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医院是提供疾病诊疗、护理和康复等医疗服务的重要场所，在增进人类健康福祉和促进医学水平提升中发挥了关键作用. 据中国2020年卫生健康事业发展统计公报显示，全国医院数量近35万个，床位910万张[1]. 大中小型医院日耗水量分别为每床650—800、500—600、350—400 L·d−1 [2]，每天产生大量含特殊污染物的医疗废水，其中含有 Cd、Cu、Ni、Hg和Sn等重金属、抗生素、消毒剂和病原微生物等[3]，COD和BOD 含量分别为450—2300 mg·L−1和150—603 mg·L−1，高出市政污水2—3倍[4]. 而医疗废水中溶解性有机物（dissolved organic matter， DOM）成分复杂、结构多样、不易降解和矿化[5]. DOM的含量及组成既增加医疗废水的处理难度，也直接影响出水水质，对水生生态环境构成潜在威胁[6]. 此外，DOM多种活性组分如多糖、蛋白质和木质素等对重金属、病毒微生物和抗生素等污染物的迁移转化和生态风险有着重要的调控作用[7-8]. 部分国家医疗废水未经处理直接排放被认为是水环境中有毒有害元素输入的主要来源[9]. 在我国，医疗废水须处理达标后进入市政污水处理厂二次处理，以提高医疗废水的可生物降解性，避免致病微生物、耐抗生素细菌的传播.
长期以来，人类活动产生的生活废水、垃圾渗滤液以及畜禽养殖等废水中的DOM受到关注[10-12]. 而医疗废水中DOM的研究报道多集中于利用荧光光谱（excitation-emission matrix spectroscopy， EEMs）对处理工艺的效果进行监测与评价. Khongnakorn等[13]利用EEMs评价了陶瓷光催化薄膜反应器处理医疗废水的效果，发现医疗废水DOM组分主要为类酪氨酸、类色氨酸、类腐殖酸和类富里酸. Tang等[14]采用臭氧氧化降解医疗废水经生物处理后出水中的药物和毒性，研究表明有机物荧光强度与废水中的药物浓度呈正相关，T1峰（λEx/λEm=275 nm/340 nm）与药物浓度的关系最为密切，可以作为废水中药物去除效果的替代物. Ouardadeng等[15]则利用紫外-可见光谱（UV-visible spectroscopy， UV-vis）和荧光光谱研究电化学氧化法处理医疗废水残留药物，认为254 nm的吸光度和总荧光强度可作为医疗废水残留药物监测的替代参数.
紫外-可见光谱、三维荧光光谱和傅里叶变换红外光谱（fourier transform infrared spectrometer， FTIR）具有使用方便、响应速度快、成本低、灵敏度高和分辨率高等优点[16-17]，已成为DOM含量、组分和结构等特性表征的重要手段[18-20]. 平行因子分析（parallel factor analysis， PARAFAC）可有效解析DOM重叠的三维荧光光谱和量化荧光组分[21]，本研究基于紫外可见吸收、三维荧光以及红外光谱表征手段与平行因子分析，对医疗废水处理前后DOM组分、含量和结构进行表征，可增进医疗废水DOM光谱特征的认识，对开展医疗废水的光谱监测和水环境保护具有十分重要的现实意义.
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样品采集于贵州省和湖南省14家医院，其中贵阳市7个、安顺市3个、毕节市2个、长沙市2个，多以综合性医院为主，3家中医药医院，专科医院1家. 所有医院均采用次氯酸钠（NaClO）进行消毒，处理工艺流程为“进水—格栅—调节池—初沉池—生物氧化—二沉池—消毒池—脱氯池—出水”，达标出水进入市政污水管网. 现场利用500 mL洁净棕色高密度聚乙烯瓶采集进出口废水，置于4 ℃冷藏箱避光带回实验室. 样品经0.45 μm滤头过滤后，供紫外光谱、三维荧光光谱和红外光谱分析. 紫外和荧光光谱分析测试于样品采集24 h内完成.
