与有机物发生反应的光催化法及光电催化氧化技术，进一步将COD的检测范围拓宽至0~23200 mg/L，为COD的准确、快速、低成本及在线监测提供了参考。Abstract: COD is regarded as an important index for representing the degree of organic pollution in water bodies, which has attracted wide attention. The water quality of 10.2% of the 972 state-controlled sections exceeded Ⅴ class among ten water areas such as the Yangtze River and the Yellow River in China in 2012. COD is one of the major pollution indicators in those water bodies. Therefore, it is of great importance to accurately monitor COD in water bodies. However, standard determination methods of COD have some disadvantages including complexity, low efficiency, high cost and severe secondary pollution. Aiming at the difficulties of traditional methods, instruments and equipment (sample digestion and determination), digestion reagents, and determination methods have been optimized and improved. In addition, certain environmentally friendly detection techniques with higher detection efficiency and accuracy have also been developed and applied. The most recent research progress of the determination methods of COD, including two main parts: the improved and optimized methods according to the standard ones, and new technologies or methods are reviewed in this paper. The traditional detection method is suitable for determining COD with the content range of 30-700 mg/L in light or moderate polluted water bodies. The improved and optimized methods extend the detection limits from 8.6 mg/L to 1600 mg/L, with the detection time shortened and cost of detection decreased significantly. However, the environmental pollution caused by chemical reagents could not be avoided, and oxidation ability to the refractory organics was insufficient. Flow injection, chemiluminescence or a combination of several techniques, which had already been used as the mature detection methods in drugs and immune analysis, mineral and rock analysis, have also been employed for the determination of COD in water bodies. Lower detection limit (0.16 mg/L) and faster detection time could be achieved, and the environmental pollution caused by the reagents was reduced dramatically. With the development of science and technology, some new methods such as ozone oxidation, electrochemical ones, especially as photocatalytic and photoelectrocatalytic determination technologies, based upon the reaction between hydroxyl radicals and organic compounds, have been developed recently. A wider detection range (0-23200 mg/L) was achieved by these new methods, which are capable of determining COD in water bodies with different pollution levels. The new techniques could provide a reference for the accurate, rapid, low-cost and on-line monitoring determination of COD.
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Keywords:
- water /
- chemical oxygen demand /
- detection method
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不知你是否有过这样的经历，终于得到那本向往已久的好书，或是觅得那张曾经深深触动你的CD，你是即刻拆封？还是放进书包带回家，等外界嘈杂喧嚣退去，静候自己那颗久别重逢的心都准备好了，才打开来细细品读或是聆听？