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DOM的UV-vis和EEMs使用三维荧光光谱分析仪（Aqualog-UV-800-C， Horiba， America）同步检测获取，激发波长范围: 240—800 nm，间隔波长3 nm; 发射波长240—800 nm，间隔波长1.17 nm; 扫描积分时间为0.3 s，扫描速度为1200 nm·min−1. 利用Millipore®超纯水于350 nm激发波长下对拉曼峰波长及仪器信噪比进行检测校正，水拉曼波长（397±1）nm，信噪比SNR≥20000，确保仪器运行稳定. 于Thermo控温仪在20 ℃下恒温完成测试，利用Aqualog®系统完成内滤（inner filter effect， IFE）、瑞利（Rayleigh masking）和拉曼散射（Raman normalize 3D） 校正. 取20 mL过滤样品于松源真空冷冻干燥机（LGJ-10FD）冷冻干燥48—72 h. 称取5 mg DOM固体粉末与KBr（光谱纯）以1:20质量比于玛瑙研钵中混合研磨均匀，在20 MPa左右压制成薄片供红外光谱测量. 使用傅里叶红外光谱仪（Nicolet6700， Thermo Fisher， America）在400—4000 cm−1范围内进行红外光谱分析，分辨率为4 cm−1，扫描次数为32次. 数据扣除背景后，使用Omnic8.0对光谱曲线进行自动基线校正和平滑处理.
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利用R语言（R4.0.2版本）中的staRdom以及Dplyr和Tidyr等相关软件包对EEMs进行PARAFAC模型分析，以残差分析确定荧光组分，组分有效性通过拆半分析完成检验[22]. StaRdom中相关函数计算荧光指数（fluorescence index， FI）、腐殖化指数（humification index， HIX）和自生源指数（biological index， BIX）等参数时，自动使用 parcma包中的interp2函数对EEMs进行插值，指数相关含义见表1. 使用Orgin2019对紫外光谱和红外光谱图进行绘制.
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医疗废水处理前后UV-vis曲线特征相似，但吸光度值略有差别，见图1. 所有医疗废水在440 nm 和700 nm附近均出现紫外吸收峰，其中440 nm是临床常用的药物载体AgNPs，其自身稳定性好，表面结构含有碳碳双键、酯基、羧基和羟基等官能团[30-32];处理后吸收峰依然存在且几乎未发生变化，表明此类物质不易被去除. 而700 nm多为胶体颗粒光散射效应引起的杂峰，常用于DOM吸收光谱的基线矫正，以降低胶体颗粒引起的光散射效应[33-34]. 280 nm吸收峰是酚类、苯胺衍生物、苯甲酸、多烯和多环芳烃等腐殖质发生π—π*电子跃迁所致[35]，仅在5家医疗废水中出现. 处理后280 nm附近吸收峰变弱甚至消失，去除效果明显.
DOM在254 nm处的紫外吸收强度越大，不饱和程度越高[23]. 如图2（a）所示，医疗废水处理前后A254均值分别为0.44和0.32. 处理后A254下降，DOM饱和程度升高，不饱和小分子有机物减少. 从图2（b）可知，处理前后E2/E4均值分别为14.57和11.29，芳香性变化. 个别医院E2/E4值较大，可能与病人治疗和康复过程中的用药有关，药物成分和药物结构不同，芳香性存在差异[36]. 在处理过程中，微生物生长可直接将小分子DOM作为碳源和能源，而消毒剂次氯酸钠（NaClO）能使菌体和病毒上的蛋白质变性，同时ClO−也能破环有机物的芳香结构[37]，故而处理后A254和E2/E4下降. E2/E3与相对分子质量成反比，如图2（c），处理前后E2/E3均值为6.25和5.44，总体高于3.5，主要以相对分子质量较小的有机质为主，其中的富里酸含量高于胡敏酸[24]，处理后E2/E3有所降低，分子质量略有增加. E4/E6与有机物的聚合程度成反比，可表征苯环C骨架的聚合程度和羰基共轭度;相对分子质量降低时，E4/E6值往往会增高[26]. 除H9和H13外，处理前后E4/E6有所降低，均值分别为2.25和1.68，DOM苯环C骨架的聚合度或羰基共轭度有所增加，如图2（d）所示. E2/E3和E4/E6降低，DOM分子量和聚合程度增加，主要是由于微生物优先代谢小分子物质，相对分子量较大的DOM得以聚集，以及聚合度较低的小分子有机物结合成为稳定度较高的大分子DOM[38]. 此外，药物化合物经过不同程度的生物转化，会形成不同的代谢产物. 在污水处理中，常见解热镇痛药布洛芬生物转化形成代谢产物羟基和羧基布洛芬[39]，这些代谢产物结合形成具有高于其母体分子的共轭（新）化合物，虽然这种生物转化利用比例不高，但这能导致DOM分子质量和有机物的聚合程度增加.
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DOM的结构复杂[40]，FTIR是表征其结构特征的重要手段之一. 从医疗废水DOM的FTIR光谱中观察到（图3）处理前后共显示出6个典型吸收峰，波长分别位于3440—3350、1649—1630、1421—1387 、1146—1044、866—830、703—599 cm−1附近.
根据文献[41-43]，3440—3350 cm−1是DOM整个光谱曲线中强度最强的吸收峰，主要由苯酚、醇及羧基中的O—H和苯胺化合物所含 —NH和NH2中N—H的伸缩振动形成; 1649—1630 cm−1 范围则是酮和醛的C═O或芳香基上的C═C伸缩振动形成; 脂肪族CH3和CH2中C—H的振动及羧基上的不对称伸缩或C—OH变形振动于1421—1387 cm−1处产生吸收峰; 1146—1044 cm−1的峰是脂肪族上C—OH和C—O伸缩、酚类或醇类上C—O不对称伸缩振动产生; 866—830 cm−1附近出现的峰与苯环上C—H弯曲振动有关; 703—599 cm−1出现的峰则表明医疗废水中含有氯和苯酚. H8、H9、H10、H11和H12等医院在1001—921 cm-1和2943—2892 cm−1范围出现特征峰，前者为芳香醚C—O—C键的C—O不对称拉伸振动或芳香族C—H振动所致; 后者主要是脂肪族C—H、酮和羧酸中O—H以及游离氨基酸N—H伸缩振动所产生[44-45]，这一差别可能是医院在病人治疗过程中的用药不同，药物成分和结构不同所致[36].
总体而言，医疗废水中DOM结构性质较为相似，多为含有苯酚类、醇类、苯胺类、脂类和芳香类有机物及氯，主要官能团有O—H、N—H、C═O、C—H、C—OH、C—O和C—O—C等. 处理前后废水中DOM的峰位、峰形和峰数相似，但处理过程中物质间相互作用时发生电子转移，导致有机物光谱特征变化，吸收峰发生不同程度的红移或蓝移. 其中3440—3350 cm−1和703—599 cm−1范围多为蓝移，说明苯酚、醇及羧基中的O—H和苯胺化合物所含—NH和NH2中N—H的伸缩振动以及氯和苯酚中官能团振动变弱，可能是类腐殖质中苯酚和醇类化合物去除导致蓝移发生[46];1649—1630 cm−1、1421—1387 cm−1、1146—1044 cm−1及866—833 cm−1间则多为红移，说明相应官能团伸缩变化加强，小分子DOM聚合形成了更加稳定的大分子腐殖质，基团间距进一步缩小，电子跃迁能量降低导致红移[47-48].
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基于PARAFAC模型对处理前后医疗废水DOM进行分析，得到4种荧光组分（如图4和表2），C1 （λEx/λEm=278 nm/352 nm）为类色氨酸，C2（λEx/λEm=281，362 nm/463 nm）和 C3（λEx/λEm=<251，320 nm/404 nm）均为类腐殖质荧光组分，C4（λEx/λEm=272 nm/297 nm）为类酪氨酸，C1和C4均属于类蛋白类荧光峰，分别相对应于T峰和B峰[49]. C2和 C3位于C峰附近，存在着高芳香度和高分子量的基团[50]，其微生物利用率较低. 此外，对处理前后废水分别进行PARAFAC模型分析，表2中已将出水C1标注为次峰，而明显的荧光峰归于类腐殖质，以便对比荧光组分和峰位变化.