上大学时，笔者第一次听到了德沃夏克的第九交响曲“自新大陆”。乐中蕴含着一股强大而内敛的力量，气势恢弘，充满自信与自豪，是充满生机的号角和热血生命的召唤，让当时年轻的心澎湃不已，至今不能忘怀。那个时候有年轻的心，有远方的梦，在时间和生命的轨迹上自由地延伸。自那时起，找寻和聆听这首交响曲，就成了心中一份默默的寄托。不知等了多少年，终于觅得了这一珍贵CD。当时拿到CD，真恨不得马上回家就听。然而，真正回到家，却总也不敢拆开那精美的包装，担心里面那颗澎湃的心所掳掠的这么多年的找寻和期待稍纵即逝，或流于指缝，或散于世俗。要重温这张CD，必须有一种“仪式”：最悦耳的音响，最静谧的夜，最清澈的星空……，只有这个时候，再奏响这火红的乐章，才能让心在足够的宁静中再一次澎湃，让灵魂再一次感受久违的呼唤与震撼。穿越这数十年的流觞，与那个年轻的自己一起，坐在大学校园的静夜里，沉醉、省思和积淀。这一等，就又是十年。
如果说科学和艺术是一双智慧和反智慧的孪生体，那么这样的“反”中，必然免不去这诸多的“同”。不久前看到一段话，大意是说，只会开卷勤读，不会掩卷悲喜，这一生就算做到中文系教授，也不过是一个文学的绝缘体。对于搞科研的人来说，这掩卷后的触动和省思更为重要。没有这点滴的“省”，你不仅会渐渐绝缘于真正意义上的科研，甚至也绝缘于自己———你永远无法体验多年后与曾经的自己再一次邂逅的快乐。2013年在《岩矿测试》上发表的文字，既有踏雪寻梅，一层一层曲折着向科学深处走去的探索，又有山重水复疑无路的回转，以及攻克了诸多技术难题的实验新作。邈远空茫之处，探寻的精神与攻克难关的乐趣尽显。
“氧同位素在岩石成因研究中的新进展”一文（Vo1.32，No.6，p841－849），初看似如入云山雾海，那些氧同位素组成的变化和分馏效应的差异，如何用来识别不同来源、不同期次岩石的形成、混染和演化？技术手段的改变，又如何否定了前人的假设与假说，导致了多种岩石成因学说的进步？层层叠叠，庐山面目不得识。然而这反倒促使你静下心来，仔细阅读，去理解科学道理与自然规律的天然自成。自然之美在这里一览无余。也不得不使你感受到作者对于该门学科独到的思辨与洞察。
“应用纤维素示踪北京市PM2．5天然植被排放来源的研究”（Vo1.32，No.5，p738－746）实在是一篇需要推荐给大家去读的文章。现在举国上下，直至欧美诸国，都在广泛谈论PM2．5与北京和全国各地的雾霾。当北京重度污染的时候，还会收到国际友人的邮件关注。印象中，我们谈论的雾霾来源都是工业污染、沙尘，甚或汽车尾气。然而，该文作者们通过精巧的设计和实验方法的改进，通过与国外文献的方法及数据对比，表明在北京，天然植被排放量占据了PM2．5质量浓度的1．37％的份额，天然植被排放源对有机碳的最大贡献可达9．2％，天然植被排放成为北京市PM2．5重要来源之一。该研究与我们大家的生活息息相关，其重要性和科学意义不言而喻。
微区定量分析中，标准物质的缺乏是其重要制约因素之一。标准物质与待测样品基体的不一致是分析误差的主要来源。“激光剥蚀电感耦合等离子体质谱分析石笋样品中多元素比值及45种元素含量”（Vo1.32，No.3，p383－391）一文，在实验与方法上，采取了一系列富有创意的、绕口令一般的“桥梁”设计，有效地避免了碳元素无法准确检测的问题，获得了与Ca内标法相匹配的校正结果。“磷灰石Sr－Nd同位素的激光剥蚀－多接收器电感耦合等离子体质谱微区分析”（Vo1.32，No.4，p547－554）研究中，作者们不仅进行了深入的研究，还详尽地进行了国内外方法与数据的比较，佐证了所建方法的先进性和可靠性。这一点十分值得推荐，这样做也需要有渊博的学识、扎实的功底和探求真知的勇气。一年来，这样的研究还有很多……
这些文字，或充满丰富的奇思妙想，或构思着精巧的实验设计，智慧、坚韧与探求，无不浸润在文中的字里行间。
于是，就想，一定要集撰这样一本好书，也一定会有这样一卷好书，在星星聚齐的时候，我们一起开卷细品，掩卷遐思！
主编：罗立强
2013年10月26日
于北京
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表 1 高盐废水检测中推荐的HgSO4/Cl-比例[12]
Table 1 Recommended HgSO4/Cl- ratios for COD analysis at high salinities [12]
COD浓度
ρ/(mg·L-1)推荐的HgSO4/Cl-比例 Cl-浓度上限：2500 mg/L Cl-浓度上限：5000 mg/L Cl-浓度上限：7500 mg/L Cl-浓度上限：10000 mg/L 0~50 10∶1~20∶1~30∶1 10∶1~20∶1~30∶1 - - 50~100 10∶1~20∶1~30∶1 10∶1~20∶1~30∶1 10∶1~20∶1~30∶1 30∶1 100~150 10∶1~20∶1~30∶1 10∶1~20∶1~30∶1 10∶1~20∶1~30∶1 20∶1~30∶1 150~200 10∶1~20∶1~30∶1 10∶1~20∶1~30∶1 10∶1~20∶1~30∶1 20∶1~30∶1 
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表 2 各类检测方法比较
Table 2 Comparison of different detection methods
方法
类型检测方法 线性范围/
(mg·L-1)检出限/
(mg·L-1)样品类型 方法优缺点 文献来源 标准方法改进 Mn3+作氧化剂，微波消解 与标准方法
一致- 废水 微波消解时间仅1 min；与标准方法比对误差 < 4%，无需汞盐；不能避免铬盐的污染 Domini等[11] CuSO4-MnSO4复合催化剂替代 45～1600 45 废水 消解时间12 min；扩展了检测范围；不需银盐，不能避免汞盐、铬盐的二次污染 邱婧伟等[36] 普通分光光度计代替专用COD测定仪 与标准方法
一致与标准方法
一致废水 降低检测成本，消解时间为12 min，降低环境污染；所需试剂与快速法一致无改进 付丽君等[9] 双波长光谱法 8.6～100 8.6 低污染
水体提高了低污染水体的灵敏度，不需标准样品校正；消解时间长，消解温度等无改进 蒋然等[14] 高氯废水检测方法优化 ≤200 - 高氯低
有机物废水优化了HgSO4的加入比例，适合Cl- < 10000 mg/L的高氯废水，增加了汞盐等的污染 Kayaalp等[12] 新的检测技术 化学发光法(KMnO4-戊二醛高通量化学发光系统) 0.16~19.24 0.1 清洁水 操作简单快速，检测效率高及污染少，检出限低，适合低含量水体中COD的检测；线性范围较窄 Yao等[15] 流动注射技术(微波
消解，ICP结合)2.6～850 1.2 清洁水
及废水多种技术结合，显著降低了检出限，Cl-含量 < 3000 mg/L不干扰测定；使用大型仪器，成本高 Almeida等[17] 臭氧氧化法
(O3/UV)与标准方法
一致0.03 海水 盐度无影响，检出限显著降低；适合海水在线监测；臭氧本身的局限导致方法氧化能力不足 刘岩等[19] 电化学法(BDD
电极-超声消解)0～23200 0.19 清洁水
及废水线性范围很宽，检出限低。检测时间仅需5 min，电极制作成本高，不适合推广 Wang等[69] 光催化法(纳米
TiO2- K2Cr2O7
体系)0～150 0.4 轻度污染
水体Cl-含量 < 2000.0 mg/L不干扰测定，无需汞盐。线性范围较窄，有待改进，成本较高 李成芳等[80] 光电催化氧化法(TNFs) 0～250 0.95 中轻度
污染水体测定快速(几分钟)，试剂污染少，氧化效率高。线性范围有待提升，成本高 Mu等[24]
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