医疗废水DOM各荧光组分含量及相对比例如图5所示，医疗废水处理前DOM 总荧光强度为13.29—75.17 R. U.，处理后荧光强度明显降低，处于0.98—33.73 R. U.之间，C1、C2、C3和C4的平均去除率分别为78.32%、36.97%、26.64%和68.44%，DOM的去除以类蛋白质为主，类腐殖质去除效果相对较低. 处理前后DOM的组分占比也发生了变化，处理前 C1、C2、C3和C4的平均占比为38.08%，14.90%、8.53%和38.49%，处理后DOM中类蛋白质占比降低，其中C1和C4分别下降15.05%和10.95%，而类腐殖质占比却出现增加，C2和C3分别增加14.74%和11.26%，主要由于C1和C4较C2和C3去除率高，使得两者相对丰度增加. 此外，处理过程中微生物分解代谢底物时生成了较多的类腐殖质等惰性代谢产物，不易生物降解也能导致C2和C3占比增加[55].
医疗废水处理过程中DOM的荧光峰出现了红移和蓝移现象，处理前后相比，处理后C1的激发和发射波长分别红移9 nm和蓝移18 nm，C2主次峰的激发和发射波长分别蓝移18 、6 、3 nm; C3和 C4仅发射波长出现红移，分别为2 nm和14 nm. C1、C3和C4的红移与官能团结构中羰基、羟基、烷氧基和氨基增加，聚合度和共轭效应增加有关[56-57]，C1和C2出现的蓝移则因p电子体系、芳环及碳链分子中共价键的减少[58].
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BIX、HIX和FI等是进一步了解DOM光谱特征的常用指标，HIX被广泛用于表征有机物腐殖化程度，其值越大DOM腐殖化程度越高，医疗废水处理前后HIX均值分别为0.46和0.67，均低于1.5，主要以腐殖化程度低生物或原生物质为主[59]，处理后HIX略有增加是由于类腐殖质占比增加所致. BIX用来表征DOM的自生源特性，医疗废水处理前BIX为0.67—0.98，处理后均值0.94，DOM的自生源性较强[60]. FI则是DOM腐殖质来源的表征参数[61]，医疗废水处理前FI均值为1.49，处理后增加至1.67，介于1.4—1.9之间，腐殖质来源于生物和非微生物，如图6所示.
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医疗废水DOM的荧光组分、紫外指数和荧光指数间的Pearson相关性分析见图7所示，处理前各荧光组分呈正相关关系，C1与C2、C3和C4的相关系数r分别为0.81（P<0.001）、0.71（P<0.01）和0.62（P<0. 05）; C2与C3和C4的r是0.91（P<0.001）和0.67（P<0.01）; C3与C4的r则为0.68（P<0.01），说明医疗废水各荧光组分具有相似的来源. A254与C1、C2和C3的荧光强度呈极显著正相关（P<0.001），r分别为0.78、0.93和0.85，与C4呈显著正相关 （r=0.74，P<0.01）. E2/E3和E2/E4呈显著正相关（r=0.97，P<0.001），且与A254（r为0.63和0.63）和C4（r为0.66和0.74）分别在P<0.05和P<0.01水平上显著正相关. 医疗废水经处理后， C1与其占比C1%和E4/E6，A254与C2、C3和C4以及C2与E4/E6间的相关性从显著正相关变为不显著，A254与C1及C2与E2/E3和E2/E4甚至由显著正相关变为不显著负相关，HIX与C4及BIX与E2/E4则由显著负相关变为不显著的负相关及正相关; 部分参数间相关性则从不显著到显著，如C1与C3%及BIX与C2和C3从不显著负相关到显著，而BIX与FI从不显著正相关到显著，C1与E2/E3和E2/E4则从不显著正相关变为显著负相关，参数之间的相关性发生变化的诱因是处理过程中的DOM降解导致组分含量、占比及其结构发生了变化.
DOM去除是含特定官能团结构有机物的降解过程，对医疗废水处理前后DOM组分的荧光强度变化与典型官能团特征峰的红外光谱变化进行相关性统计分析，发现DOM中类腐殖质C2和C3的去除与其结构存在显著的相关性，其中C2与3440—3350 cm−1、1421—1387 cm−1和703—599 cm−1波数范围内的O—H和N—H、C—H与C—OH以及苯酚和Cl等官能团的特征峰的变化呈显著正相关，相关系数r分别为0.60、0.56和0.63（P<0. 05）. C3的相关性与C2类似，与上述官能团的相关系数r分别为0.55、0.59和0.64（P<0. 05），含上述官能团的主要有机物分别是苯酚、醇及羧基和苯胺化合物、脂肪族和氯和苯酚等. 此外，C3的去除还与1146—1044 cm−1波段特征官能团C—OH和C—O特征峰的变化显著正相关（r=0.59，P<0. 05），主要为脂肪族或者酚类和醇类物质，如表3所示. 相关性统计结果表明医疗废水处理过程中，DOM中类腐殖质C2与C3的去除主要是酚类、醇类、羧基、脂肪族以及苯酚和Cl等物质.
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通过对14家医院处理前后废水的紫外-可见吸收、三维荧光和红外光谱特征等分析，在医疗废水处理前后DOM结构和荧光组分变化方面取得初步的认识：
（1）医疗废水DOM结构性质相似，多为含O—H、N—H、C═O、C—H、C—OH、C—O和C—O—C等官能团的苯酚类、醇类、苯胺类、脂类、芳香类有机物及氯等物质. 废水中出现临床常用抗菌药物载体AgNPs，处理后紫外吸收光谱特征峰依然存在且变化小，不易被降解去除.
（2）DOM荧光组分主要是类蛋白质（类色氨酸C1和类酪氨酸C4）及类腐殖质（C2和C3）两大类，自生源性较强，腐殖化程度低，腐殖质来源于生物源和非生物源.
（3）生化和消毒等处理后，DOM的主要结构未出现明显变化，不饱和程度略有降低，苯环C骨架的聚合度增加，腐殖化程度增加. DOM的去除以类蛋白质为主，总荧光强度由13.29—75.17 R.U.降至0.98—33.73 R.U.，类腐殖质C2和C3去除效果相对较低，与3440—3350 cm−1、1421—1387 cm−1和703—599 cm−1波段范围含O—H、N—H、C—H和C—OH以及苯环等官能团的有机物有关.
医疗废水处理前后溶解性有机物的光谱特征分析
Spectral characteristics of dissolved organic matter in medical wastewater before and after treatment
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摘要: 医院诊疗过程中产生大量富含溶解性有机物（DOM）的医疗废水，DOM会影响医疗废水的处理效率和出水水质. 本研究利用紫外可见吸收、三维荧光以及红外光谱技术分析了14家医疗废水处理前后DOM的光谱特征. 结果表明，医疗废水DOM的荧光组分由类蛋白质（类色氨酸C1和类酪氨酸C4）及类腐殖质（C2和C3）两大类组成，结构性质相似，多为含O—H、N—H、C═O、C—H、C—OH、C—O和C—O—C等官能团的苯酚类、醇类、苯胺类、脂类、芳香类有机物及氯等物质. DOM自生源性较强，腐殖化程度低，腐殖质来源于生物源和非生物源. 处理后DOM结构未出现明显变化，不饱和程度略有降低，苯环C骨架的聚合度和腐殖化程度增加. DOM的去除以类蛋白质为主，总荧光强度由13.29—75.17 R.U.降至0.98—33.73 R.U.. 类腐殖质C2和C3去除效果相对较低，其去除与3440—3350 cm−1、1421—1387 cm−1和703—599 cm−1波段范围含O—H、N—H，C—H和C—OH以及苯环等官能团的有机物有关. 而临床使用的抗菌药物载体AgNPs在医疗废水中不易被降解去除.Abstract: The hospital diagnosis and treatment process produce a large amount of medical wastewater (MW). These kinds of wastewaters are rich in dissolved organic matter (DOM), which can affect the efficiency and effluent quality of MW treatment. In this study, ultraviolet-visible spectroscopy (UV-vis), excitation-emission matrix spectroscopy (EEMs), and Fourier transform infrared spectroscopy (FTIR) were used to analyze the spectral characteristics of DOM in MW before and after treatment from 14 hospitals. The results show that fluorescent components of DOM are composed of protein-like (tryptophan-like C1 and tyrosine-like C4) and humic-like (C2 and C3) with similar structural properties, mostly containing phenols, alcohols, anilines, lipids, aromatic organics, and chlorine with functional groups such as O—H, N—H, C═O, C—H, C—OH, C—O, and C—O—C. The DOM is highly authigenic and has a low degree of humification. Both allochthonous and autochthonous sources are contributed to humic substances. The structure of DOM does not change significantly after treatment, the degree of unsaturation decreases slightly, while the degree of polymerization of benzene ring C skeleton and humification increases. The removal of DOM is mainly protein-like. The total fluorescence intensity decreased from 13.29—75.17 R.U. to 0.98—33.73 R.U.. The removal rate of humic-like substances(C2 and C3) are relatively low and related to the organic matters with functional groups O—H, N—H, C—H and C—OH and benzene rings in the bands 3440—3350 cm−1, 1421—1387 cm−1, and 703—599 cm−1. Respectively, AgNPs, as clinically used antimicrobial drug carriers, are not easily removed by degradation in medical wastewater.
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图 4 医疗废水DOM荧光组分及其波长位置
Figure 4. Fluorescent components of DOM and their wavelength of medical wastewater
图 5 医疗废水DOM组分荧光强度及相对比例
Figure 5. The fluorescence intensity and percentage of DOM in medical wastewater
图 7 医疗废水DOM荧光组分和光谱指数间相关性
Figure 7. Correlations between fluorescence components and spectral index in medical wastewater
表 1 紫外光谱和荧光光谱相关参数及其指示意义
Table 1. The summary and implications of ultraviolet and fluorescence spectra index
类型
Spectral type光谱参数
Spectral parameters参数定义
Parameter definition指示意义
Indicative meaningUV-vis A254 254 nm处的紫外吸光度 表征DOM的不饱和程度[23] E2/E3 250 nm和365 nm处的紫外吸光度之比 反应DOM相对分子质量大小[24] E2/E4 254 nm和436 nm处的紫外吸光度之比 表征DOM的芳香性[25] E4/E6 465 nm和665 nm处的紫外吸光度之比 表征DOM聚合程度[26] EEMs FI Ex=370 nm时,Em在470 nm与520 nm处的荧光强度比值 判断DOM腐殖质来源[27] HIX Ex为250 nm时,Em在435—480 nm以及300—345 nm间荧光峰值面积之比 表示DOM腐殖化程度[28] BIX Ex为310 nm时,Em在380 nm和430 nm处荧光强度的比值 反应DOM的自生源特性[29] 
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表 2 医疗废水DOM的荧光组分特征
Table 2. Characteristics of fluorescent components of DOM in medical wastewater
组分
ComponentsλEx/λEm /nm 物质
Type参考文献
Reference前后
Before and after前
Before后
AfterC1 278/352 278/354 287/336* 类色氨酸 280/354[51] C2 281，362/463 278，368/461 260，362/458 类腐殖质 260（345）/476[52] C3 <251，320/404 <251，314/413 251，314/415 类腐殖质 < 250（320）/410[53] C4 272/297 272/297 272/311 类酪氨酸 270/302[54] *.出水C1组分 （λEx/λEm=287 nm/ 494 nm和λEx/λEm=413 nm/ 500 nm）为类腐殖质,本表标注 （λEx/λEm = 287 nm/336 nm）为类色氨酸.
*. Component C1 （λEx/λEm = 287 nm/494 nm and λEx/λEm = 413 nm/500 nm） is humic-like in effluent, while （λEx/λEm = 287 nm/336 nm） is tryptophan-like and labeled.
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表 3 医疗废水处理前后DOM荧光强度变化与红外光谱特征峰变化的相关性
Table 3. Correlations between change of DOM fluorescence intensity and infrared spectrum before and after treatment of medical wastewater
ΔT3440—3350 ΔT1421—1387 ΔT1146—1044 ΔT1649—1630 ΔT866—830 ΔT703—599 ΔC1 0.30 0.40 0.41 0.30 0.44 0.52 ΔC2 0.60* 0.56* 0.53 0.33 0.31 0.63* ΔC3 0.55* 0.59* 0.59* 0.29 0.39 0.64* ΔC4 0.20 0.19 0.24 0.21 0.22 0.35
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